CN103720711A - Method for preparing amphiphilic chitosan group nano iodine disinfectant - Google Patents
Method for preparing amphiphilic chitosan group nano iodine disinfectant Download PDFInfo
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Abstract
The invention relates to a method for preparing amphiphilic chitosan group nano iodine disinfectant, which comprises the following steps: carrying out a grafting copolymerization reaction for chitosan or carboxymethyl chitosan and pyrrolidone derivatives and hydrophilic monomers for preparing an amphiphilic chitosan graft copolymer or amphiphilic carboxymethyl chitosan graft copolymer; carrying out a reaction between the obtained graft copolymer and iodine in a certain solvent for preparing the amphiphilic chitosan group nano iodine disinfectant or the amphiphilic carboxymethyl chitosan group nano iodine disinfectant. Compared with the prior art, the chitosan chain is grafted with pyrrolidone derivatives and other hydrophilic monomers, thereby generating the graft copolymer with amphiphilic chitosan group, and the copolymer ensures the iodine to uniformly disperse in the chitosan chain molecules; because nano iodine has good stability, compared with the existed product, the nano iodine disinfectant can remain on skin or wound for a longer time, thereby enhancing bacteriostasis effect, reducing stimulation effect of iodine on skin or wound with more security.
Description
Technical field
The present invention relates to the preparation method of the nano-complex of chitosan derivatives and iodine, especially relate to a kind of method of preparing amphipathic chitose Ji Na meter iodine disinfectant, belong to biomedical materials field.
Background technology
Iodine itself not only has very strong bactericidal properties, and has the specific functions such as absorption, oxidation, antiviral and DNA reciprocal action.But because iodine is easy to distillation conventionally by composite to improve its stability to iodine and various base material, traditional iodine compound is as povidone iodine, povidone iodine, iodine tincture, An Er iodine etc.But it is little to the complexation amount of iodine that these compounds exist, bad dispersibility is unstable, and iodine easily scatters and disappears, and during with contact skin, to skin, particularly the zest of wound is large, and iodine is in skin or the defect such as the wound time of staying is short.Therefore in biomedicine, how more good utilisation iodine need solve two subject matters as broad spectrum antimicrobicide, and the one, the stability of iodine in iodine and various base material compound; The 2nd, how to control release iodine.
Iodine molecule is nonpolar molecule, mainly leans on intermolecular force with chitosan-based combination.No matter research find in water or in organic solvent that iodine and chitosan all can not generate stable complex, illustrate that the intermolecular force between them is less.Chitosan is not almost allowed in all organic solvents simultaneously.If therefore natural macromolecular material chitosan is carried out to functional modification, make chitosan derivatives dissolubility after modification reach the requirement of preparing product, simultaneously can with iodine stable bond, can increase the stability of iodine molecule, can make on the other hand iodine there is good dispersion.
Because amphipathic graft copolymerization is chitosan-based, human body wound surface is had to hemostasis, antiinflammatory and tissue repair function, reduce the stimulation of iodine to wound simultaneously, can at wound surface place, stop the longer time by chelated iodine, improved fungistatic effect and safety.Therefore the dual-use function of this chitosan-based and iodine provides desirable healing environment for wound surface.
The chitosan-based nanometer Surgidine of amphipathic graft copolymerization disinfectant, its nanometer iodine particle size distribution is 10～40nm range scale, there is skin effect, the small scale effect of nanometer, iodine molecule specific surface area, along with granule diminishes and increases sharply, has increased iodine molecule and antibacterial, viral contact frequency on the one hand; Antibacterial, antiviral activity and persistence have been improved on the other hand.Therefore the prepared amphipathic chitose Ji Na meter iodine disinfectant of the present invention can improve the effective rate of utilization of iodine, increases the stability of iodine, reduces wound surface is stimulated.
Summary of the invention
Object of the present invention is exactly to provide a kind of method of preparing amphipathic chitose Ji Na meter iodine disinfectant in order to overcome the defect that above-mentioned prior art exists, and the method can make iodine have good dispersibility and stability.
Object of the present invention can be achieved through the following technical solutions:
A method of preparing amphipathic chitose Ji Na meter iodine disinfectant, comprises the following steps:
(1) chitosan or carboxymethyl chitosan and pyrrolidinone derivatives and hydrophilic monomer are carried out to graft copolymerization and prepare amphipathic chitose graft copolymer or amphipathic carboxymethyl chitosan grafted graft copolymer;
(2) by amphipathic chitose graft copolymer or amphipathic carboxymethyl chitosan grafted graft copolymer and iodine generation amphipathic chitose Ji Na meter Surgidine or amphipathic carboxymethyl chitosan glycosyl nanometer Surgidine, in certain solvent, prepare amphipathic chitose Ji Na meter iodine disinfectant or amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant.
The concrete grammar of step (1) is as follows:
It is in 2～5% acetum or water that chitosan or carboxymethyl chitosan are dissolved in to mass fraction, under nitrogen protection, in 60 ℃～80 ℃ heated and stirred 0.5h, adding weight is the initiator of chitosan or carboxymethyl chitosan 1～3%, reaction 0.5～2h, add pyrrolidinone derivatives, add hydrophilic monomer simultaneously, at 60 ℃～80 ℃, react 4～6h, sucking filtration, filtrate decompression is distilled to 1/3 of original volume, add the organic solvent of 2～3 times of volumes, standing 8～10h, precipitation sucking filtration, solids washed with acetone 2 times, obtain amphipathic chitose graft copolymer or amphipathic carboxymethyl chitosan grafted graft copolymer.
The glutinous equal relative molecular mass of described chitosan is 100,000～300,000, described initiator is that the two Methylimidazole. quinoline propane hydrochloride salt of azo, azo-bis-isobutyl cyanide or the two isobutyls of azo are narrowed hydrochlorate, described pyrrolidinone derivatives is polyvinylpyrrolidone or N-vinylpyrrolidone, described hydrophilic monomer is one or more in vinylsulfonate, methyl methacrylate, lignocaine ethyl chloride hydrochlorate or trichlorine dihydroxypropyl trimethyl ammonium chloride, and described organic solvent is one or more in ethanol, ether, petroleum ether or acetone.
The mass ratio of chitosan and pyrrolidinone derivatives and hydrophilic monomer is 1: (1.5～3.5): (0.15～0.35); The mass ratio of carboxymethyl chitosan and pyrrolidinone derivatives and hydrophilic monomer is 1: (2～4): (0.2～0.4).
The concrete grammar of step (2) is as follows:
It is 1 that iodine is dissolved in its mass ratio: in the liquor kalii iodide of (0.8～1.2), the dilute hydrochloric acid that is 1%～2% with mass fraction regulates pH between 2～6, adding gross mass mark is 0.5～1.6% surfactant, with 300r/min stirring and emulsifying 0.5～1.0h, add the aqueous solution of the amphipathic carboxymethyl chitosan grafted graft copolymer that is equivalent to the amphipathic chitose graft copolymer of 4～6 times of iodine qualities or 3～5 times in above-mentioned solution, add total volume fraction is 40～70% organic solvent simultaneously, with 800～1000r/min stirring and emulsifying, 3～6h, obtain amphipathic chitose Ji Na meter iodine disinfectant or amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant.
Described surfactant is one or more in the polyvinyl chloride-based ether of dodecyl sodium sulfate, dodecylbenzene sodium sulfonate, hexadecyltrimethylammonium chloride or lauryl alcohol, and described organic solvent is one or more in ethanol, ether, petroleum ether, propanol, isopropyl alcohol or the tert-butyl alcohol.
In amphipathic chitose Ji Na meter iodine disinfectant, the mass fraction of iodine is 0.5～1.8%, and in amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant, the mass fraction of iodine is 0.5～2.0%.
The average-size of described amphipathic chitose Ji Na meter Surgidine or amphipathic carboxymethyl chitosan glycosyl nanometer Surgidine is 10～40nm.
The graft copolymer of chitosan or carboxymethyl chitosan and pyrrolidinone derivatives has amphipathic, pyrrolidinone derivatives has special affinity to iodine, can wrap up iodine molecule and form stable complex, can be dissolved in water and part organic solvent simultaneously, and the also good dissolubility of tool in mixed solvent, form the uniform amphipathic chitose Ji Na meter of form iodine particle, in prepared amphipathic chitose Ji Na meter iodine disinfectant, iodine has very high stability.
The biocidal property of amphipathic chitose Ji Na meter iodine disinfectant is to measure by antibacterials minimum inhibitory concentration (MIC) method, and the negative bacteria adopting is escherichia coli, and positive bacteria is staphylococcus aureus.Concrete determination step: antibacterials stock solution concentration is not less than 1000ug/mL or 10 times to high assay concentration, and the antimicrobial fluid preparing is stored in below-60 ℃.Culture medium is used Mueller-Hinton (MH) meat soup, adds 2% (w/v) sodium chloride, pH7.2～7.4 in meat soup.The antimicrobial fluid of variable concentrations after doubling dilution is added to respectively in 96 hole polystyrene plates of sterilizing, the 1st to the 11st hole adds medicinal liquid, every hole 10uL, and the 12nd not dosing of hole, as growth control, seals after lyophilization, and-20 ℃ save backup below.Now, the 1st hole to the 11 hole drug level be respectively 128,64,32,16,8,4,2,1,0.5,0.25,0.125ug/mL.Concentration is equivalent to 0.5 Maxwell than the bacteria suspension of turbid standard, and after the dilution in 1: 1000 of MH soup, Xiang Kongzhong adds 100uL, in the rearmounted 35 ℃ of normal air incubators of sealing, hatches 20～24h judged result.
In amphipathic chitose Ji Na meter iodine disinfectant, the mensuration of iodine content adopts iodimetric titration, concrete testing procedure: pipette 25.00mL iodine disinfectant in 250mL volumetric flask, be released into scale.In 250mL volumetric flask, pipette 25.00mL in conical flask, add 25mL water, with normal sodium thiosulfate solution, be titrated to faint yellowly, add 5mL mass fraction and be 5% starch solution, continue to be titrated to colourless, parallel titration 3 times.According to titration consumption sodium thiosulfate stereometer, calculate the mass fraction of iodine in iodine disinfectant.
Nanoparticle form and nanometer particle size testing procedure in amphipathic chitose Ji Na meter iodine disinfectant: on clean sheet glass, drip 1 iodine disinfectant, dry rear by scanning electron microscope (SEM) test particle form.By the particle size distribution of laser diffraction analyzer test iodine disinfectant.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) biocompatibility of chitosan and tissue repair function, become the bio-medical material that a class is good, the present invention is grafting pyrrolidinone derivatives and other hydrophilic monomers on natural macromolecular material chitosan chain, generation has amphipathic chitose base graft copolymer, this copolymer can make iodine be dispersed in chitosan chain molecule, change temperature or concentration and can control release iodine molecule, reduced the stimulation of iodine to skin or wound, made this series products have more safety.
(2) reasonable two subject matters of iodine as broad-spectrum disinfectant, the one, the dispersibility of iodine of having solved of method of preparing amphipathic chitose Ji Na meter iodine disinfectant of the present invention; The 2nd, the stability problem of iodine, due to skin effect and the small-size effect of amphipathic chitose Ji Na meter iodine, has strengthened antibacterial, antiviral activity and persistence, has improved the effective rate of utilization of iodine.
(3) amphipathic chitose Ji Na meter iodine disinfectant of the present invention is easy to use, and good stability is ideal antibacterial, antiinflammatory bio-medical product of a class, can be used for health system, family and social public place.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
A method of preparing amphipathic chitose Ji Na meter iodine disinfectant, comprises the following steps:
(1) chitosan and pyrrolidinone derivatives and hydrophilic monomer are carried out to graft copolymerization and prepare amphipathic chitose graft copolymer;
(2) amphipathic chitose graft copolymer and iodine are generated to amphipathic chitose Ji Na meter Surgidine, in certain solvent, prepare amphipathic chitose Ji Na meter iodine disinfectant.
The concrete grammar of step (1) is as follows:
It is in 2% acetum that the chitosan that is 100,000 by glutinous equal relative molecular mass is dissolved in mass fraction; under nitrogen protection; in 60 ℃ of heated and stirred 0.5h; adding weight is the two Methylimidazole. quinoline propane hydrochloride salt of azo of chitosan 1%; reaction 0.5h; add polyvinylpyrrolidone; add vinylsulfonate simultaneously, at 60 ℃, react 6h, sucking filtration; filtrate decompression is distilled to 1/3 of original volume; add the ethanol of 2 times of volumes, standing 8h, precipitation sucking filtration; solids washed with acetone 2 times, obtains amphipathic chitose graft copolymer.Wherein, the mass ratio of chitosan and polyvinylpyrrolidone and vinylsulfonate is 1: 1.5: 0.15.
The concrete steps of step (2) are as follows:
By in the iodine liquor kalii iodide that to be dissolved in its mass ratio be 1: 0.8, the dilute hydrochloric acid that is 1% with mass fraction regulates pH between 2～6, adding gross mass mark is 0.5% dodecyl sodium sulfate, with 300r/min stirring and emulsifying 0.5h, add the aqueous solution of the amphipathic chitose graft copolymer that is equivalent to 4 times of iodine qualities in above-mentioned solution, add total volume fraction is 40% ethanol/propanol mixed solvent (volume ratio is 1: 0.1～0.3) simultaneously, with 800r/min stirring and emulsifying 6h, obtain amphipathic chitose Ji Na meter iodine disinfectant.
Wherein, in amphipathic chitose Ji Na meter iodine disinfectant, the mass fraction of iodine is 0.5%, and the average-size of amphipathic chitose Ji Na meter Surgidine is 10nm.The minimum inhibitory concentration (MIC) of amphipathic chitose Ji Na meter iodine disinfectant is 0.3g/L.
The graft copolymer of chitosan and pyrrolidinone derivatives has amphipathic, pyrrolidinone derivatives has special affinity to iodine, can wrap up iodine molecule and form stable complex, can be dissolved in water and part organic solvent simultaneously, and the also good dissolubility of tool in mixed solvent, form the uniform amphipathic chitose Ji Na meter of form Surgidine, in prepared amphipathic chitose Ji Na meter iodine disinfectant, iodine has very high stability.
The biocidal property of amphipathic chitose Ji Na meter iodine disinfectant is to measure by antibacterials minimum inhibitory concentration (MIC) method, and the negative bacteria adopting is escherichia coli, and positive bacteria is staphylococcus aureus.Concrete determination step: antibacterials stock solution concentration is not less than 1000ug/mL or 10 times to high assay concentration, and the antimicrobial fluid preparing is stored in below-60 ℃.Culture medium is used Mueller-Hinton (MH) meat soup, adds 2% (w/v) sodium chloride, pH7.2～7.4 in meat soup.The antimicrobial fluid of variable concentrations after doubling dilution is added to respectively in 96 hole polystyrene plates of sterilizing, the 1st to the 11st hole adds medicinal liquid, every hole 10uL, and the 12nd not dosing of hole, as growth control, seals after lyophilization, and-20 ℃ save backup below.Now, the 1st hole to the 11 hole drug level be respectively 128,64,32,16,8,4,2,1,0.5,0.25,0.125ug/mL.Concentration is equivalent to 0.5 Maxwell than the bacteria suspension of turbid standard, and after the dilution in 1: 1000 of MH soup, Xiang Kongzhong adds 100uL, in the rearmounted 35 ℃ of normal air incubators of sealing, hatches 20～24h judged result.
In amphipathic chitose Ji Na meter iodine disinfectant, the mensuration of iodine content adopts iodimetric titration, concrete testing procedure: pipette 25.00mL iodine disinfectant in 250mL volumetric flask, be released into scale.In 250mL volumetric flask, pipette 25.00mL in conical flask, add 25mL water, with normal sodium thiosulfate solution, be titrated to faint yellowly, add 5mL mass fraction and be 5% starch solution, continue to be titrated to colourless, parallel titration 3 times.According to titration consumption sodium thiosulfate stereometer, calculate the mass fraction of iodine in iodine disinfectant.
Nanoparticle form and nanometer particle size testing procedure in amphipathic chitose Ji Na meter iodine disinfectant: on clean sheet glass, drip 1 iodine disinfectant, dry rear by scanning electron microscope (SEM) test particle form.By the particle size distribution of laser diffraction analyzer test iodine disinfectant.
Embodiment 2
A method of preparing amphipathic chitose Ji Na meter iodine disinfectant, comprises the following steps:
(1) it is 5% acetum that the chitosan that is 300,000 by glutinous equal relative molecular mass is dissolved in mass fraction; under nitrogen protection; in 80 ℃ of heated and stirred 0.5h; adding weight is the azo-bis-isobutyl cyanide of chitosan 3%; reaction 2h; add N-vinylpyrrolidone; add methyl methacrylate simultaneously, at 80 ℃, react 4h, sucking filtration; filtrate decompression is distilled to 1/3 of original volume; add the ether of 3 times of volumes, standing 10h, precipitation sucking filtration; solids washed with acetone 2 times, obtains amphipathic chitose graft copolymer.Wherein, the mass ratio of chitosan and N-vinylpyrrolidone and methyl methacrylate is 1: 3.5: 0.35.
(2) in the liquor kalii iodide that iodine to be dissolved in its mass ratio be 1: 1.2, the dilute hydrochloric acid that is 2% with mass fraction regulates pH between 2～5, adding gross mass mark is 1.6% dodecylbenzene sodium sulfonate, with 300r/min stirring and emulsifying 1.0h, add the aqueous solution of the amphipathic chitose graft copolymer that is equivalent to 6 times of iodine qualities in above-mentioned solution, add total volume fraction is propanol/ether mixed solvent (volume ratio is 1: 0.1～0.3) of 70% simultaneously, with 1000r/min stirring and emulsifying 3h, obtain amphipathic chitose Ji Na meter iodine disinfectant.
Wherein, in amphipathic chitose Ji Na meter iodine disinfectant, the mass fraction of iodine is 1.8%, and the average-size of amphipathic chitose Ji Na meter Surgidine is 40nm.The minimum inhibitory concentration (MIC) of amphipathic chitose Ji Na meter iodine disinfectant is 0.3g/L.
Embodiment 3
A method of preparing amphipathic chitose Ji Na meter iodine disinfectant, comprises the following steps:
(1) it is 3% acetum that the chitosan that is 200,000 by glutinous equal relative molecular mass is dissolved in mass fraction, under nitrogen protection, in 70 ℃ of heated and stirred 0.5h, adding weight is that the two isobutyls of azo of chitosan 2% are narrowed hydrochlorate, reaction 1h, add polyvinylpyrrolidone, add lignocaine ethyl chloride hydrochlorate simultaneously, at 70 ℃, react 5h, sucking filtration, filtrate decompression is distilled to 1/3 of original volume, add the petroleum ether of 2.5 times of volumes, standing 9h, precipitation sucking filtration, solids washed with acetone 2 times, obtain amphipathic chitose graft copolymer, wherein, the mass ratio of chitosan and polyvinylpyrrolidone and lignocaine ethyl chloride hydrochlorate is 1: 2: 0.2.
(2) in the liquor kalii iodide that iodine to be dissolved in its mass ratio be 1: 1, the dilute hydrochloric acid that is 1.5% with mass fraction regulates pH between 2～5, adding gross mass mark is 0.8% hexadecyltrimethylammonium chloride, with 300r/min stirring and emulsifying 0.8h, add the aqueous solution of the amphipathic chitose graft copolymer that is equivalent to 5 times of iodine qualities in above-mentioned solution, add total volume fraction is ethanol/tert-butyl alcohol mixed solvent (volume ratio is 1: 0.3～0.5) of 50% simultaneously, with 900r/min stirring and emulsifying 4h, obtain amphipathic chitose Ji Na meter iodine disinfectant.
Wherein, in amphipathic chitose Ji Na meter iodine disinfectant, the mass fraction of iodine is 1.5%.The average-size of amphipathic chitose Ji Na meter Surgidine is 20nm.The minimum inhibitory concentration (MIC) of amphipathic chitose Ji Na meter iodine disinfectant is 0.3g/L.
Embodiment 4
A method of preparing amphipathic chitose Ji Na meter iodine disinfectant, comprises the following steps:
(1) carboxymethyl chitosan and ketopyrrolidine and hydrophilic monomer are carried out to graft copolymerization and prepare amphipathic carboxymethyl chitosan grafted graft copolymer;
(2) amphipathic carboxymethyl chitosan grafted graft copolymer and iodine are generated to amphipathic carboxymethyl chitosan glycosyl nanometer Surgidine, in certain solvent, prepare amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant.
The concrete grammar of step (1) is as follows:
Carboxymethyl chitosan is dissolved in water, under nitrogen protection, in 60 ℃ of heated and stirred 0.5h, adding weight is that the two isobutyls of azo of carboxymethyl chitosan 1% are narrowed hydrochlorate, reaction 0.5h, add N-vinylpyrrolidone, add trichlorine dihydroxypropyl trimethyl ammonium chloride simultaneously, at 60 ℃, react 6h, sucking filtration, filtrate decompression is distilled to 1/3 of original volume, add the acetone of 2 times of volumes, standing 8h, precipitation sucking filtration, solids washed with acetone 2 times, obtain amphipathic carboxymethyl chitosan grafted graft copolymer, wherein, the mass ratio of carboxymethyl chitosan and N-vinylpyrrolidone and trichlorine dihydroxypropyl trimethyl ammonium chloride is 1: 2: 0.2.
The concrete grammar of step (2) is as follows:
By in the iodine liquor kalii iodide that to be dissolved in its mass ratio be 1: 0.8, the dilute hydrochloric acid that is 1% with mass fraction regulates pH between 4～6, adding gross mass mark is 1% the polyvinyl chloride-based ether of lauryl alcohol, with 300r/min stirring and emulsifying 0.5h, add the aqueous solution of the amphipathic carboxymethyl chitosan grafted graft copolymer that is equivalent to 3 times of iodine qualities in above-mentioned solution, add total volume fraction is 40% ethanol/propanol mixed solvent (volume ratio is 1: 0.2) simultaneously, with 800r/min stirring and emulsifying 6h, obtain amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant.Wherein in amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant, the mass fraction of iodine is 0.5%.The average-size of amphipathic carboxymethyl chitosan glycosyl nanometer Surgidine is 10nm.The minimum inhibitory concentration (MIC) of amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant is 0.3g/L.
Embodiment 5
A method of preparing amphipathic chitose Ji Na meter iodine disinfectant, comprises the following steps:
(1) carboxymethyl chitosan is dissolved in water, under nitrogen protection, in 80 ℃ of heated and stirred 0.5h, adding weight is the azo-bis-isobutyl cyanide of carboxymethyl chitosan 3%, reaction 2h, add polyvinylpyrrolidone, add lignocaine ethyl chloride hydrochlorate simultaneously, at 80 ℃, react 4h, sucking filtration, filtrate decompression is distilled to 1/3 of original volume, add the ethanol of 3 times of volumes, standing 10h, precipitation sucking filtration, solids washed with acetone 2 times, obtain amphipathic carboxymethyl chitosan grafted graft copolymer, wherein, the mass ratio of carboxymethyl chitosan and polyvinylpyrrolidone and lignocaine ethyl chloride hydrochlorate is 1: 4: 0.4.
(2) in the liquor kalii iodide that iodine to be dissolved in its mass ratio be 1: 1.2, the dilute hydrochloric acid that is 2% with mass fraction regulates pH between 4～6, adding gross mass mark is 0.5% dodecylbenzene sodium sulfonate, with 300r/min stirring and emulsifying 1.0h, add the aqueous solution of the amphipathic carboxymethyl chitosan grafted graft copolymer that is equivalent to 5 times of iodine qualities in above-mentioned solution, add total volume fraction is ethanol/isopropyl alcohol mixed solvent (volume ratio is 1: 0.3) of 70% simultaneously, with 1000r/min stirring and emulsifying 3h, obtain amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant.
Wherein, in amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant, the mass fraction of iodine is 2.0%.The average-size of amphipathic carboxymethyl chitosan glycosyl nanometer Surgidine is 40nm.The minimum inhibitory concentration (MIC) of amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant is 0.3g/L.
Embodiment 6
A method of preparing amphipathic chitose Ji Na meter iodine disinfectant, comprises the following steps:
(1) carboxymethyl chitosan is dissolved in water, under nitrogen protection, in 70 ℃ of heated and stirred 0.5h, adding weight is the two Methylimidazole. quinoline propane hydrochloride salt of azo of carboxymethyl chitosan 2%, reaction 1.5h, add N-vinylpyrrolidone, add methyl methacrylate simultaneously, at 70 ℃, react 5h, sucking filtration, filtrate decompression is distilled to 1/3 of original volume, add the ethanol of 2.5 times of volumes, standing 9h, precipitation sucking filtration, solids washed with acetone 2 times, obtain amphipathic carboxymethyl chitosan grafted graft copolymer, wherein, the mass ratio of carboxymethyl chitosan and N-vinylpyrrolidone and methyl methacrylate is 1: 3: 0.3.
(2) in the liquor kalii iodide that iodine to be dissolved in its mass ratio be 1: 1, the dilute hydrochloric acid that is 2% with mass fraction regulates pH between 3～6, adding gross mass mark is 0.8% hexadecyltrimethylammonium chloride, with 300r/min stirring and emulsifying 0.8h, add the aqueous solution of the amphipathic carboxymethyl chitosan grafted graft copolymer that is equivalent to 4 times of iodine qualities in above-mentioned solution, add total volume fraction is ethanol/tert-butyl alcohol mixed solvent (volume ratio is 1: 0.3) of 60% simultaneously, with 900r/min stirring and emulsifying 5h, obtain amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant.
Wherein, in amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant, the mass fraction of iodine is 1.5%.The average-size of amphipathic carboxymethyl chitosan glycosyl nanometer Surgidine is 30nm.The minimum inhibitory concentration (MIC) of amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant is 0.3g/L.
Claims (8)
1. a method of preparing amphipathic chitose Ji Na meter iodine disinfectant, is characterized in that, the method comprises the following steps:
(1) chitosan or carboxymethyl chitosan and pyrrolidinone derivatives and hydrophilic monomer are carried out to graft copolymerization and prepare amphipathic chitose graft copolymer or amphipathic carboxymethyl chitosan grafted graft copolymer;
(2) by amphipathic chitose graft copolymer or amphipathic carboxymethyl chitosan grafted graft copolymer and iodine generation amphipathic chitose Ji Na meter Surgidine or amphipathic carboxymethyl chitosan glycosyl nanometer Surgidine, in certain solvent, prepare amphipathic chitose Ji Na meter iodine disinfectant or amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant.
2. a kind of method of preparing amphipathic chitose Ji Na meter iodine disinfectant according to claim 1, is characterized in that, the concrete grammar of step (1) is as follows:
It is in 2～5% acetum or water that chitosan or carboxymethyl chitosan are dissolved in to mass fraction, under nitrogen protection, in 60 ℃～80 ℃ heated and stirred 0.5h, adding weight is the initiator of chitosan or carboxymethyl chitosan 1～3%, reaction 0.5～2h, add pyrrolidinone derivatives, add hydrophilic monomer simultaneously, at 60 ℃～80 ℃, react 4～6h, sucking filtration, filtrate decompression is distilled to 1/3 of original volume, add the organic solvent of 2～3 times of volumes, standing 8～10h, precipitation sucking filtration, solids washed with acetone 2 times, obtain amphipathic chitose graft copolymer or amphipathic carboxymethyl chitosan grafted graft copolymer.
3. a kind of method of preparing amphipathic chitose Ji Na meter iodine disinfectant according to claim 2, it is characterized in that, the glutinous equal relative molecular mass of described chitosan is 100,000～300,000, described initiator is the two Methylimidazole. quinoline propane hydrochloride salt of azo, the two isobutyls of azo-bis-isobutyl cyanide or azo are narrowed hydrochlorate, described pyrrolidinone derivatives is polyvinylpyrrolidone or N-vinylpyrrolidone, described hydrophilic monomer is vinylsulfonate, methyl methacrylate, one or more in lignocaine ethyl chloride hydrochlorate or trichlorine dihydroxypropyl trimethyl ammonium chloride, described organic solvent is ethanol, ether, petroleum ether or acetone.
4. a kind of method of preparing amphipathic chitose Ji Na meter iodine disinfectant according to claim 2, it is characterized in that, the mass ratio of chitosan and pyrrolidinone derivatives and hydrophilic monomer is 1: (1.5～3.5): (0.15～0.35); The mass ratio of carboxymethyl chitosan and pyrrolidinone derivatives and hydrophilic monomer is 1: (2～4): (0.2～0.4).
5. a kind of method of preparing amphipathic chitose Ji Na meter iodine disinfectant according to claim 1, is characterized in that, the concrete grammar of step (2) is as follows:
It is 1 that iodine is dissolved in its mass ratio: in the liquor kalii iodide of (0.8～1.2), the dilute hydrochloric acid that is 1%～2% with mass fraction regulates pH between 2～6, adding gross mass mark is 0.5～1.6% surfactant, with 300r/min stirring and emulsifying 0.5～1.0h, add the aqueous solution of the amphipathic carboxymethyl chitosan grafted graft copolymer that is equivalent to the amphipathic chitose graft copolymer of 4～6 times of iodine qualities or 3～5 times in above-mentioned solution, add total volume fraction is 40～70% organic solvent simultaneously, with 800～1000r/min stirring and emulsifying, 3～6h, obtain amphipathic chitose Ji Na meter iodine disinfectant or amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant.
6. a kind of method of preparing amphipathic chitose Ji Na meter iodine disinfectant according to claim 5, it is characterized in that, described surfactant is one or more in the polyvinyl chloride-based ether of dodecyl sodium sulfate, dodecylbenzene sodium sulfonate, hexadecyltrimethylammonium chloride or lauryl alcohol, and described organic solvent is one or more in ethanol, ether, petroleum ether, propanol, isopropyl alcohol or the tert-butyl alcohol.
7. a kind of method of preparing amphipathic chitose Ji Na meter iodine disinfectant according to claim 5, it is characterized in that, in amphipathic chitose Ji Na meter iodine disinfectant, the mass fraction of iodine is 0.5～1.8%, and in amphipathic carboxymethyl chitosan glycosyl nanometer iodine disinfectant, the mass fraction of iodine is 0.5～2.0%.
8. a kind of method of preparing amphipathic chitose Ji Na meter iodine disinfectant according to claim 1, it is characterized in that, the average-size of described amphipathic chitose Ji Na meter Surgidine or amphipathic carboxymethyl chitosan glycosyl nanometer Surgidine is 10～40nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210382921.XA CN103720711A (en) | 2012-10-10 | 2012-10-10 | Method for preparing amphiphilic chitosan group nano iodine disinfectant |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104147610A (en) * | 2014-06-26 | 2014-11-19 | 中国人民解放军第三○九医院 | Antibiotic constituent loaded polymer micro-nanoparticle and preparation method thereof |
| CN111657297A (en) * | 2020-07-10 | 2020-09-15 | 四川成邦药业有限公司 | Chelated povidone iodine solution and preparation method thereof |
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| KR20080060463A (en) * | 2006-12-27 | 2008-07-02 | (재)대구경북과학기술연구원 | A preparing method for x-ray opaque embolic material and the x-ray opaque embolic material by using the method |
| CN101524366A (en) * | 2009-03-21 | 2009-09-09 | 刘维峰 | Method for preparing compound biological activity sterilizing fluid |
| CN101654499A (en) * | 2009-09-02 | 2010-02-24 | 陈煜� | Composite of natural macromolecule or amphiphilic grafting copolymer of water-soluble derivant and nanometer iodine and preparation method thereof |
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| KR20080060463A (en) * | 2006-12-27 | 2008-07-02 | (재)대구경북과학기술연구원 | A preparing method for x-ray opaque embolic material and the x-ray opaque embolic material by using the method |
| CN101524366A (en) * | 2009-03-21 | 2009-09-09 | 刘维峰 | Method for preparing compound biological activity sterilizing fluid |
| CN101654499A (en) * | 2009-09-02 | 2010-02-24 | 陈煜� | Composite of natural macromolecule or amphiphilic grafting copolymer of water-soluble derivant and nanometer iodine and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104147610A (en) * | 2014-06-26 | 2014-11-19 | 中国人民解放军第三○九医院 | Antibiotic constituent loaded polymer micro-nanoparticle and preparation method thereof |
| CN111657297A (en) * | 2020-07-10 | 2020-09-15 | 四川成邦药业有限公司 | Chelated povidone iodine solution and preparation method thereof |
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