CN1490349A - Preparation of chitin-beta-cyclodextrin resin - Google Patents
Preparation of chitin-beta-cyclodextrin resin Download PDFInfo
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Abstract
A process for preparing the chitosan-beta-cyclodextrin resin (CTS-CS-CD) with porous structure is disclosed. Its advantages are simple process and high content of beta-CD solid. The resultant resin can be used as biologic adsorbent.
Description
One, technical field
The present invention relates to the relevant preparation method of the chitin-beta-cyclodextrin resin (CTS-CS-CD) of vesicular structure that has.More specifically be meant the preparation method of the glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD) of the oxalic dialdehyde cross-linked chitosan-beta-cyclodextrin resin (CTS-GLY-CD) of vesicular structure and vesicular structure.
Two, background technology
Chitin-beta-cyclodextrin resin is that the affine fractionation by adsorption that is used for enzyme is purified, alkaloid, natural product fractionation by adsorption, and microbiotic is purified, water treatment, agricultural chemicals waste water, dyeing waste-water is handled, medical sorbing material, the biological adsorption agent of medicament slow release etc.
Chitosan (chitosan) can pass through hydrogen bond, net is caught throwing out, mode adsorb organic compound matter such as electric charge adsorption, affine fractionation by adsorption at enzyme is purified, alkaloid, natural product fractionation by adsorption, microbiotic is purified, water treatment, agricultural chemicals waste water, dyeing waste-water is handled, medical sorbing material, fields such as medicament slow release (the 1.Martin G Peter that is widely used, Applications and environmental aspects of chitin and chitosan.Macromole Sci PureAppl Chem.1995, A32 (4): 629-640.2. Jiang Ting is big. " chitin " Beijing: China Environmental Science Press, 1995).It is big to have adsorptive capacity when chitosan is made sorbent material, and speed is fast, and physical strength is good, easily process advantages such as film forming, one-tenth silk, but therefore its no specificity adsorption can carry out chemical modification to improve its absorption rerum natura to chitosan.
Cyclodextrin (β-cyclodextrin; β-CD) has a uniform hydrophobic cavity, can utilize hydrophobic interaction, hydrogen bond carries out molecular recognition, to guest molecule specificity inclusion, the separation, purification (the Jozsef Szejtli that can be used for material, Utilization of cyclodextrins in industrial products and processes.J Mater Chem, 1997,7 (4): 575-587).Have the strong advantage of specificity when cyclodextrin is made sorbent material, but shortcomings such as easily water-soluble, no film-forming properties are arranged.And cyclodextrin and other polymer crosslinked be it to be received on the polymer by bifunctional or multi-group crosslink agent, β-CD superpolymer that crosslinked back forms had both kept the effect of cyclodextrin specificity identification inclusion, has superpolymer physical strength preferably again, better chemical stability (Liu Yong, Zhang Daodao, the research of cyclodextrin superpolymer, functional polymer journal, 1995,8 (1): 101-109.Gaio?Paradossi,Francesca?Cavalieri,Vittorio?Crescenzi.1H?NMR?relaxationstudy?of?a?chitosan-cyclodextrin?network.Carbohydrate?Research,1997,300,77-84)。
For the advantage of bringing into play both overcomes its shortcoming, prepare chitin-beta-cyclodextrin resin at present and mainly adopt two kinds of methods.1. mechanical mixing: β-CD is dispersed in the chitosan solution, and dry evaporative removal solvent is trapped in β-CD in the grid of chitosan.
This preparation method is simple, but resulting resin chemical stability is poor, and when making sorbent material, adsorptive capacity is little, and specificity is low.2. chemical bonding: at first chitosan or β-CD are carried out chemically modified, introduce new functional group, again that β-CD is immobilized to chitosan.As with the cyclodextrin oxidation, make in its structure to have aldehyde radical, by forming Schiff's base that β-CD is immobilized with chitosan.(1.Tomoya?Tojima,Hironori?Katsura,Sang-mun?Han,et?al,Preparation?of?anα-cyclodextrin-linked?chitosan?derivative?via?reductive?amination?strategy,J?PolymSci,Part?A:Polym?Chem,1998,36:1965-1968。2.Fusao?Tanida,Tomoya?Tojima,Sang-MunHan,et?al,Novel?synthesis?of?a?water-soluble?cyclodextrin-polymer?having?a?chitosanskeleton,Polym?39(21):5261-5263)。Chitosan and 1,6 hexamethylene diisocyanate (OCN (CH
2)
6NCO) reaction generates the derivative of chitosan, and is again that β-CD is immobilized to the derivative of chitosan.(k?Sreenivasan,Synthesis?andpreliminary?studies?on?a?β-cyclodextrin-coupled?chitosan?as?a?novel?adsorbent?matrix,J?Appl?Polym?Sci,1998,69:1051-1055)。Chitosan carries out amidation with dicarboxylic anhydride (as the propylenedicarboxylic acid acid anhydride), use Racemic glycidol trimethylammonium ammonia chloride quaternized again to it, at last with β-CD immobilized to chitosan (PCT Int Appl WO97 45,453 US Appl 654,929,29May 1996).But chemical bonding exists reaction complicated, and the resin yield is low, problems such as cost height.
Three, summary of the invention
The present invention is poor in order to overcome the resulting resin chemical stability of mechanical mixing, and when making sorbent material, adsorptive capacity is little, and specificity is low; It is complicated to overcome the chemical bonding reaction, and the resin yield is low, problems such as cost height.Adopted comparatively easy and cheaply chemical synthesis process to synthesize physical strength big, the absorption specificity is strong, good biocompatibility, stable chemical performance and have the chitin-beta-cyclodextrin resin of vesicular structure.
Chemical equation of the present invention is as follows:
Oxalic dialdehyde cross-linked chitosan-beta-cyclodextrin resin (CTS-GLY-CD)
Glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD) oxalic dialdehyde cross-linked chitosan-beta-cyclodextrin resin (CTS-GLY-CD) and glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD)
Preparation method of the present invention is as follows:
The present invention take oxalic dialdehyde, glutaraldehyde as cross linker, synthesized oxalic dialdehyde cross-linked chitosan-beta-cyclodextrin resin (CTS-GLY-CD) and glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD).Weight ratio at beta-cyclodextrin and chitosan is 1: 1~6: 1, beta-cyclodextrin and linking agent oxalic dialdehyde (glyoxal) or glutaraldehyde (glutaraldehyde) mol ratio are 0.1~0.5, the reaction solvent system is 0.2 mole~6 mole hydrochloride aqueous solution, or 0.5%~3% acetic acid aqueous solution, or in the aqueous solution.Reaction times is 0.5 hour~5 hours, temperature of reaction is 40 ℃~120 ℃, with concentration range be 20%~40% oxalic dialdehyde or glutaraldehyde directly with beta-cyclodextrin and chitosan crosslinked, must have the oxalic dialdehyde cross-linked chitosan-beta-cyclodextrin resin (CTS-GLY-CD) and the glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD) of vesicular structure.
Vesicular oxalic dialdehyde cross-linked chitosan of the present invention-beta-cyclodextrin resin (CTS-GLY-CD) and glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD) are to micromolecular compound such as bilirubin, Nicotine has good adsorptive power, and DL amino acid is had the effect of chirality fractionation by adsorption.Because they form the big space reticulated structure of physical strength better chemical stability is arranged.Well antiacid, alkaline energy is arranged.
Preparation method of the present invention has overcome that the resin chemical stability is poor, and adsorptive capacity is little, and specificity is low, the chemical reaction complexity, and the resin yield is low, problems such as cost height.It is big to have synthesized physical strength, and the absorption specificity is strong, good biocompatibility, stable chemical performance and have the chitin-beta-cyclodextrin resin of vesicular structure.
Four, embodiment
Embodiment 1
This patent invention adopts chitosan (chitosan) to use after refining.Process for purification is as follows; Chitosan is dissolved in 0.2~2% the acetic acid solution, remove impurity, NaOH with 30-50% neutralizes up to precipitation no longer occurring, precipitate 1~2 time with distilled water wash, it is neutral regulating the pH value, again with repeatedly washing precipitation of distilled water, soaked 24~48 hours with acetone, filter, be lower than 40~60 ℃ of dryings, must make with extra care chitosan.Measuring deacetylating degree of chitosan is 75%~98%, and molecular weight is 1500~45000.Beta-cyclodextrin is used the distilled water recrystallizing and refining before using.
Oxalic dialdehyde cross-linked chitosan-beta-cyclodextrin resin (CTS-GLY-CD) synthetic method is as follows; (β-CD/chitosan) the weight feed ratio is 6: 1~3 water-soluble back the adding in the three-necked bottle of beta-cyclodextrin with beta-cyclodextrin/chitosan, (the weight feed ratio of β-CD/chitosan) is that (deacetylating degree of chitosan is 94.3% for 1~3: 6 chitosan with beta-cyclodextrin/chitosan again, molecular weight is 23000 or 45000) be dissolved among 1~6MHCl, also add in the three-necked bottle.Start stirrer, after treating that the two mixes, under 0-80 ℃ temperature, drip 40% oxalic dialdehyde linking agent, react after 0.5~6.0 hour with 0.5~2MNaOH adjust pH to pH=7~8, continuation stirring reaction stopped reaction after 0.5~2.0 hour, cooling is washed with water to neutrality with the precipitation of separating out, and uses washing with acetone again 2~3 times, 40-60 ℃ of vacuum-drying obtains oxalic dialdehyde cross-linked chitosan-beta-cyclodextrin resin (CTS-GLY-CD).
The synthetic influence that is subjected to various reaction conditionss of oxalic dialdehyde cross-linked chitosan-beta-cyclodextrin resin (CTS-GLY-CD); Generally speaking, oxalic dialdehyde cross-linked chitosan-beta-cyclodextrin resin (CTS-GLY-CD) preparation feedback temperature is 60 ℃, and in the aqueous solution of 1~2% acetate or 0.5~1MHCl, it is maximum that the supported quantity of β-CD reaches generally speaking.
β-CD the supported quantity of oxalic dialdehyde cross-linked chitosan-beta-cyclodextrin resin (CTS-GLY-CD) is measured as follows; Accurately take by weighing the 25.00mg chitin-beta-cyclodextrin resin, place 15mL tool plug test tube, add the 15mL0.5mol/L sulphuric acid soln, 100 ℃ of hydrolysis 8h are transferred to hydrolyzed solution in the 50mL volumetric flask, use the distilled water constant volume, the hydrolyzed solution of accurately measuring behind the 1ml constant volume places the 15mL test tube, add 1mL distilled water successively, the 1mL8% phenol and the 5mL vitriol oil leave standstill 30min in 25 ℃ behind the mixing.Carry out colorimetric analysis at the 490nm place, calculate glucose content, calculate β-CD content thus according to working curve.
Accurately take by weighing chitosan 25.00mg, do control experiment as stated above, the result shows that the system that chitosan and phenol and the vitriol oil form absorbs in 490nm place nothing, therefore measures β-CD supported quantity to this method and does not disturb after aforesaid method is handled.
Molecular weight is 1500~45000, and deacetylation is 75%~98% chitosan, also can the same method, and the oxalic dialdehyde cross-linked chitosan-beta-cyclodextrin resin (CTS-GLY-CD) of preparation different molecular weight and deacetylation.
Embodiment 2
Chitosan (chitosan) process for purification, deacetylating degree of chitosan, the chitosan molecule weight range, the beta-cyclodextrin process for purification, the β of glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD)-CD supported quantity measuring method is with embodiment 1.
Glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD) synthetic method is as follows; (β-CD/chitosan) the weight feed ratio is 6: 1~3 water-soluble back the adding in the three-necked bottle of beta-cyclodextrin with beta-cyclodextrin/chitosan, (the weight feed ratio of β-CD/chitosan) is that (deacetylating degree of chitosan is 94.3% for 1~3: 6 chitosan with beta-cyclodextrin/chitosan again, molecular weight is 23000 or 45000) be dissolved among 1~6MHCl, also add in the three-necked bottle.Start stirrer, after treating that the two mixes, under 0~80 ℃ temperature, drip 25% glutaraldehyde cross-linking agent, react after 0.5~6.0 hour with 0.5~2MNaOH adjust pH to pH=7~8, continuation stirring reaction stopped reaction after 0.5~2.0 hour, cooling is washed with water to neutrality with the precipitation of separating out, and uses washing with acetone again 2~3 times, 40~60 ℃ of vacuum-dryings obtain glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD).
The synthetic influence that is subjected to various reaction conditionss of glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD); Generally speaking, glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD) preparation feedback temperature is 80 ℃.In the aqueous solution of 1~2% acetate or 0.5~1MHCl, it is maximum that the supported quantity of β-CD reaches generally speaking.
Molecular weight is 1500~45000, and deacetylation is 75%~98% chitosan, also can the same method, and the glutaraldehyde cross-linking chitin-beta-cyclodextrin resin (CTS-GLU-CD) of preparation different molecular weight and deacetylation.
Claims (5)
1, a kind of preparation method of chitin-beta-cyclodextrin resin, chemical equation is as follows:
Chitin-beta-cyclodextrin resin (CTS-CS-CD) n=0,3
It is characterized in that described linking agent is oxalic dialdehyde or glutaraldehyde, the weight ratio of described beta-cyclodextrin and chitosan is 1: 1~6: 1, the mol ratio of beta-cyclodextrin and linking agent is 0.1~0.5, the reaction solvent system is 0.2 mole~6 mole hydrochloride aqueous solution, or 0.5%~3% acetic acid aqueous solution, or in the aqueous solution, reaction times is 0.5 hour~5 hours, temperature of reaction is 40 ℃~120 ℃, is that the glutaraldehyde of 20%~40% oxalic dialdehyde or 25%~50% is directly with beta-cyclodextrin and chitosan crosslinked with concentration range.
2, the preparation method of chitin-beta-cyclodextrin resin according to claim 1 is characterized in that described chitosan process for purification is as follows; Chitosan is dissolved in 0.2~2% the acetic acid solution, removes impurity, and with the NaOH neutralization of 30-50%, with the distilled water wash precipitation, it be neutral regulating pH value, and with acetone immersion 24~48 hours, filtration was lower than 40~60 ℃ of dryings, must make with extra care chitosan.
3, the preparation method of chitin-beta-cyclodextrin resin according to claim 1 and 2 is characterized in that described deacetylating degree of chitosan is 75%~98%, and molecular weight is 1500~45000.
4, chitin-beta-cyclodextrin resin preparation method according to claim 1 is characterized in that described beta-cyclodextrin supported quantity measuring method is: the phenol aqueous sulfuric acid with 5%~8%, carry out colorimetric analysis at UV spectrum 490nm place.
5, chitin-beta-cyclodextrin resin preparation method according to claim 1 is characterized in that described purification processing method is: the distilled water wash that the usefulness weight resin is 5 times~10 times 3~6 times, the washing with acetone that the usefulness weight resin is 2 times~4 times 2~4 times.Wet resin is 30 ℃~70 ℃ vacuum-dryings.
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