CN100417666C - Lysine-chitosan resin and preparation method thereof - Google Patents
Lysine-chitosan resin and preparation method thereof Download PDFInfo
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- CN100417666C CN100417666C CNB2006100950993A CN200610095099A CN100417666C CN 100417666 C CN100417666 C CN 100417666C CN B2006100950993 A CNB2006100950993 A CN B2006100950993A CN 200610095099 A CN200610095099 A CN 200610095099A CN 100417666 C CN100417666 C CN 100417666C
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Abstract
The present invention is lysine-chitosan resin and its preparation process, and relates to chitosan modifying technology with lysine. The lysine-chitosan resin consists of chitosan, glutaraldehyde and lysine simply. The preparation process of lysine-chitosan resin includes the first reverse suspending process to prepare chitosan microsphere, the subsequent cross-linking with glutaraldehyde as cross-linking agent to prepare cross-linked chitosan resin and final modification with lysine to prepare the lysine-chitosan resin. The lysine-chitosan resin has homogeneous granularity, rich pores, high acid and alkali resistance and excellent effect of adsorbing acid radical anion, amino acid and protein, is regenerable, and may be used widely in medicine, food, cosmetics, water treatment, chemical and other fields.
Description
One, technical field
The invention belongs to the reaction field of polymer technology, particularly chitosan resin of polylysine modification and preparation method thereof.
Two, technical background
Along with the raising day by day of people's quality of the life, produce, consume environmental protection day by day, demand is further developed natural renewable resource.Chitosan is the deacetylation product of chitin; have graceful function character and distinctive molecular structure such as abundant, nontoxic, renewable, the easy chemistry modification property in source, biocompatibility; weakly-basic anion there is exchange interaction; many heavy metal ion there is good effect; therefore, chitosan is widely used in fields such as medicine, food, makeup, water treatment, chemical industry, agriculturals.But it is Powdered that the chitosan of native state mostly is greatly, and specific surface area is little, is soluble in acidic medium and runs off, and influenced its direct application.Yet,, just can give full play to its good characteristic as if the rosin products of chitosan being made as configurations such as microballoon, porous globules.
Existing chitosan resin normally adopts the chitosan of high degree of deacetylation, makes through chemically crosslinked.If any with the direct cross-linked chitosan of glutaraldehyde, make non-swelling substantially resin under acidity and alkaline condition, this resin only is made up of chitosan and glutaraldehyde, the cross-linked network densification of its product, the duct is little, is unfavorable for the mass transfer of macromolecule material; And because that a large amount of amino have taken place is crosslinked, its chela and capacity and anion-exchange capacity are than obviously reducing before crosslinked; The change that and for example has direct crosslinked way, use Cu earlier
2+With the chitosan chelating, its complexing group is protected, just use glutaraldehyde cross-linking then, again with diluted acid with Cu
2+Elute, thereby obtain cross-linked chitosan-glutaraldehyde resin that chelation group is kept in a large number, this resin also only is made up of chitosan and glutaraldehyde; The even crosslinking of employing water that has prepares the glutaraldehyde cross-linking chitosan resin, is activator with the cyanuric chloride, has synthesized Trimethylamine 99 modified glutaraldehyde crosslinked chitosan resin, and this resin shell glycan, glutaraldehyde and Trimethylamine 99 are formed, and be better by the product absorption property.But all there is the duct in the chitosan resin of these two kinds of method preparations seldom, is unfavorable for shortcomings such as macromole mass transfer.
Three, summary of the invention
The objective of the invention is weak point, a kind of lysine-chitosan resin and preparation method thereof is provided at existing chitosan resin and preparation method thereof.Its resin Composition is simple, and the resin of preparing has epigranular, many micropores, and acid-fast alkali-proof is good, and acid radical anion, amino acid, protein are all had characteristics such as adsorption effect preferably; And reproducible utilization, make full use of resource.
Mechanism of the present invention: owing to contain a large amount of free amine groups in the chitosan molecule chain, free amine group has lone-pair electron, has very strong nucleophilicity, and glutaraldehyde is a kind of bifunctional reagent commonly used, can generate schiff base structure with the amino generation crosslinking reaction of chitosan, crosslinked mainly is in intermolecular generation; Dicyclohexylcarbodiimide (DCC) is a kind of peptide condensing agent that connects commonly used, and it can activated carboxyl, promptly strengthens the Electron Affinities of carboxyl carbon atom, makes nucleophilic nonionic amino be easy to it is attacked, and generates peptide bond thereby condensation reaction takes place.The present invention has utilized above-mentioned two mechanism exactly, and control glutaraldehyde component makes a spot of amino of chitosan and glutaraldehyde generation crosslinking reaction, the carboxyl generation condensation reaction of a large amount of amino and Methionin in little percentage range.
The object of the present invention is achieved like this: a kind of component of lysine-chitosan resin and quality percentage composition thereof are:
Chitosan 42～44%
Glutaraldehyde 20～22%
Methionin 34～36%
A kind of preparation method of lysine-chitosan resin: adopt inverse suspension method preparation chitosan microball earlier, make the part amino on the chitosan molecule participate in crosslinking reaction with glutaraldehyde as cross linker again, make linear chitosan molecule be transformed into net high-polymer, make crosslinked chitosan resin, at room temperature the crosslinked chitosan resin of gained is suspended in the distilled water again, for connecing the peptide condensing agent, make all the other amino carboxyl generation condensation reactions of chitosan make lysine-chitosan resin with dicyclohexylcarbodiimide (DCC) with Methionin.Its concrete method steps is as follows:
(1) preparation chitosan microball
Each component of weighing is standby in proportion, and promptly the quality percentage composition of chitosan, glutaraldehyde and Methionin is respectively 42～44%, 20～22% and 34～36%.Earlier chitosan is dissolved in concentration and is in 0.1～0.3% the dilute hydrochloric acid (HCl), stirring and dissolving at room temperature, make the quality percentage composition and be 1～2% chitosan acidic sol, again fill with concentration be in the container of the isopyknic whiteruss of 0.1～0.3% hydrochloric acid, under agitation, slowly add the chitosan acidic sol, continue to stir 20～30min, make chitosan colloidal sol drop homodisperse become microballoon, just prepare the chitosan microball system.
(2) preparation crosslinked chitosan resin
The chitosan microball system that (1) step was prepared is warmed up to 40～50 ℃, continues to stir, and drips Tween80 (soil temperature 80), makes its percent by volume in system account for 0.4～0.6%, behind 20～30min, adds glutaraldehyde solution, adds CaCO then
3As pore-creating agent.Behind reaction 60～80min, with dilute sodium hydroxide (NaOH) solution regulation system pH to 9～10, temperature control to 60～70 ℃, stir 2.5～3.5h, filter, abandon filtrate, collect filter residue, filter residue is respectively washed 3～5 times with sherwood oil, ethanol successively, use the CaCO in dilute hydrochloric acid (HCl) the dissolving filter residue again
3, be washed with distilled water to neutrality at last, prepare crosslinked chitosan resin.
(3) preparation of lysine-chitosan resin
Under the room temperature, the crosslinked chitosan resin that (2) step was prepared is suspended in the distilled water, and making its quality percentage composition is 4～6%.Under stirring condition, at first add Methionin, the ethanolic soln that adds dicyclohexylcarbodiimide again, wherein the mole number of dicyclohexylcarbodiimide equates with the mole number of Methionin, reacts 20～40min, filters then, abandon filtrate, collect filter residue, to filter residue with washing with alcohol 3～5 times, water dialysis 8～12h again.Filter then, abandon filtrate, collect filter residue, filter residue is dried to constant weight earlier under 60～80 ℃, be cooled to room temperature again.Sieve with 60～100 purpose sub-sieves at last, make lysine-chitosan resin.
Resin Composition of the present invention is simple, and its preparation method is also simple.The inventive method not only makes amino of chitosan and the condensation reaction of Methionin carboxyl generate the polyfunctional group macromolecular compound with two amino, and form netted micropore, most of active function groups are exposed on the surface, in the complexing adsorption process, adsorption site rolls up effective its adsorptive power that improved on the internal surface of hole.In addition, owing to active α-NH in the molecular structural formula of Methionin
2And ε-NH
2Between have a long fat chain structure-(CH
2)
4, after cross-linked chitosan and Methionin react, just look like to have connected many " cantilevers " to it, this structure makes lysine-chitosan resin both keep the bioaffinity of chitosan, has increased certain flexibility again.The resin that adopts the inventive method to prepare has epigranular, many micropores, and acid-fast alkali-proof is good, acid radical anion, amino acid, protein is all had preferably characteristics such as adsorption effect; And reproducible utilization, make full use of resource.Resin of the present invention can be applicable to medicine, food, makeup, water treatment, in the fields such as chemical industry, agricultural and environmental protection.
Three, description of drawings
Fig. 1 is that the chitosan-Methionin resin of present embodiment 1 amplifies 1000 times electron scanning micrograph;
Fig. 2 is that the chitosan-Methionin resin of present embodiment 3 amplifies 250 times electron scanning micrograph.
Four, embodiment
Embodiment below in conjunction with concrete further specifies the present invention.
Embodiment 1
A kind of component of lysine-chitosan resin and quality percentage composition thereof are:
Chitosan 42%
Glutaraldehyde 22%
Methionin 35%
A kind of lysine-chitosan resin preparation method's concrete grammar step is as follows:
(1) preparation chitosan microball
Each component of weighing is standby in proportion, and promptly the quality percentage composition of chitosan, glutaraldehyde and Methionin is respectively 42%, 22% and 35%.Earlier chitosan is dissolved in concentration and is in 0.1% the dilute hydrochloric acid (HCl), stirring and dissolving at room temperature, make the quality percentage composition and be 1% chitosan acidic sol, again fill with concentration be in the container of the isopyknic whiteruss of 0.1% hydrochloric acid, under agitation, slowly add the chitosan acidic sol, continue to stir 20min, make chitosan colloidal sol drop homodisperse become microballoon, just prepare the chitosan microball system.
(2) preparation crosslinked chitosan resin
The chitosan microball system of (1) step preparation is warmed up to 40 ℃, continues to stir, drip Tween80, make its percent by volume in system account for 0.4%, behind the 20min, add glutaraldehyde solution, add CaCO then
3As pore-creating agent.Behind the reaction 60min, with dilute sodium hydroxide (NaOH) solution regulation system pH to 9, temperature control to 60 ℃ stirs 2.5h, filters, and abandons filtrate, collects filter residue, and filter residue is respectively washed 3 times with sherwood oil, ethanol successively, uses dilute hydrochloric acid (HCl) to dissolve CaCO in the filter residue again
3, be washed with distilled water to neutrality at last, prepare crosslinked chitosan resin.
(3) preparation of lysine-chitosan resin
Under the room temperature, the crosslinked chitosan resin that (2) step was prepared is suspended in the distilled water, and making its quality percentage composition is 4%.Under stirring condition, at first add Methionin, the ethanolic soln that adds dicyclohexylcarbodiimide again, wherein the mole number of dicyclohexylcarbodiimide equates with the mole number of Methionin, reacts 20min, filters then, abandon filtrate, collect filter residue, to filter residue with washing with alcohol 3 times, water dialysis 8h again.Filter then, abandon filtrate, collect filter residue, filter residue is dried to constant weight earlier under 60 ℃, be cooled to room temperature again.Sieve with 100 purpose sub-sieves at last, make lysine-chitosan resin.This resin pattern is seen accompanying drawing 1.
Embodiment 2:
A kind of component of lysine-chitosan resin and quality percentage composition thereof are:
Chitosan 43%
Glutaraldehyde 20%
Methionin 36%
A kind of lysine-chitosan resin preparation method's concrete grammar step is as follows:
(1) preparation chitosan microball
Each component of weighing is standby in proportion, and promptly the quality percentage composition of chitosan, glutaraldehyde and Methionin is respectively 43%, 20% and 36%.Earlier chitosan is dissolved in concentration and is in 0.2% the dilute hydrochloric acid (HCl), stirring and dissolving at room temperature, make the quality percentage composition and be 1.5% chitosan acidic sol, again fill with concentration be in the container of the isopyknic whiteruss of 0.2% hydrochloric acid, under agitation, slowly add the chitosan acidic sol, continue to stir 25min, make chitosan colloidal sol drop homodisperse become microballoon, just prepare the chitosan microball system.
(2) preparation crosslinked chitosan resin
The chitosan microball system that (1) step was prepared is warmed up to 45 ℃, continues to stir, and drips Tween80, makes its percent by volume in system account for 0.5%, behind the 25min, adds glutaraldehyde solution, adds CaCO then
3As pore-creating agent.Behind the reaction 70min, with dilute sodium hydroxide (NaOH) solution regulation system pH to 9.5, temperature control to 65 ℃ stirs 3h, filters, and abandons filtrate, collects filter residue, and filter residue is respectively washed 4 times with sherwood oil, ethanol successively, uses dilute hydrochloric acid (HCl) to dissolve CaCO in the filter residue again
3, be washed with distilled water to neutrality at last, prepare crosslinked chitosan resin.
(3) preparation of lysine-chitosan resin
Under the room temperature, the crosslinked chitosan resin that (2) step was prepared is suspended in the distilled water, and making its quality percentage composition is 5%.Under stirring condition, at first add Methionin, the ethanolic soln that adds dicyclohexylcarbodiimide again, wherein the mole number of dicyclohexylcarbodiimide equates with the mole number of Methionin, reacts 30min, filters then, abandon filtrate, collect filter residue, to filter residue with washing with alcohol 4 times, water dialysis 10h again.Filter then, abandon filtrate, collect filter residue, filter residue is dried to constant weight earlier under 70 ℃, be cooled to room temperature again.Sieve with 80 purpose sub-sieves at last, make lysine-chitosan resin.
Embodiment 3:
A kind of component of lysine-chitosan resin and quality percentage composition thereof are:
Chitosan 44%
Glutaraldehyde 21%
Methionin 34%
A kind of lysine-chitosan resin preparation method's concrete grammar step is as follows:
(1) preparation chitosan microball
Each component of weighing is standby in proportion, and promptly the quality percentage composition of chitosan, glutaraldehyde and Methionin is respectively 44%, 21% and 34%.Earlier chitosan is dissolved in concentration and is in 0.3% the dilute hydrochloric acid (HCl), stirring and dissolving at room temperature, make the quality percentage composition and be 2% chitosan acidic sol, again fill with concentration be in the container of the isopyknic whiteruss of 0.3% hydrochloric acid, under agitation, slowly add the chitosan acidic sol, continue to stir 30min, make chitosan colloidal sol drop homodisperse become microballoon, just prepare the chitosan microball system.
(2) preparation crosslinked chitosan resin
The chitosan microball system that (1) step was prepared is warmed up to 50 ℃, continues to stir, and drips Tween80, makes its percent by volume in system account for 0.6%, behind the 30min, adds glutaraldehyde solution, adds CaCO then
3As pore-creating agent.Behind the reaction 80min, with dilute sodium hydroxide (NaOH) solution regulation system pH to 10, temperature control to 70 ℃ stirs 3.5h, filters, and abandons filtrate, collects filter residue, and filter residue is respectively washed 5 times with sherwood oil, ethanol successively, uses dilute hydrochloric acid (HCl) to dissolve CaCO in the filter residue again
3, be washed with distilled water to neutrality at last, prepare crosslinked chitosan resin.
(3) preparation of lysine-chitosan resin
Under the room temperature, the crosslinked chitosan resin that (2) step was prepared is suspended in the distilled water, and making its quality percentage composition is 6%.Under stirring condition, at first add Methionin, the ethanolic soln that adds dicyclohexylcarbodiimide again, wherein the mole number of dicyclohexylcarbodiimide equates with the mole number of Methionin, reacts 40min, filters then, abandon filtrate, collect filter residue, to filter residue with washing with alcohol 5 times, water dialysis 12h again.Filter then, abandon filtrate, collect filter residue, filter residue is dried to constant weight earlier under 80 ℃, be cooled to room temperature again.Sieve with 60 purpose sub-sieves at last, make lysine-chitosan resin.This resin pattern is seen accompanying drawing 2.
Claims (2)
1. lysine-chitosan resin is characterized in that its component and quality percentage composition thereof are:
Chitosan 42～44%
Glutaraldehyde 20～22%
Methionin 34～36%.
2. the preparation method of a lysine-chitosan resin is characterized in that its concrete method steps is as follows:
(1) preparation chitosan microball
Each component of weighing is standby in proportion, the quality percentage composition that is chitosan, glutaraldehyde and Methionin is respectively 42～44%, 20～22% and 34～36%, earlier chitosan is dissolved in concentration and is in 0.1～0.3% the dilute hydrochloric acid, stirring and dissolving at room temperature, make the quality percentage composition and be 1～2% chitosan acidic sol, again fill with concentration be in the container of the isopyknic whiteruss of 0.1～0.3% hydrochloric acid, under agitation, slowly add the chitosan acidic sol, continue to stir 20～30min;
(2) preparation crosslinked chitosan resin
The chitosan microball system that (1) step was prepared is warmed up to 40～50 ℃, continues to stir, and drips Tween80, makes its percent by volume in system account for 0.4～0.6%, behind 20～30min, adds glutaraldehyde solution, adds CaCO then
3As pore-creating agent, behind reaction 60～80min, with diluted sodium hydroxide solution regulation system pH to 9～10, temperature control to 60～70 ℃, stir 2.5～3.5h, filter, abandon filtrate, collect filter residue, filter residue is respectively washed 3～5 times with sherwood oil, ethanol successively, use the CaCO in the diluted hydrochloric acid dissolution filter residue again
3, be washed with distilled water to neutrality at last;
(3) preparation of lysine-chitosan resin
Under the room temperature, the crosslinked chitosan resin that (2) step was prepared is suspended in the distilled water, making its quality percentage composition is 4～6%, under stirring condition, at first adds Methionin, the ethanolic soln that adds dicyclohexylcarbodiimide again, wherein the mole number of dicyclohexylcarbodiimide equates with the mole number of Methionin, reacts 20～40min, filters then, abandon filtrate, collect filter residue, to filter residue with washing with alcohol 3～5 times, water dialysis 8～12h again, filter then, abandon filtrate, collect filter residue, filter residue is dried to constant weight earlier under 60～80 ℃, be cooled to room temperature again, sieve with 60～100 purpose sub-sieves at last.
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| US20130096081A1 (en) | 2011-06-03 | 2013-04-18 | Allergan, Inc. | Dermal filler compositions |
| CA2848833C (en) * | 2011-09-14 | 2017-04-04 | Gabriel N. NJIKANG | Ascorbate modified crosslinked hyaluronic acid dermal filler compositions that exhibit reduced tyndall effect |
| CN102580791B (en) * | 2011-12-12 | 2013-10-16 | 重庆大学 | Preparation method for lysine-modified amphoteric macroporous ion exchange resin |
| CN105601764B (en) * | 2016-02-22 | 2017-11-28 | 南京师范大学 | A kind of amino-acid modified chitosan flocculant and its preparation method and application |
| CN107802567A (en) * | 2017-11-11 | 2018-03-16 | 孙祎 | A kind of preparation method of anti-wrinkle emulsion |
| CN109999767A (en) * | 2019-04-17 | 2019-07-12 | 江苏师范大学 | A kind of method of glutaraldehyde modification of chitosan resin adsorption separation purple sweet potato anthocyanin |
| CN112409524B (en) * | 2020-11-07 | 2022-07-19 | 潍坊华诺医药科技有限公司 | Ion exchange resin for deoxynucleoside triphosphate purification and preparation method thereof |
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| CN1262961A (en) * | 1999-11-19 | 2000-08-16 | 清华大学 | Chitosan catheter for repair of nerve |
| CN1616657A (en) * | 2003-11-10 | 2005-05-18 | 中国科学院大连化学物理研究所 | Method for preparing fixed yeast cell micro capsule |
| CN1739850A (en) * | 2004-08-27 | 2006-03-01 | 中国科学院海洋研究所 | A kind of adsorbing base of big molecule chromoprotein and application |
| CN1795935A (en) * | 2004-12-28 | 2006-07-05 | 广汉恒宇新材料有限公司 | Artificial skin prepard from Nano chitosan and preparing method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262961A (en) * | 1999-11-19 | 2000-08-16 | 清华大学 | Chitosan catheter for repair of nerve |
| CN1616657A (en) * | 2003-11-10 | 2005-05-18 | 中国科学院大连化学物理研究所 | Method for preparing fixed yeast cell micro capsule |
| CN1739850A (en) * | 2004-08-27 | 2006-03-01 | 中国科学院海洋研究所 | A kind of adsorbing base of big molecule chromoprotein and application |
| CN1795935A (en) * | 2004-12-28 | 2006-07-05 | 广汉恒宇新材料有限公司 | Artificial skin prepard from Nano chitosan and preparing method |
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Assignee: Guangzhou Huanya Cosmetics Technology Co., Ltd. Assignor: Chongqing University Contract record no.: 2010440001239 Denomination of invention: Lysine-chitosan resin and preparation method thereof Granted publication date: 20080910 License type: Exclusive License Open date: 20070314 Record date: 20100818 |
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