CN103626916B - A kind of preparation method of NIPA-co-acylhydrazone sorbent material - Google Patents
A kind of preparation method of NIPA-co-acylhydrazone sorbent material Download PDFInfo
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- CN103626916B CN103626916B CN201310556755.5A CN201310556755A CN103626916B CN 103626916 B CN103626916 B CN 103626916B CN 201310556755 A CN201310556755 A CN 201310556755A CN 103626916 B CN103626916 B CN 103626916B
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- nipa
- acylhydrazone
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Abstract
The present invention relates to a kind of preparation method of NIPA-co-acylhydrazone sorbent material.In a kettle., under gas shield, by various reaction monomers dispersion in organic solvent, add radical initiator, polymerization reaction take place generates random copolymers, and hydrazinolysis reacts the small molecules with aldehyde radical in also grafting then, synthesis final product.By controlling the conditions such as temperature of reaction, time and each material proportioning, final obtained poly-(NIPA-co-acylhydrazone) with chelating ability.Advantage of the present invention: inner complex heavy metal ion has good absorption property, meanwhile, adopt the NIPA with Thermo-sensitive as monomer, raised temperature polymkeric substance is separated out, and is separated inner complex after being convenient to adsorb.
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, not easily transforms in the environment.Heavy metal ion in environment enters water body by all means, and in water body, the enrichment of various biologic chain, finally enters human body by fishery products, and produces harm to the health of people.The research of people's heavy metal wastewater treatment is in recent years attached great importance to, and develops many kinds for the treatment of processs and removes heavy metal in waste water, to make it to reach emission standard.The process of macromolecular heavy metal chelating agent heavy metal waste water has the advantages such as cost is low, effect stability.People attach great importance to the research of macromolecular heavy metal chelating agent in wastewater treatment in recent years.
Except the method for 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.Suitable sorbent material is selected, for process is significant containing the waste water of heavy metal ion economically according to practical situation.Macromolecular heavy metal chelating agent is water miscible one, and macromolecule matrix has hydrophilic chelating and forms base, it with water in heavy metal ion optionally react, generation 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.Compared with traditional soluble chelating thing, the present invention prepare owing to Polymeric complexes main chain having Thermo-sensitive unit NIPA, can pass through raised 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 the shortcoming being to overcome above-mentioned prior art, provides a kind of preparation method that is simple, adsorbent for heavy metal efficiently.
In the present invention, in the polymerization of employing conventional free radical, form high polymer main chain, reacted by hydrazine, and then grafting has the monomer of adsorption function on diazanyl, thus realize the adsorption function of 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, adding mass fraction is in a kettle.: monomer NIPA 4 ~ 6 parts, 1 ~ 3 part, monomeric acrylic fat, organic solvent 20 ~ 30 parts, and magnetic agitation is uniformly dissolved in a solvent to monomer;
2) after being uniformly dissolved, 2 ~ 4 parts of oleosoluble radical initiators are added in reactor, keep bath temperature 70 DEG C, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get obtained random copolymers 2 ~ 3 parts, be dissolved in 15 ~ 25 parts of organic solvents, magnetic agitation is even, adds hydrazine hydrate 15 ~ 25 parts, keeps bath temperature 90 DEG C, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get the obtained NIPA of step and propylene hydrazide copolymers 3 ~ 7 parts, add 1 ~ 2 part of 2,4-dinitrobenzal-dehyde, be dissolved in 50 ~ 60 parts of organic solvents, magnetic agitation is even;
7) keep bath temperature 60 DEG C, 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 identical; Step 4), 5) in the portion rate benchmark of each material identical; Step 6), 7) in the portion rate benchmark of each material identical.
Described CALCIUM ACRYLATE is preferably the one in methyl acrylate or methyl methacrylate;
Described organic solvent is preferably the one in ethanol or acetone;
Described radical initiator is preferably the one in Diisopropyl azodicarboxylate or benzoyl peroxide.
Due in the present invention, adopt NIPA and the acrylic ester copolymer with Thermo-sensitive, make multipolymer have Thermo-sensitive and have again the unit that can react with chelating monomer simultaneously, the adsorbent for heavy metal productive rate that this method obtains is higher, and technique is simple, without the need to 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 the NIPA-co-acylhydrazone sorbent material of preparation.
Embodiment
Embodiment 1:
1), under nitrogen protection, adding mass fraction is in a kettle.: monomer NIPA 4 parts (0.4g), 1 part, monomeric acrylic fat (0.1g), ethanol 30 parts (3g), and magnetic agitation is uniformly dissolved in a solvent to monomer;
2) after being uniformly dissolved, 2.5 parts of (0.25g) Diisopropyl azodicarboxylate initiators are added in reactor, keep bath temperature 70 DEG C, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get obtained random copolymers 2 parts (0.2g), be dissolved in 15 parts of (1.5g) ethanol, magnetic agitation is even, adds hydrazine hydrate 15 parts (1.5g), keeps bath temperature 90 DEG C, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get the obtained NIPA of step and propylene hydrazide copolymers 3 parts (0.3g), add 1 part (0.1g) 2,4-dinitrobenzal-dehyde, be dissolved in 55 parts of (5.5g) acetone, magnetic agitation is even;
7) keep bath temperature 60 DEG C, 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, adding mass fraction is in a kettle.: monomer NIPA 4 parts (0.4g), 1 part, monomer methacrylic acid fat (0.1g), 30 parts, acetone (3g), and magnetic agitation is uniformly dissolved in a solvent to monomer;
2) after being uniformly dissolved, 3 parts of (0.3g) benzoyl peroxide initiators are added in reactor, keep bath temperature 70 DEG C, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get obtained random copolymers 2 parts (0.2g), be dissolved in 15 parts of (1.5g) acetone, magnetic agitation is even, adds hydrazine hydrate 15 parts (1.5g), keeps bath temperature 90 DEG C, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get the obtained NIPA of step and propylene hydrazide copolymers 5 parts (0.5g), add 1.5 parts (0.15g) 2,4-dinitrobenzal-dehyde, be dissolved in 50 parts of (5g) ethanol, magnetic agitation is even;
7) keep bath temperature 60 DEG C, 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, adding mass fraction is in a kettle.: monomer NIPA 5 parts (0.5g), 1 part, monomeric acrylic fat (0.1g), ethanol 25 parts (2.5g), and magnetic agitation is uniformly dissolved in a solvent to monomer;
2) after being uniformly dissolved, 2.5 parts of (0.25g) Diisopropyl azodicarboxylate initiators are added in reactor, keep bath temperature 70 DEG C, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get obtained random copolymers 2.5 parts (0.25g), be dissolved in 15 parts of (1.5g) ethanol, magnetic agitation is even, adds hydrazine hydrate 20 parts (2g), keeps bath temperature 90 DEG C, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get the obtained NIPA of step and propylene hydrazide copolymers 5 parts (0.5g), add 1.5 parts (0.15g) 2,4-dinitrobenzal-dehyde, be dissolved in 55 parts of (5.5g) ethanol, magnetic agitation is even;
7) keep bath temperature 60 DEG C, 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 at about 1 ~ 2ppm, the spike of chemical shift at 7.26ppm place is the solvent peak of deuterochloroform, chemical shift is characteristic peak hydrocarbon on phenyl ring at the assorted peak of about 7 ~ 7.5ppm, chemical shift is at broad peak (the peak a at 6 ~ 7ppm place, peak b, peak c) represent-CH-on acylhydrazone key and the proton characteristic peak on this ring, chemical shift represents the proton characteristic peak of-NH-on acylhydrazone key at the fignal center (peak d) at 8.5 ~ 9ppm place, and 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, adding mass fraction is in a kettle.: monomer NIPA 5 parts (0.5g), 2 parts, monomeric acrylic fat (0.2g), 20 parts, acetone (2g), and magnetic agitation is uniformly dissolved in a solvent to monomer;
2) after being uniformly dissolved, 3 parts of (0.3g) oleosoluble radical initiators are added in reactor, keep bath temperature 70 DEG C, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get obtained random copolymers 2.5 parts (0.25g), be dissolved in 20 parts of (2g) ethanol, magnetic agitation is even, adds hydrazine hydrate 20 parts (2g), keeps bath temperature 90 DEG C, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get the obtained NIPA of step and propylene hydrazide copolymers 7 parts (0.7g), add 2 parts (0.2g) 2,4-dinitrobenzal-dehyde, be dissolved in 60 parts of (6g) acetone, magnetic agitation is even;
7) keep bath temperature 60 DEG C, 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, adding mass fraction is in a kettle.: monomer NIPA 5 parts (0.5g), 2 parts, monomer methacrylic acid fat (0.2g), ethanol 20 parts (2g), and magnetic agitation is uniformly dissolved in a solvent to monomer;
2) after being uniformly dissolved, 4 parts of (0.4g) benzoyl peroxide initiators are added in reactor, keep bath temperature 70 DEG C, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get obtained random copolymers 2.5 parts (0.25g), be dissolved in 20 parts of (2g) acetone, magnetic agitation is even, adds hydrazine hydrate 25 parts (2.5g), keeps bath temperature 90 DEG C, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get the obtained NIPA of step and propylene hydrazide copolymers 7 parts (0.7g), add 2 parts (0.2g) 2,4-dinitrobenzal-dehyde, be dissolved in 60 parts of (6g) ethanol, magnetic agitation is even;
7) keep bath temperature 60 DEG C, 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, adding mass fraction is in a kettle.: monomer NIPA 6 parts (0.6g), 3 parts, monomeric acrylic fat (0.3g), 25 parts, acetone (2.5g), and magnetic agitation is uniformly dissolved in a solvent to monomer;
2) after being uniformly dissolved, 2 parts of (0.2g) benzoyl peroxide initiators are added in reactor, keep bath temperature 70 DEG C, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get obtained random copolymers 3 parts (0.3g), be dissolved in 25 parts of (2.5g) ethanol, magnetic agitation is even, adds hydrazine hydrate 15 parts (1.5g), keeps bath temperature 90 DEG C, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get the obtained NIPA of step and propylene hydrazide copolymers 3 parts (0.3g), add 1.5 parts (0.15g) 2,4-dinitrobenzal-dehyde, be dissolved in 50 parts of (5g) acetone, magnetic agitation is even;
7) keep bath temperature 60 DEG C, 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, adding mass fraction is in a kettle.: monomer NIPA 6 parts (0.6g), 3 parts, monomer methacrylic acid fat (0.3g), ethanol 25 parts (2.5g), and magnetic agitation is uniformly dissolved in a solvent to monomer;
2) after being uniformly dissolved, 2 parts of (0.2g) Diisopropyl azodicarboxylate initiators are added in reactor, keep bath temperature 70 DEG C, stirring reaction 12h.
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get obtained random copolymers 3 parts (0.3g), be dissolved in 25 parts of (2.5g) acetone, magnetic agitation is even, adds hydrazine hydrate 25 parts (2.5g), keeps bath temperature 90 DEG C, stirring reaction 24h.
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get the obtained NIPA of step and propylene hydrazide copolymers 3 parts (0.3g), add 2 part of 2,4-dinitrobenzal-dehyde, be dissolved in 55 parts of (5.5g) acetone, magnetic agitation is even;
7) keep bath temperature 60 DEG C, 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.
By obtained for embodiment poly-(NIPA-co-acylhydrazone) for the absorption of heavy metal ion, test it to Cu
2+and Cr
3+adsorption effect under specified temp, specific pH condition.Test finds, heavy metal ion sequestrant 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, adding mass fraction is in a kettle.: monomer NIPA 4 ~ 6 parts, monomeric acrylic 1 ~ 3 part, organic solvent 20 ~ 30 parts, and magnetic agitation 5min, makes monomer be uniformly dissolved in a solvent;
2) after being uniformly dissolved, 2 ~ 4 parts of oleosoluble radical initiators are added in reactor, keep bath temperature 70 DEG C, stirring reaction 12h;
3) dialysis freeze-drying, obtains the random copolymers of NIPA and acrylate;
4) get obtained random copolymers 2 ~ 3 parts, be dissolved in 15 ~ 25 parts of organic solvents, magnetic agitation is even, adds hydrazine hydrate 15 ~ 25 parts, keeps bath temperature 90 DEG C, stirring reaction 24h;
5) dialysis freeze-drying, obtains the NIPA of hydrazine and the random copolymers of acrylate;
6) get the obtained NIPA of step and propylene hydrazide copolymers 3 ~ 7 parts, add 1 ~ 2 part of 2,4-dinitrobenzal-dehyde, be dissolved in 50 ~ 60 parts of organic solvents, magnetic agitation is even;
7) keep bath temperature 60 DEG C, 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 acrylate is the one 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 the one in ethanol or acetone.
4. the preparation method of sorbent material as claimed in claim 1, is characterized in that described radical initiator is the one in Diisopropyl azodicarboxylate or benzoyl peroxide.
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| CN105860104B (en) * | 2016-06-15 | 2018-12-11 | 邯郸沃伦多科技开发有限公司 | A kind of Thermo-sensitive selfreparing hydrogel and the preparation method and application thereof |
| CN106928414A (en) * | 2017-03-31 | 2017-07-07 | 天津大学 | A kind of preparation method of polymeric sorbent predecessor di-block copolymer |
| CN106905472B (en) * | 2017-04-18 | 2019-01-29 | 北京蛋白质组研究中心 | A kind of functionalization responsive to temperature type polymer and the preparation method and application thereof |
| 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 |
| CN110841599B (en) * | 2019-11-22 | 2021-06-15 | 山东农业大学 | Preparation method and application of bisphenol compound efficient adsorption material |
| CN113083240B (en) * | 2021-03-26 | 2022-04-15 | 西南石油大学 | Preparation method of polymethacrylhydrazone 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 |
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| CN101717472A (en) * | 2009-12-07 | 2010-06-02 | 广州大学 | Graft copolymer of amino-containing starch and methyl acrylate |
| CN102863725A (en) * | 2012-09-10 | 2013-01-09 | 江南大学 | Preparations and applications of polymer probes for detecting copper ions on basis of naked eye visual colorimetry |
| CN103087264A (en) * | 2013-01-27 | 2013-05-08 | 桂林理工大学 | Preparation method of amphipathic acrylic acid/maleic anhydride (AA/MA) grafted esterified hydroxypropyl cassava starch |
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| JP5322116B2 (en) * | 2007-07-18 | 2013-10-23 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing nanofibers and mesofibers by electrospinning a colloidal dispersion having at least one substantially water-insoluble polymer |
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| CN101717472A (en) * | 2009-12-07 | 2010-06-02 | 广州大学 | Graft copolymer of amino-containing starch and methyl acrylate |
| CN102863725A (en) * | 2012-09-10 | 2013-01-09 | 江南大学 | Preparations and applications of polymer probes for detecting copper ions on basis of naked eye visual colorimetry |
| CN103087264A (en) * | 2013-01-27 | 2013-05-08 | 桂林理工大学 | Preparation method of amphipathic acrylic acid/maleic anhydride (AA/MA) grafted esterified hydroxypropyl cassava starch |
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