CN102690516B - Biodegradable cross-linked chitosan chelating resin and preparation method thereof - Google Patents
Biodegradable cross-linked chitosan chelating resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of biodegradable cross-linked chitosan chelating resin and a preparation method thereof which includes the following steps of: (1) taking phosphoric acid as catalyst and L-aspartate as the raw material to perform dehydration condensation under high temperature to prepare polysuccinimide; (2) making the polysuccinimide react with L-cystine to obtain solid material; (3) hydrolyzing the solid material obtained in step (2) in sodium hydroxide solution to open the loops to obtain polysuccinimide provided with amino side chains and -S-S-groups; and (4) taking glutaraldehyde as the cross-linking agent and making the polysuccinimide provided with amino side chains and -S-S- groups and chitosan be subjected to cross-linking reaction to obtain the cross-linked chitosan chelating resin. The cross-linked chitosan chelating resin synthesized through the method provided by the invention can be used repeatedly, is biodegradable and has good thermal stability. The cross-linked chitosan chelating resin can remove the heavy metal ions of Pb<2+>, Hg<2+>, Co<2+> and Ni<2+> in sewage, and has good effects of adsorbing various heavy metal ions in waste water. The cross-linked chitosan chelating resin is biodegradable and can be recovered for repeated use.
Description
Technical field
What the present invention relates to is a kind of biodegradable cross-linked chitosan resin.The present invention also relates to a kind of synthetic method of biodegradable cross-linked chitosan resin.
Background technology
Along with the developing rapidly of China's economy, population growth and urbanization process are accelerated, water pollution problems becomes increasingly conspicuous.The root that affects at present China's quality of water environment is mainly organism and heavy metal ion, and these pollutents are mainly from industries such as metallurgy, plating, process hides, mining, dyestuffs, and wherein some metal ion is expensive, rare, as Ag
+, Pt
2+, Re
2+, Au
3+deng, some metal ion is poisonous, as Hg
2+, Ni
2+, Pb
2+, Cd
2+deng.Thereby enrichment with separate these heavy metal ion, can meet social demand to a certain extent, can reclaim heavy metal ion again, alleviate the pollution to environment, promote the mankind and Environmental Health coordinated development.
Traditional method does not generally have biodegradable characteristic for the resin material of water treatment, as people (Efficient removal of Cu (II) such as Li Niu, Pb (II), Cr (VI) and As (V) from aqueous solution using an aminated resin prepared by surface-initiated atom transfer radical polymerization.Chemical Engineering Journal.2010, 165, 751-757.) take chloromethylated polystyrene as the synthetic a kind of novel amine resin of parent, it has good adsorption effect, to Cu (II), Pb (II), the loading capacity of Cr (VI) and As (V) is followed successively by 2.6, 0.97, 3.0 and 2.2mmol/g, but this resin regeneration ability, and do not there is biodegradability, its waste and old resin can produce secondary pollution to environment.
Chitosan is the product of chitin deacetylase base; chitin is to be only second to cellulosic second largest natural biological polymer substance; on the annual earth, chitin Nature creating amount is up to 10,000,000,000 tons; its output and Mierocrystalline cellulose are suitable; reserves are huge, and chitosan can be applied at numerous areas such as water treatment, chemical industry, food.Yet the chitosan specific surface area of native state is little, be soluble in acidic medium and softening the loss, be unfavorable for reusing, restrict its direct application.Chitosan is carried out to chemical modification, and the resin product of making can not produce secondary pollution, is easy to regeneration, simultaneously biodegradable, has good economic benefit, social benefit and environmental benefit.In the patent document of China Patent Publication No.: 102002116A, disclose a kind of Quaterisation chitosan cross-linked resin, many kinds of metal ions and azoic dyestuff RB-5 have all been had to good adsorption effect.People (the Preparation of Biomimetic Materials Made from Polyaspartyl Polymer and Chitosan for Heavy-Metal Removal.Ind.Eng.Chem.Res.2009 such as Bo Sun, 48,9823-9829.) and the patent document of China Patent Publication No.: CN1869105 in, adopt the raw materials such as ASPARTIC ACID, 1B, chitosan and Thiovanic acid, with glutaraldehyde as cross linker, synthesize and a kind ofly there is peptide-polyose like structure copolymer, not only increased in resin-NH
2quantity, introduced sulfydryl, and had the biological degradability of poly-aspartic-acid and chitosan concurrently, this is a kind of environmentally friendly, bionical degradable novel materials, but this copolymeric material is only applicable to the solution system of extremely low concentration, and saturated extent of adsorption is lower, and swelling ratio is larger, be unfavorable for the bed operation, and adopted poisonous Thiovanic acid in the reaction building-up process.
Summary of the invention
The object of the present invention is to provide a kind ofly be repeatedly used, the biodegradable cross-linked chitosan resin of biodegradable, good thermal stability.The present invention also aims to provide a kind of preparation method of biodegradable cross-linked chitosan resin.
The object of the present invention is achieved like this:
Biodegradable cross-linked chitosan resin of the present invention has following structural formula:
Wherein x is less than or equal to 110, m+n and is less than or equal to 30.
The preparation method of biodegradable cross-linked chitosan resin of the present invention is:
(1) take phosphoric acid as catalyzer, ASPARTIC ACID is that dehydrating condensation at high temperature occurs raw material, prepares polysuccinimide;
(2) polysuccinimide of gained is reacted with CYSTINE, obtain solid matter;
(3) solid matter hydrolysis in sodium hydroxide solution of step (2) reaction gained, obtain with amino side-chain and-polysuccinimide of S-S-group;
(4) use glutaraldehyde as cross linker, will with amino side-chain and-polysuccinimide and the chitosan of S-S-group carry out crosslinking reaction, obtain the cross-linked chitosan resin.
The preparation method of biodegradable cross-linked chitosan resin of the present invention can also comprise:
1, describedly take phosphoric acid as catalyzer, ASPARTIC ACID is that dehydrating condensation at high temperature occurs raw material, the method for preparing polysuccinimide comprises: in container, add successively the 20-50ml whiteruss, 0.2-0.4g the phosphoric acid that volume by volume concentration is 85% and 10-20g ASPARTIC ACID, be heated to 190-230 ℃, insulation 2-5h, react complete, reaction mixture is cooled to room temperature, filtering separation supernatant liquid paraffin, solid particulate is successively with normal heptane washing three times, the washing with alcohol that volume by volume concentration is 95% three times, finally be washed with distilled water to neutrality, suction filtration, at 40 ℃ of lower drying under reduced pressure 48h, obtain polysuccinimide yellow powder powder material.
2, described polysuccinimide reacts and comprises with CYSTINE: the 2-10g polysuccinimide is dissolved in the 10-50ml DMF, is heated with stirring to 40-60 ℃, obtain red tan solution A; 1-5g CYSTINE and 0.5-2.0g solid NaOH are dissolved with 10-50ml distilled water, obtain light green solution B; Solution B is poured in solution A and mixed, mixed solution proceeds in microwave reactor immediately, and regulating power, at 80-120W, is reacted 4-10min, be cooled to room temperature after reaction, reaction mixture is slowly splashed in the absolute methanol solution of 50-250ml, and vigorous stirring, until separate out all flockss, then the triplicate centrifugation precipitates, suction filtration, at 40 ℃ of lower drying under reduced pressure 24h, obtain solid matter.
3, solid matter is hydrolysis in sodium hydroxide solution, obtain with amino side-chain and-method of the polysuccinimide of S-S-group is: will get the described solid matter of 2-10g and add in the NaOH solution that 10-50ml concentration is 2mol/L, the pH of solution is controlled at 10-12, until form yellow solution clearly, it is slowly splashed in the 40-200ml anhydrous methanol under vigorous stirring, separate out flocks, then centrifugation precipitates, and with methyl alcohol repeated washing three times, suction filtration, at 40 ℃ of lower drying under reduced pressure 24h, obtain with amino side-chain and-polysuccinimide of S-S-group.
4, described use glutaraldehyde as cross linker, will with amino side-chain and-polysuccinimide and the chitosan of S-S-group carry out crosslinking reaction, the method that obtains the cross-linked chitosan resin is: by 0.2-0.4g with amino side-chain and-polysuccinimide of S-S group adds in the 5-10ml deionized water, carry out acidifying with dilute hydrochloric acid, control pH value of solution in the 4-5 scope, it is dissolved fully, and then add the glutaraldehyde 0.2-0.4ml of 50wt%, obtain solution C;
In the container that 0.1-0.2g chitosan powder is housed, add successively the acetum 10-20ml that hydrochloric acid soln 2-4ml that volume by volume concentration is 2% and volume by volume concentration are 5%, under room temperature, stir, until powder dissolves fully, obtain settled solution D;
Solution C is poured in solution D, and the vigorous stirring mixed solution, mix it fully, at room temperature maintain 15min, then 2mol/L NaOH solution is added drop-wise in above-mentioned mixed solution, pH value of solution is controlled in the 7-8 scope, until precipitation fully, then centrifugation, use the deionized water rinsing throw out, until washings pH is neutrality, then suction filtration, solid matter, at 40 ℃ of lower drying under reduced pressure 24h, is obtained to biodegradable cross-linked chitosan resin.
The implementation procedure of method of the present invention can be as follows with reaction formula:
For solving serious water pollution problems, the present invention synthesized a kind ofly be repeatedly used, the cross-linked chitosan resin of biodegradable, good thermal stability.Introduce the segment of poly-aspartic-acid and chitosan in crosslinked resin, make this resin there is biological degradability, avoided the secondary pollution of resin; Simultaneously introduce-NH of single step reaction in resin in addition
2with-S-S-functional group, make in resin structure to have the atoms such as N, O, S simultaneously, more assist in removing the Pb in sewage
2+, Hg
2+, Co
2+and Ni
2+etc. heavy metal ion.
Resin Composition of the present invention is simple, and the resin size of preparing is even, and acid and alkali-resistance has good adsorption effect to contents of many kinds of heavy metal ion in waste water, has biodegradability, renewable reusing.
Embodiment
Below for example the present invention is described in more detail:
Embodiment 1:
(1) in being housed, the 100ml three-necked bottle of water trap, reflux exchanger, thermometer and whipping appts adds successively the 20-50ml whiteruss, 0.2-0.4g 85% phosphoric acid and 10-20g ASPARTIC ACID, be heated to about 190-230 ℃ with oil bath, then be incubated approximately 2 ~ 5h, react complete, reaction mixture is cooled to room temperature, filtering separation supernatant liquid paraffin, solid particulate is successively by normal heptane washing three times, 95% washing with alcohol three times, finally be washed with distilled water to neutrality, suction filtration, at 40 ℃ of lower drying under reduced pressure 48h, obtain yellow powder powder material (1).
(2) get 2-10g material (1) and be dissolved in the 10-50ml DMF, be heated with stirring to 40-60 ℃, until all dissolve, obtain a red tan solution A; 1-5g CYSTINE and 0.5-2.0g solid NaOH are added in the flask that about 10-50ml distilled water is housed, at room temperature stir and make its whole dissolvings, obtain a light green solution B; Solution B is poured in solution A and mixed, mixed solution proceeds in microwave reactor immediately, and regulating power is in the scope of 80-120W, and set of time is at 4-10min, be cooled to room temperature after reaction, reaction mixture is slowly splashed in the absolute methanol solution of about 50-250ml, and vigorous stirring, until separate out all flockss, then the triplicate centrifugation precipitates, suction filtration, at 40 ℃ of lower drying under reduced pressure 24h, obtain solid matter (2).
(3) getting 2-10g material (2) adds in 10-50ml NaOH solution (2mol/L), the pH of solution is controlled at 10-12, until form yellow solution clearly, it is slowly splashed in the 40-200ml anhydrous methanol under vigorous stirring, separate out flocks, then the centrifugation precipitation, and with methyl alcohol repeated washing three times, suction filtration, at 40 ℃ of lower drying under reduced pressure 24h, obtain material (3).
(4) get 0.2-0.4g material (3) and add in the 5-10ml deionized water, with dilute hydrochloric acid, carry out acidifying, control pH value of solution in the 4-5 scope, it is dissolved fully, and then add the glutaraldehyde 0.2-0.4ml of 50wt%, obtain solution (4).
(5) get 0.1-0.2g chitosan powder and add in beaker, add successively 2%(v/v) hydrochloric acid soln 2-4ml and 5%(v/v) acetum 10-20ml, under room temperature, stir, until powder dissolves fully, obtain settled solution (5).
(6) solution (4) is poured in solution (5), the vigorous stirring mixed solution, mix it fully, at room temperature maintain 15min, then 2mol/L NaOH solution is added drop-wise in above-mentioned mixed solution, pH value of solution is controlled in the 7-8 scope, until precipitation fully, then centrifugation, use the deionized water rinsing throw out, until washings pH is neutral, then suction filtration, solid matter, at 40 ℃ of lower drying under reduced pressure 24h, is obtained to filemot material (6), and this is the cross-linked chitosan resin.
Resulting resin can be used for containing Ni
2+, Co
2+, Pb
2+, Hg
2+wastewater treatment etc. heavy metal ion.
Embodiment 2:
In being housed, the 100ml three-necked bottle of water trap, reflux exchanger, thermometer and whipping appts adds successively the 25ml whiteruss, 0.241g 85% phosphoric acid and 10g ASPARTIC ACID.Be heated to approximately 220 ℃ with oil bath, then be incubated about 2.5h.
[0011] react complete, reaction mixture is cooled to room temperature, filtering separation supernatant liquid paraffin, solid particulate is successively with normal heptane washing (80ml * 3), 95% washing with alcohol (80ml * 3), finally be washed with distilled water to neutrality, suction filtration, drying under reduced pressure 48h, obtain yellow powder powder polysuccinimide.
Get the 4.85g polysuccinimide and put into the 100ml flask that fills the 25ml DMF, be heated with stirring to 50 ℃, guarantee whole dissolvings.
Get the 2.403g CYSTINE and 1.0g solid NaOH adds in the flask that about 20ml distilled water is housed, at room temperature stir, make its whole dissolvings.
Consoluet CYSTINE solution is poured in polysuccinimide solution and mixed, and mixed solution proceeds in microwave reactor immediately, and reactor parameter is set to power 120W, and time 5min stirs.Be cooled to room temperature, reaction mixture slowly splashed in the absolute methanol solution of about 120ml, and vigorous stirring is complete to precipitation.Then centrifugation, use anhydrous methanol repeated washing three times, and suction filtration, at 40 ℃ of lower drying under reduced pressure, obtain about 6.5g pressed powder.
Get above-mentioned pressed powder 5g, add the NaOH solution of about 25ml 2mol/L, pH is controlled in 11 ~ 12 scopes, until form yellow solution clearly.Be slowly dropped in the 100ml anhydrous methanol under vigorous stirring, separate out flocks, then centrifugation, with methyl alcohol repeated washing three times, suction filtration, then 40 ℃ of lower drying under reduced pressure 24 hours.
Get 0.1g chitosan powder and add in beaker, add successively 2%(v/v) hydrochloric acid soln 2ml and 5%(v/v) acetum 10ml, under room temperature, stir, until powder dissolves fully, prepare chitosan solution.
0.2g is added in the flask that the 5ml deionized water is housed with the polysuccinimide powder of amino side-chain, carry out acidifying with dilute hydrochloric acid, regulate pH and be approximately 4 ~ 5, it is dissolved fully, and then add the glutaraldehyde 0.2ml of 50wt%, its solution is poured in chitosan solution and mixed, vigorous stirring is mixed two kinds of solution fully, at room temperature maintain 15min, then dropwise add 2mol/LNaOH solution, pH to be controlled in 7 ~ 8 scopes, until precipitation fully, then precipitation separation, use the deionized water rinsing several times, until the pH of washings is neutral.Then by the gained solid particulate at 40 ℃ of lower drying under reduced pressure 24h, obtain about 0.9g tawny particulate material, be resin.
The resin that present embodiment is prepared, be about Ni under 7 condition at room temperature and pH
2+clearance be 88.2%; Be about Co under 7 condition at room temperature and pH
2+clearance be 70.3%; Be about Pb under 7 condition at room temperature and pH
2+clearance be 94.5%; At room temperature and pH, be about under 7 condition Hg
2+clearance be 85.8%.
Claims (10)
1. a biodegradable cross-linked chitosan resin is characterized in that having following structural formula:
2. the preparation method of a biodegradable cross-linked chitosan resin, is characterized in that comprising the steps:
(1) take phosphoric acid as catalyzer, ASPARTIC ACID is that dehydrating condensation at high temperature occurs raw material, prepares polysuccinimide;
(2) polysuccinimide of gained is reacted with CYSTINE, obtain solid matter;
(3) solid matter hydrolysis in sodium hydroxide solution of step (2) reaction gained, obtain with amino side-chain and-polysuccinimide of S-S-group;
(4) use glutaraldehyde as cross linker, will with amino side-chain and-polysuccinimide and the chitosan of S-S-group carry out crosslinking reaction, obtain the cross-linked chitosan resin.
3. the preparation method of biodegradable cross-linked chitosan resin according to claim 2, it is characterized in that describedly take phosphoric acid as catalyzer, ASPARTIC ACID is that dehydrating condensation at high temperature occurs raw material, the method for preparing polysuccinimide comprises: in container, add successively the 20-50ml whiteruss, 0.2-0.4g the phosphoric acid that volume by volume concentration is 85% and 10-20g ASPARTIC ACID, be heated to 190-230 ℃, insulation 2-5h, react complete, reaction mixture is cooled to room temperature, filtering separation supernatant liquid paraffin, solid particulate is successively with normal heptane washing three times, the washing with alcohol that volume by volume concentration is 95% three times, finally be washed with distilled water to neutrality, suction filtration, at 40 ℃ of lower drying under reduced pressure 48h, obtain polysuccinimide yellow powder powder material.
4. according to the preparation method of the described biodegradable cross-linked chitosan resin of claim 2 or 3, it is characterized in that described polysuccinimide reacts and comprises with CYSTINE: the 2-10g polysuccinimide is dissolved in to 10-50ml N, in dinethylformamide, be heated with stirring to 40-60 ℃, obtain red tan solution A; 1-5g CYSTINE and 0.5-2.0g solid NaOH are dissolved with 10-50ml distilled water, obtain light green solution B; Solution B is poured in solution A and mixed, mixed solution proceeds in microwave reactor immediately, and regulating power, at 80-120W, is reacted 4-10min, be cooled to room temperature after reaction, reaction mixture is slowly splashed in the absolute methanol solution of 50-250ml, and vigorous stirring, until separate out all flockss, then the triplicate centrifugation precipitates, suction filtration, at 40 ℃ of lower drying under reduced pressure 24h, obtain solid matter.
5. according to the preparation method of the described biodegradable cross-linked chitosan resin of claim 2 or 3, it is characterized in that solid matter hydrolysis in sodium hydroxide solution, obtain with amino side-chain and-method of the polysuccinimide of S-S-group is: will get the described solid matter of 2-10g and add in the NaOH solution that 10-50ml concentration is 2mol/L, the pH of solution is controlled at 10-12, until form yellow solution clearly, it is slowly splashed in the 40-200ml anhydrous methanol under vigorous stirring, separate out flocks, then centrifugation precipitates, and with methyl alcohol repeated washing three times, suction filtration, at 40 ℃ of lower drying under reduced pressure 24h, obtain with amino side-chain and-polysuccinimide of S-S-group.
6. the preparation method of biodegradable cross-linked chitosan resin according to claim 4, it is characterized in that solid matter hydrolysis in sodium hydroxide solution, obtain with amino side-chain and-method of the polysuccinimide of S-S-group is: will get the described solid matter of 2-10g and add in the NaOH solution that 10-50ml concentration is 2mol/L, the pH of solution is controlled at 10-12, until form yellow solution clearly, it is slowly splashed in the 40-200ml anhydrous methanol under vigorous stirring, separate out flocks, then centrifugation precipitates, and with methyl alcohol repeated washing three times, suction filtration, at 40 ℃ of lower drying under reduced pressure 24h, obtain with amino side-chain and-polysuccinimide of S-S-group.
7. according to the preparation method of the described biodegradable cross-linked chitosan resin of claim 2 or 3, it is characterized in that described use glutaraldehyde as cross linker, will with amino side-chain and-polysuccinimide and the chitosan of S-S-group carry out crosslinking reaction, the method that obtains the cross-linked chitosan resin is: by 0.2-0.4g with amino side-chain and-polysuccinimide of S-S group adds in the 5-10ml deionized water, carry out acidifying with dilute hydrochloric acid, control pH value of solution in the 4-5 scope, it is dissolved fully, and then add the glutaraldehyde 0.2-0.4ml of 50wt%, obtain solution C,
In the container that 0.1-0.2g chitosan powder is housed, add successively the acetum 10-20ml that hydrochloric acid soln 2-4ml that volume by volume concentration is 2% and volume by volume concentration are 5%, under room temperature, stir, until powder dissolves fully, obtain settled solution D;
Solution C is poured in solution D, and the vigorous stirring mixed solution, mix it fully, at room temperature maintain 15min, then 2mol/L NaOH solution is added drop-wise in above-mentioned mixed solution, pH value of solution is controlled in the 7-8 scope, until precipitation fully, then centrifugation, use the deionized water rinsing throw out, until washings pH is neutrality, then suction filtration, solid matter, at 40 ℃ of lower drying under reduced pressure 24h, is obtained to biodegradable cross-linked chitosan resin.
8. the preparation method of biodegradable cross-linked chitosan resin according to claim 4, it is characterized in that described use glutaraldehyde as cross linker, will with amino side-chain and-polysuccinimide and the chitosan of S-S-group carry out crosslinking reaction, the method that obtains the cross-linked chitosan resin is: by 0.2-0.4g with amino side-chain and-polysuccinimide of S-S-group adds in the 5-10ml deionized water, carry out acidifying with dilute hydrochloric acid, control pH value of solution in the 4-5 scope, it is dissolved fully, and then add the glutaraldehyde 0.2-0.4ml of 50wt%, obtain solution C,
In the container that 0.1-0.2g chitosan powder is housed, add successively the acetum 10-20ml that hydrochloric acid soln 2-4ml that volume by volume concentration is 2% and volume by volume concentration are 5%, under room temperature, stir, until powder dissolves fully, obtain settled solution D;
Solution C is poured in solution D, and the vigorous stirring mixed solution, mix it fully, at room temperature maintain 15min, then 2mol/L NaOH solution is added drop-wise in above-mentioned mixed solution, pH value of solution is controlled in the 7-8 scope, until precipitation fully, then centrifugation, use the deionized water rinsing throw out, until washings pH is neutrality, then suction filtration, solid matter, at 40 ℃ of lower drying under reduced pressure 24h, is obtained to biodegradable cross-linked chitosan resin.
9. the preparation method of biodegradable cross-linked chitosan resin according to claim 5, it is characterized in that described use glutaraldehyde as cross linker, will with amino side-chain and-polysuccinimide and the chitosan of S-S-group carry out crosslinking reaction, the method that obtains the cross-linked chitosan resin is: by 0.2-0.4g with amino side-chain and-polysuccinimide of S-S-group adds in the 5-10ml deionized water, carry out acidifying with dilute hydrochloric acid, control pH value of solution in the 4-5 scope, it is dissolved fully, and then add the glutaraldehyde 0.2-0.4ml of 50wt%, obtain solution C,
In the container that 0.1-0.2g chitosan powder is housed, add successively the acetum 10-20ml that hydrochloric acid soln 2-4ml that volume by volume concentration is 2% and volume by volume concentration are 5%, under room temperature, stir, until powder dissolves fully, obtain settled solution D;
Solution C is poured in solution D, and the vigorous stirring mixed solution, mix it fully, at room temperature maintain 15min, then 2mol/L NaOH solution is added drop-wise in above-mentioned mixed solution, pH value of solution is controlled in the 7-8 scope, until precipitation fully, then centrifugation, use the deionized water rinsing throw out, until washings pH is neutrality, then suction filtration, solid matter, at 40 ℃ of lower drying under reduced pressure 24h, is obtained to biodegradable cross-linked chitosan resin.
10. the preparation method of biodegradable cross-linked chitosan resin according to claim 6, it is characterized in that described use glutaraldehyde as cross linker, will with amino side-chain and-polysuccinimide and the chitosan of S-S-group carry out crosslinking reaction, the method that obtains the cross-linked chitosan resin is: by 0.2-0.4g with amino side-chain and-polysuccinimide of S-S-group adds in the 5-10ml deionized water, carry out acidifying with dilute hydrochloric acid, control pH value of solution in the 4-5 scope, it is dissolved fully, and then add the glutaraldehyde 0.2-0.4ml of 50wt%, obtain solution C,
In the container that 0.1-0.2g chitosan powder is housed, add successively the acetum 10-20ml that hydrochloric acid soln 2-4ml that volume by volume concentration is 2% and volume by volume concentration are 5%, under room temperature, stir, until powder dissolves fully, obtain settled solution D;
Solution C is poured in solution D, and the vigorous stirring mixed solution, mix it fully, at room temperature maintain 15min, then 2mol/L NaOH solution is added drop-wise in above-mentioned mixed solution, pH value of solution is controlled in the 7-8 scope, until precipitation fully, then centrifugation, use the deionized water rinsing throw out, until washings pH is neutrality, then suction filtration, solid matter, at 40 ℃ of lower drying under reduced pressure 24h, is obtained to biodegradable cross-linked chitosan resin.
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| CN1587282A (en) * | 2004-07-29 | 2005-03-02 | 上海交通大学 | Process for preparing poly succinimide crosslinking modified chitosan material |
| CN1869105A (en) * | 2006-02-10 | 2006-11-29 | 天津理工大学 | Method of preparing mercaptopoly asparagic acid and chitin copolymer and use |
| CN101200504A (en) * | 2006-12-11 | 2008-06-18 | 上海百瑞吉生物医药有限公司 | Macromolecule thiolated modified derivatives and cross-linking material thereof |
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| CN1587282A (en) * | 2004-07-29 | 2005-03-02 | 上海交通大学 | Process for preparing poly succinimide crosslinking modified chitosan material |
| CN1869105A (en) * | 2006-02-10 | 2006-11-29 | 天津理工大学 | Method of preparing mercaptopoly asparagic acid and chitin copolymer and use |
| CN101200504A (en) * | 2006-12-11 | 2008-06-18 | 上海百瑞吉生物医药有限公司 | Macromolecule thiolated modified derivatives and cross-linking material thereof |
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