CN105131186A - Functionalized starch chelating agent and preparation method thereof - Google Patents
Functionalized starch chelating agent and preparation method thereof Download PDFInfo
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- CN105131186A CN105131186A CN201510618430.4A CN201510618430A CN105131186A CN 105131186 A CN105131186 A CN 105131186A CN 201510618430 A CN201510618430 A CN 201510618430A CN 105131186 A CN105131186 A CN 105131186A
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Abstract
The invention discloses a functionalized starch chelating agent and a preparation method thereof. The functionalized starch chelating agent takes starch as a substrate, the starch undergoes a grafting reaction with glycidyl methacrylate under the action of an initiator, and a part of epoxy groups in the glycidyl methacrylate are subjected to loop opening under a high-temperature alkaline condition and react with amino on 5-aminosalicylic acid to synthesize the functionalized starch chelating agent. The preparation method comprises the following steps: preparing gelatinized starch from starch; then adding the initiator and reacting with the glycidyl methacrylate to obtain a crude product; purifying the crude product to obtain a starch graft copolymerized purified product; swelling the purified product and reacting with the 5-aminosalicylic acid dissolved in a sodium hydroxide aqueous solution, and washing the product with water and drying to obtain the functionalized starch chelating agent. The functionalized starch chelating agent has favorable selective adsorptivity on heavy metal ions in water, and is high in adsorption capacity and wide in applicable pH range; the preparation method for the functionalized starch chelating agent is mild in synthesis conditions, simple and convenient to operate and simple and easily available in raw materials.
Description
Technical field
The invention belongs to natural macromolecular material field, particularly relate to a kind of functionalization starch sequestrant and preparation method thereof.
Background technology
In recent years, the event of Electroplate Factory's in violation of rules and regulations discharge occurs again and again, pollutes water and the soil resource of surrounding, causes farmland contaminated by heavy metals simultaneously, and the Direct and indirect damage life and health of the mankind, causes the attention of the whole society for heavy metals emission.
Existing heavy metal absorbent mostly is organic synthesis polymeric sorbent, have that monomer toxicity is large, the shortcoming of difficult degradation, and natural macromolecule adsorbent has advantages such as raw material sources are wide, cost is low, synthesis technique is simple, product is easily degraded, so research and development modified natural polymer trapping agent is the focus of research both at home and abroad at present.In the research of flocculation, the research and development of starch conversion sorbent material are the most noticeable because starch not only resource is wide, cheap, product can be biodegradable completely, forms benign cycle at nature.The people such as Xie Guoren have developed a kind of heavy metal absorbent of starch-containing skeleton.This sorbent material take tapioca (flour) as raw material, grafting functional monomer methacrylic acid glycidyl ester, with quadrol, modification is carried out to starch graft copolymer again, the novel amino treated starch of obtained high nitrogen-containing, heavy metal ion in energy planar water is to reach the object of process heavy metal wastewater thereby, this technology is disclosed in " Journal of Chemical Industry and Engineering " in April, 2011, and the 62nd volume the 4th phase 970 ~ 976 pages, title of article is: quadrol treated starch GMA multipolymer is to the absorption property of Pb (II).Sorbent material disclosed in this article is in pH=6 ~ 8 time, just can reach good absorption property, at starting point concentration 100mg/L, during pH=6.0, be 0.0481mmol/g to the maximum adsorption capacity of Pb (II) at 25 DEG C, the ability of its Adsorption of Heavy Metal Ions has much room for improvement, applicable pH interval needs to be expanded, meanwhile, this liquid as similar ammonia odor of quadrol, not participating in reaction due to part quadrol during product discharge can aggravating working environment.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of functionalization starch sequestrant and preparation method thereof, this functionalization starch sequestrant has good Selective adsorption to heavy metal ion in water, and loading capacity is large, and applicable pH range is wide; Its preparation method synthesis condition is gentle, and easy and simple to handle, raw material is simple and easy to get.
For this reason, technical scheme of the present invention is as follows:
A kind of functionalization starch sequestrant take starch as matrix, starch and glycidyl methacrylate generation graft reaction under the effect of initiator, and the percentage of grafting of glycidyl methacrylate on starch is 21.37 ~ 84.86%; Be grafted to the PART EPOXY group open loop in the glycidyl methacrylate on starch and the amino on 5-aminosalicylic acid reacts, synthesis has the functionalization starch sequestrant of chelation group.
A preparation method for functionalization starch sequestrant, comprises the steps:
1) starch is made pasted starch;
2) in described pasted starch, add initiator, glycidyl methacrylate reaction, then use alcohol settling, distilled water wash, dry to constant weight and obtain starch graft copolymer crude product;
3) by the homopolymer of described starch graft copolymer crude product apparatus,Soxhlet's removing glycidyl methacrylate, then drying obtains starch graft copolymer pure products;
4) described starch graft copolymer pure products is added the aqueous solution of dimethyl sulfoxide (DMSO) or dimethyl sulfoxide (DMSO), swelling, obtain A;
5) 5-aminosalicylic acid is dissolved in aqueous sodium hydroxide solution, obtains the solution B that degree of neutralization is 30-90%;
6) by step 5) solution B that obtains adds step 4) in the A that obtains, logical N
2at 60 ~ 90 DEG C of reaction 15 ~ 24h, then products in water is washed till neutrality, dries to constant weight, namely obtain described functionalization starch sequestrant.
Preferably, described starch is tapioca (flour), yam starch or W-Gum.
Preferably, step 1) in the condition of pasted starch be: mixed by the water of starch with its quality 3 ~ 20 times, at 60 ~ 70 DEG C, pass into nitrogen, stirring 0.5 ~ 1h, obtains pasted starch.
Preferably, step 2) described initiator is cerium salt, persulphate or manganese salt, or the mixture of persulphate and Sulfothiorine, forms initiator system.More preferably, described cerium salt is ceric ammonium nitrate or ammonium cerous sulfate; Described persulphate is ammonium persulphate or Potassium Persulphate; Described manganese salt is potassium permanganate or manganese pyrophosphate.
Preferably, step 2) temperature of reaction be 30 ~ 70 DEG C.
Preferably, step 3) utilize during the homopolymer of apparatus,Soxhlet's removing glycidyl methacrylate and make solvent with acetone.
Preferably, step 4) described in the swelling condition of starch graft copolymer pure products be: swelling 1 ~ 5h under 60 ~ 80 DEG C of conditions.
Preferably, step 5) quality of described 5-aminosalicylic acid is 0.5 ~ 5 times of described starch graft copolymer pure products quality, the concentration of described aqueous sodium hydroxide solution is 0.1 ~ 2mol/L.
When functionalization starch sequestrant provided by the invention is used for the pollutant effluents containing heavy metal ion, functional group in molecule and metal ion generation sequestering action, generate insoluble product, precipitation rapid flocculation is precipitated, reach the object of metal ion in removing waste water.The adsorption effect of this functionalization starch sequestrant to cadmium, copper is good, also has adsorption effect to zinc, nickel.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the functionalization starch sequestrant that embodiment 1 obtains;
Fig. 2 is the infrared spectrogram of the functionalization starch sequestrant that embodiment 1 obtains.
Embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is described in detail;
Glycidyl methacrylate graft in each embodiment records as follows to the percentage of grafting on matrix starch:
Adopt gravimetric determination percentage of grafting (G, %).Wrapped by dried starch graft copolymer crude product filter paper, be placed in the extracting of 250ml Soxhlet extractor and remove homopolymer, washing, suction filtration vacuum-drying, to constant weight, obtain starch graft copolymer pure products.
Calculation formula is as follows:
In formula: W
0for reacting the quality of starch, g; W
2for the quality that pure graft copolymerization is produced, g.
Embodiment 1
Extracting corn starch 2g and distilled water 16mL adds in 250mL there-necked flask, pass into nitrogen pasted starch 1h at 70 DEG C, 0.06g Potassium Persulphate is added to 60 DEG C after cooling, 3ml glycidyl methacrylate, reaction 2h, with alcohol settling, distilled water wash, after drying, obtain starch-grafted glycidyl methacrylate copolymerization crude product.By dry for this starch-grafted glycidyl methacrylate copolymerization crude product acetone extracting 24h final vacuum in apparatus,Soxhlet's, obtain starch graft copolymer pure products, weighing and obtaining percentage of grafting (G) data after calculating is 82.73%.
Getting starch graft copolymer pure products 2g adds in 250mL there-necked flask, use 2mol/LNaOH aqueous dissolution 4g5-aminosallcylic acid again, its degree of neutralization is 75%, also add in 250mL there-necked flask, stir, logical nitrogen, condensing reflux 20h at 60 DEG C, then product distilled water is washed till neutrality, vacuum-drying at 60 DEG C, obtains functionalization starch sequestrant.Fig. 1 gives the shape appearance figure of this functionalization starch sequestrant, and Fig. 2 is the infrared spectrum of this functionalization starch sequestrant, by the known sequestrant surface irregularity of scanning electron microscope (SEM) photograph, loosely organized, is conducive to the carrying out of absorption behavior; By the known strong absorption peak of OH stretching vibration having starch in 3413cm-1 vicinity of infrared spectrum, near 2935cm-1, there is CH2 antisymmetric stretching vibration absorption peak, and have the charateristic avsorption band of starch at 755cm-1,575cm-1 place; There is the C=O stretching vibration peak of ester group at 1723cm-1 place; There is phenyl ring characteristic peak at 1569cm-1,1496cm-1,1446cm-1, show that 5-aminosalicylic acid is successfully modified on graft starch.
Get the functionalization starch sequestrant 20mg finally obtained, joining pH=6Cd (II) ion starting point concentration is in the 50mL waste water of 200mg/L, after stirred at ambient temperature 60min, recording concentration of heavy metal ion with atomic absorption analyzer and calculating Cd (II) ionic equilibrium loading capacity is 139mg/g.
Get the functionalization starch sequestrant 20mg finally obtained, joining pH=3Cd (II) ion starting point concentration is in the 50mL waste water of 180mg/L, after stirred at ambient temperature 60min, recording concentration of heavy metal ion with atomic absorption analyzer and calculating Cd (II) ionic equilibrium loading capacity is 109mg/g.
Get the functionalization starch sequestrant 20mg finally obtained, joining pH=4.5Cu (II) ion starting point concentration is in the 50mL waste water of 100mg/L, after stirred at ambient temperature 60min, atomic absorption analyzer records concentration of heavy metal ion and calculates Cu (II) ionic equilibrium loading capacity is 96mg/g.
Embodiment 2
Extracting corn starch 5g and distilled water 100mL adds in 250mL there-necked flask, nitrogen pasted starch 0.5h is passed at 70 DEG C, add 0.5g ammonium persulphate and 8ml glycidyl methacrylate again, at 50 DEG C of reaction 2h, with alcohol settling, distilled water wash, obtains starch-grafted glycidyl methacrylate copolymerization crude product after drying.By dry for this starch-grafted glycidyl methacrylate copolymerization crude product acetone extracting 24h final vacuum in apparatus,Soxhlet's, obtain starch graft copolymer pure products, weighing and obtaining percentage of grafting (G) data after calculating is 67.46%.
Getting starch graft copolymer pure products 2g adds in 250mL there-necked flask, also add in 250mL there-necked flask with 1mol/LNaOH aqueous dissolution 3g5-aminosallcylic acid again, stir, logical nitrogen, condensing reflux 20h at 65 DEG C, then product distilled water is washed till neutrality, vacuum-drying at 60 DEG C, obtains functionalization starch sequestrant.
Embodiment 3
Extracting corn starch 6g and distilled water 100mL adds in 250mL there-necked flask, nitrogen pasted starch 1h is passed at 65 DEG C, add 0.5g ammonium persulphate, 0.43g Sulfothiorine and 9.5ml glycidyl methacrylate again, at 60 DEG C of reaction 1.5h, with alcohol settling, distilled water wash, obtains starch-grafted glycidyl methacrylate copolymerization crude product after drying.By dry for this starch-grafted glycidyl methacrylate copolymerization crude product acetone extracting 24h final vacuum in apparatus,Soxhlet's, obtain starch graft copolymer pure products, weighing and obtaining percentage of grafting (G) data after calculating is 78.06%.
Getting starch graft copolymer pure products 2g adds in 250mL there-necked flask, also add in 250mL there-necked flask with 1mol/LNaOH aqueous dissolution 4g5-aminosallcylic acid again, stir, logical nitrogen, condensing reflux 15h at 65 DEG C, then product distilled water is washed till neutrality, vacuum-drying at 60 DEG C, obtains functionalization starch sequestrant.
Comparative example 1
6g starch, distilled water are loaded in the four-hole boiling flask with thermometer and nitrogen protection device; emulsifying agent is added after stirring for some time; monomer GMA12.0g and initiator is added after mixing; react at 60 DEG C to 1h discharging; take out from reaction system fast and pour breakdown of emulsion in dehydrated alcohol into, soak at room temperature 30min remove unreacted monomer, after suction filtration 60 DEG C dry must thick grafts; remove homopolymer through acetone soxhlet type 24h again, obtain pure graft product.Get the pure graft product of 2g and 30ml quadrol, catalyzer loads and stir with in the there-necked flask of agitator, condensing reflux at 90 DEG C, yellow sticky shape product is obtained after reaction 12h, precipitation is separated out with dehydrated alcohol, neutral rear suction filtration is washed till with distilled water, after 70 DEG C of vacuum-dryings amino modified starch (quadrol treated starch GMA multipolymer is to the absorption property of Pb (II). Xie Guoren etc. Journal of Chemical Industry and Engineering, in April, 2011, the 62nd volume the 4th phase 970 ~ 976 pages).
Take the starch-grafted glycidyl methacrylate copolymer 20mg of above-mentioned quadrol amination, joining pH=6Pb (II) ion starting point concentration is in the 100mL waste water of 100mg/L, and after stirred at ambient temperature 120min, atomic absorption analyzer records and calculates Pb (II) ionic equilibrium loading capacity is 93mg/g.
As can be seen from the contrast of comparative example and embodiment 1 ~ 3, functionalization starch sequestrant provided by the invention is larger to capacity heavy metal ion adsorbed in water, and applicable pH range is wider, and range of application is more extensive.
Claims (10)
1. a functionalization starch sequestrant take starch as matrix, and with glycidyl methacrylate generation graft reaction under the effect of initiator, and the percentage of grafting of glycidyl methacrylate on starch is 21.37 ~ 84.86%; It is characterized in that: be grafted to the PART EPOXY group open loop in the glycidyl methacrylate on starch and the amino on 5-aminosalicylic acid reacts, synthesis has the functionalization starch sequestrant of chelation group.
2. the preparation method of functionalization starch sequestrant as claimed in claim 1, is characterized in that comprising the steps:
1) starch is made pasted starch;
2) in described pasted starch, add initiator, glycidyl methacrylate reaction, then use alcohol settling, after distilled water wash, dry to constant weight, obtain starch graft copolymer crude product;
3) by the homopolymer of described starch graft copolymer crude product apparatus,Soxhlet's removing glycidyl methacrylate, then drying obtains starch graft copolymer pure products;
4) described starch graft copolymer pure products is added the aqueous solution of dimethyl sulfoxide (DMSO) or dimethyl sulfoxide (DMSO), swelling, obtain A;
5) 5-aminosalicylic acid is dissolved in aqueous sodium hydroxide solution, obtains the solution B that degree of neutralization is 30-90%;
6) by step 5) solution B that obtains adds step 4) in the A that obtains, logical N
2at 60 ~ 90 DEG C of reaction 15 ~ 24h, then products in water is washed till neutrality, dries to constant weight, namely obtain described functionalization starch sequestrant.
3. preparation method as claimed in claim 2, is characterized in that: described starch is tapioca (flour), yam starch or W-Gum.
4. preparation method as claimed in claim 2, is characterized in that: step 2) described initiator is cerium salt, persulphate or manganese salt, or the mixture of persulphate and Sulfothiorine.
5. preparation method as claimed in claim 4, is characterized in that: described cerium salt is ceric ammonium nitrate or ammonium cerous sulfate; Described persulphate is ammonium persulphate or Potassium Persulphate; Described manganese salt is potassium permanganate or manganese pyrophosphate.
6. preparation method as claimed in claim 2, is characterized in that: step 5) quality of described 5-aminosalicylic acid is 0.5 ~ 5 times of described starch graft copolymer pure products quality, the concentration of described aqueous sodium hydroxide solution is 0.1 ~ 2mol/L.
7. preparation method as claimed in claim 2, is characterized in that: step 1) in the condition of pasted starch be: mixed by the water of starch with its quality 3 ~ 20 times, at 60 ~ 70 DEG C, pass into nitrogen, stirring 0.5 ~ 1h, obtains pasted starch.
8. preparation method as claimed in claim 2, is characterized in that: step 2) temperature of reaction be 30 ~ 70 DEG C.
9. preparation method as claimed in claim 2, is characterized in that: step 3) make solvent with acetone when utilizing apparatus,Soxhlet's to remove the homopolymer of glycidyl methacrylate.
10. preparation method as claimed in claim 2, is characterized in that: step 4) described in the swelling condition of starch graft copolymer pure products be: swelling 1 ~ 5h under 60 ~ 80 DEG C of conditions.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106117426A (en) * | 2016-06-20 | 2016-11-16 | 上海东升新材料有限公司 | A kind of preparation method of modified corn starch chelating agen and products thereof |
| CN107433189A (en) * | 2017-08-14 | 2017-12-05 | 天津科技大学 | A kind of preparation method and applications of novel microporous starch |
| CN113603283A (en) * | 2021-08-16 | 2021-11-05 | 温州科锐环境资源利用有限公司 | Nickel-containing wastewater resource utilization process |
| CN114789046A (en) * | 2022-05-23 | 2022-07-26 | 燕山大学 | Heavy metal trapping agent and application thereof |
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| WO2008094451A1 (en) * | 2007-01-26 | 2008-08-07 | Plantic Technologies Limited | Composition comprising biopolymer |
| CN101717473A (en) * | 2009-12-07 | 2010-06-02 | 广州大学 | Graft copolymer of starch and methacrylic dehydrated glyceride |
| CN102040713A (en) * | 2009-10-23 | 2011-05-04 | 中国科学院上海应用物理研究所 | Graft modified polymer material and preparation method thereof |
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| WO2008094451A1 (en) * | 2007-01-26 | 2008-08-07 | Plantic Technologies Limited | Composition comprising biopolymer |
| CN102040713A (en) * | 2009-10-23 | 2011-05-04 | 中国科学院上海应用物理研究所 | Graft modified polymer material and preparation method thereof |
| CN101717473A (en) * | 2009-12-07 | 2010-06-02 | 广州大学 | Graft copolymer of starch and methacrylic dehydrated glyceride |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117426A (en) * | 2016-06-20 | 2016-11-16 | 上海东升新材料有限公司 | A kind of preparation method of modified corn starch chelating agen and products thereof |
| CN107433189A (en) * | 2017-08-14 | 2017-12-05 | 天津科技大学 | A kind of preparation method and applications of novel microporous starch |
| CN113603283A (en) * | 2021-08-16 | 2021-11-05 | 温州科锐环境资源利用有限公司 | Nickel-containing wastewater resource utilization process |
| CN114789046A (en) * | 2022-05-23 | 2022-07-26 | 燕山大学 | Heavy metal trapping agent and application thereof |
| CN114789046B (en) * | 2022-05-23 | 2024-04-02 | 燕山大学 | Heavy metal trapping agent and application thereof |
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