CN103720712A - Method for preparing quaternized chitosan nano iodine disinfectant - Google Patents
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Abstract
The invention relates to a method for preparing quaternized chitosan nano iodine disinfectant, and hydroxy or amino of chitosan or chitosan with low molecular weight are respectively connected with quaternary ammonium salt monomers, and a quaternized chitosan derivative or a quaternized chitosan derivative with low molecular weight is prepared, and the original biological activity of chitosan is still maintained in the derivative, and simultaneously solubilities of the product in water and other solvents are increased; the quaternized chitosan derivative or quaternized chitosan derivative with low molecular weight are reacted with iodine for generating chitosan group nano iodine compound or low molecular weight chitosan group nano iodine compound, and the chitosan group nano iodine disinfectant or low molecular weight chitosan group nano iodine disinfectant is prepared by dissolving in solvent. Compared with the prior art, the iodine has good dispersibility and stability in the invention, and because of surface effect and subsize effect of chitosan group nano iodine, bacteriostasis, antiviral activity and continuity of the product are improved, and effective utilization rate of iodine is increased.
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 n-trimethyl chitosan chloride nanometer 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 due to iodine be easy to distillation conventionally that iodine and various base material is composite to improve its stability, 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, unstable 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 almost insoluble 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.
Due to 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.
Summary of the invention
Object of the present invention is exactly to provide a kind of method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant in order to overcome the defect of above-mentioned prior art existence, 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 n-trimethyl chitosan chloride nanometer iodine disinfectant, comprises the following steps:
(1) on the hydroxyl of chitosan or low-molecular weight chitoglycan or amino, access respectively quaternary ammonium salt monomer, prepare n-trimethyl chitosan chloride derivant or low-molecular-weight n-trimethyl chitosan chloride derivant;
(2) n-trimethyl chitosan chloride derivant or low-molecular-weight n-trimethyl chitosan chloride derivant are reacted to generation n-trimethyl chitosan chloride nanometer Surgidine or low-molecular-weight n-trimethyl chitosan chloride nanometer Surgidine with iodine, and in solvent, prepare n-trimethyl chitosan chloride nanometer iodine disinfectant or low-molecular-weight n-trimethyl chitosan chloride nanometer iodine disinfectant.
The concrete grammar of step (1) is as follows:
Chitosan is added in organic solvent or by low-molecular weight chitoglycan and is dissolved in water, add the sodium hydroxide solution 2～3h that alkalizes at 40 ℃～60 ℃, slowly drip again the aqueous solution of quaternary ammonium salt monomer, at 40 ℃～60 ℃, react 3～6h, reacted rear filtration, the salt acid for adjusting pH to 7.0 that filtrate is 10% with mass fraction, the mixed solvent that adds 3 times of filtrate volumes, standing 8～12h, precipitation sucking filtration, obtains n-trimethyl chitosan chloride derivant or low-molecular-weight n-trimethyl chitosan chloride derivant.
Described organic solvent is the tert-butyl alcohol, isopropyl alcohol, cyclohexane or chloroform, and described quaternary ammonium salt monomer is trichlorine dihydroxypropyl trimethyl ammonium chloride or lignocaine ethyl chloride hydrochlorate.
The glutinous equal relative molecular mass of described chitosan is 100,000～300,000, described chitosan and the mol ratio of quaternary ammonium salt monomer are 1: (3～5), the glutinous equal relative molecular mass of described low-molecular weight chitoglycan is 1～90,000, and described low-molecular weight chitoglycan and the mol ratio of quaternary ammonium salt monomer are 1: (2～4).
When chitosan carries out quaterisation, the mass fraction of the sodium hydroxide solution adding is 20～40%, and required mixed solvent is that volume ratio is the ethanol of 2: 1 and the mixed liquor of ether; When low-molecular weight chitoglycan carries out quaterisation, the mass fraction of the sodium hydroxide solution adding is 15～25%, and required mixed solvent is that volume ratio is the acetone of 1: 2 and the mixed liquor of petroleum ether.
The preparation method of low-molecular weight chitoglycan is as follows:
It is 5% hydrogenperoxide steam generator that chitosan is added to mass fraction, stirring reaction 2～4h at 50 ℃～80 ℃, reacted rear filtration, filtrate rotary evaporation is to 1/3 of original volume, the ethanol that is 95% to the volume fraction that adds 3 times of volumes in filtrate, standing 8～12h, sucking filtration, vacuum drying obtain low-molecular weight chitoglycan.
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 acetic acid that is 5% with mass fraction or 1% dilute hydrochloric acid regulate pH between 3.5～7, adding gross mass mark is 0.5～1.5% surfactant, with 300r/min stirring and emulsifying 0.5～1.0h; Add the aqueous solution of n-trimethyl chitosan chloride derivant or low-molecular-weight n-trimethyl chitosan chloride derivant in above-mentioned solution, generate n-trimethyl chitosan chloride nanometer Surgidine or low-molecular-weight n-trimethyl chitosan chloride nanometer Surgidine, add total volume fraction is 30～50% organic solvent simultaneously, with 800～1000r/min rotating speed emulsifying, 3～6h, obtain n-trimethyl chitosan chloride nanometer iodine disinfectant or low-molecular-weight n-trimethyl chitosan chloride 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; Described organic solvent is one or more in ethanol, ether, petroleum ether, propanol, isopropyl alcohol or the tert-butyl alcohol.
The quality of the n-trimethyl chitosan chloride derivant adding is iodine quality 5～8 times, the quality of the low-molecular-weight n-trimethyl chitosan chloride derivant adding is iodine quality 4～6 times, in n-trimethyl chitosan chloride nanometer iodine disinfectant, the mass fraction of iodine is 0.5～1.5%, and in low-molecular-weight n-trimethyl chitosan chloride nanometer iodine disinfectant, the mass fraction of iodine is 0.5～1.5%.
The average-size of n-trimethyl chitosan chloride nanometer Surgidine or low-molecular-weight n-trimethyl chitosan chloride nanometer Surgidine is 10～40nm.
Ammonium salt in prepared n-trimethyl chitosan chloride derivant or low-molecular-weight n-trimethyl chitosan chloride derivant is positively charged, easily forms stable complex with iodine, can control effective release of iodine.Complex through quaternised modified chitosan and iodine formation all has certain dissolubility in water and various solvent simultaneously, form granularity nanoparticle comparatively uniformly, therefore can prepare chitosan-based nanometer iodine disinfectant by mixed solvent by a certain percentage.
The biocidal property of n-trimethyl chitosan chloride nanometer 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 n-trimethyl chitosan chloride nanometer iodine disinfectant, the mensuration of iodine content adopts iodimetric titration, concrete testing procedure: pipette 25.00mL n-trimethyl chitosan chloride nanometer 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, consume the mass fraction that sodium thiosulfate stereometer is calculated iodine in n-trimethyl chitosan chloride nanometer iodine disinfectant.
Nanoparticle form and nanometer particle size testing procedure in chitosan-based nanometer iodine disinfectant: on clean sheet glass, drip 1 n-trimethyl chitosan chloride nanometer iodine disinfectant, dry rear by scanning electron microscope (SEM) test particle form.Particle size distribution with laser diffraction analyzer test n-trimethyl chitosan chloride nanometer 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 accesses quaternary ammonium salt monomer on natural macromolecular material chitosan chain, generate n-trimethyl chitosan chloride derivant, this derivant 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, make 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 n-trimethyl chitosan chloride nanometer iodine disinfectant of the present invention; The 2nd, the stability problem of iodine, due to skin effect and the small-size effect of n-trimethyl chitosan chloride nanometer iodine, has strengthened antibacterial, antiviral activity and persistence, has improved the effective rate of utilization of iodine.
(3) n-trimethyl chitosan chloride nanometer 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 n-trimethyl chitosan chloride nanometer iodine disinfectant, comprises the following steps:
(1) will stick equal relative molecular mass is that 200,000 chitosans add in isopropanol solvent, adding mass fraction is that 30% sodium hydroxide solution is in 40 ℃ of alkalization 2h, slowly drip lignocaine ethyl chloride hydrochlorate solution, the mol ratio of chitosan and quaternary ammonium salt monomer is 1: 3, in 40 ℃ of stirring reaction 6h, reacted rear filtration, the hydrochloric acid that filtrate is 10% with mass fraction is adjusted pH to 7.0, the ethanol that the volume ratio that adds 3 times of filtrate volumes is 2: 1 and ether mixed liquor, standing 8h, precipitation sucking filtration, obtains n-trimethyl chitosan chloride derivant;
(2) in the liquor kalii iodide that iodine to be dissolved in its mass ratio be 1: 0.8, the hydrochloric acid solution that is 1% with mass fraction adjusts pH between 3.5～6.5, and adding gross mass mark is 0.5% dodecyl sodium sulfate, with 300r/min stirring and emulsifying 0.5h.Add and be equivalent to 5 times of n-trimethyl chitosan chloride aqueous solutions of iodine quality in above-mentioned iodine solution, add total volume fraction is ethanol/isopropyl alcohol mixed solvent (volume ratio is 1: 0.3) of 30% simultaneously, with 800r/min stirring and emulsifying 5h, obtain n-trimethyl chitosan chloride Ji Na meter iodine disinfectant.Wherein the mass fraction of iodine is 0.5%; Nanometer iodine particle size distribution is interval at 10～35nm; Minimum inhibitory concentration (MIC) is 0.3g/L.
Embodiment 2
A method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant, the method comprises the following steps:
(1) chitosan that is 100,000 by glutinous equal relative molecular mass adds in the tert-butyl alcohol, adding mass fraction is 20% the sodium hydroxide solution 3h that alkalizes at 60 ℃, slowly drip again trichlorine dihydroxypropyl trimethyl ammonium chloride solution, the mol ratio of chitosan and quaternary ammonium salt monomer is 1: 5, at 60 ℃, react 4h, reacted rear filtration, the salt acid for adjusting pH to 7.0 that filtrate is 10% with mass fraction, the ethanol that the volume ratio that adds 3 times of filtrate volumes is 2: 1 and the mixed liquor of ether, standing 12h, precipitation sucking filtration, obtains n-trimethyl chitosan chloride derivant;
(2) in the liquor kalii iodide that iodine to be dissolved in its mass ratio be 1: 1.2, the vinegar acid for adjusting pH that is 5% with mass fraction is between 3.5～6.5, and adding gross mass mark is 1.5% dodecylbenzene sodium sulfonate, with 300r/min stirring and emulsifying 1.0h; Add the aqueous solution of the n-trimethyl chitosan chloride derivant that is equivalent to 8 times of iodine qualities in above-mentioned solution, generating chitosan Ji Na meter Surgidine, add total volume fraction is propanol/ether mixed solvent (volume ratio is 1: 0.1～0.3) of 50% simultaneously, with 1000r/min rotating speed emulsifying 3h, obtain chitosan-based nanometer iodine disinfectant, wherein the mass fraction of iodine is 1.5%.The average-size of chitosan-based nanometer Surgidine is 20nm.Minimum inhibitory concentration (MIC) is 0.3g/L.
The biocidal property of n-trimethyl chitosan chloride nanometer 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 n-trimethyl chitosan chloride nanometer iodine disinfectant, the mensuration of iodine content adopts iodimetric titration: pipette 25.00mL n-trimethyl chitosan chloride nanometer 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, consume the mass fraction that sodium thiosulfate stereometer is calculated iodine in n-trimethyl chitosan chloride nanometer iodine disinfectant.
Nanoparticle form and nanometer particle size testing procedure in n-trimethyl chitosan chloride nanometer iodine disinfectant: on clean sheet glass, drip 1 n-trimethyl chitosan chloride nanometer iodine disinfectant, dry rear by scanning electron microscope (SEM) test particle form.Particle size distribution with laser diffraction analyzer test n-trimethyl chitosan chloride nanometer iodine disinfectant.
Embodiment 3
A method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant, the method comprises the following steps:
(1) chitosan that is 300,000 by glutinous equal relative molecular mass adds in chloroform, adding mass fraction is 30% the sodium hydroxide solution 2.5h that alkalizes at 50 ℃, slowly drip again lignocaine ethyl chloride hydrochlorate, wherein, the mol ratio of chitosan and lignocaine ethyl chloride hydrochlorate is 1: 4, at 50 ℃, react 5h, reacted rear filtration, the salt acid for adjusting pH to 7.0 that filtrate is 10% with mass fraction, the ethanol that the volume ratio that adds 3 times of filtrate volumes is 2: 1 and ether mixed liquor, standing 10h, precipitation sucking filtration, obtains n-trimethyl chitosan chloride derivant;
(2) in the liquor kalii iodide that iodine to be dissolved in its mass ratio be 1: 1, the vinegar acid for adjusting pH that is 5% with mass fraction is between 3.5～6.5, and adding gross mass mark is 1% hexadecyltrimethylammonium chloride, with 300r/min stirring and emulsifying 0.8h; Add the aqueous solution of the n-trimethyl chitosan chloride derivant that is equivalent to 7 times of iodine qualities in above-mentioned solution, generating chitosan Ji Na meter Surgidine, add simultaneously total volume fraction be 40% ethanol/tert-butyl alcohol mixed solvent (volume ratio is 1: 0.3～0.5), with 900r/min rotating speed emulsifying 4h, obtain chitosan-based nanometer iodine disinfectant, wherein the mass fraction of iodine is 1%.Minimum inhibitory concentration (MIC) is 0.3g/L.The particle size distribution of chitosan-based nanometer Surgidine is between 10～40nm.
Embodiment 4
A method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant, the method comprises the following steps:
(1) chitosan being added to mass fraction is 5% hydrogenperoxide steam generator, at 50 ℃ of stirring reaction 4h, reacted rear filtration, filtrate rotary evaporation is to 1/3 of original volume, the ethanol that is 95% to the volume fraction that adds 3 times of volumes in filtrate, standing 8h, sucking filtration, vacuum drying obtain low-molecular weight chitoglycan, the low-molecular weight chitoglycan that is 10,000 by glutinous equal relative molecular mass is dissolved in water, adding mass fraction is that 15% sodium hydroxide solution is in 40 ℃ of alkalization 1h, slowly drip lignocaine ethyl chloride hydrochlorate solution, wherein, the mol ratio of low-molecular weight chitoglycan and lignocaine ethyl chloride hydrochlorate is 1: 2, 40 ℃ of stirring reaction 5h, reacted rear filtration, the salt acid for adjusting pH to 7.0 that filtrate is 10% with mass fraction, the acetone that the volume ratio that adds 3 times of volumes is 1: 2 and the mixed liquor of petroleum ether, standing 8h, precipitation sucking filtration, obtain low-molecular-weight n-trimethyl chitosan chloride derivant,
(2) in the liquor kalii iodide that iodine to be dissolved in its mass ratio be 1: 0.8, the dilute hydrochloric acid that is 1% with mass fraction regulates pH between 5～7, and adding gross mass mark is 0.5% the polyvinyl chloride-based ether of lauryl alcohol, with 300r/min stirring and emulsifying 0.5h; Add and be equivalent to 4 times of low-molecular-weight n-trimethyl chitosan chloride derivant aqueous solutions of iodine quality in above-mentioned iodine liquid, generate low-molecular weight chitoglycan Ji Na meter Surgidine, add total volume fraction is 30% ethanol/propanol mixed solvent (volume ratio is 1: 0.1～0.3) simultaneously, with 800r/min stirring and emulsifying 6h, obtain low-molecular weight chitoglycan Ji Na meter iodine disinfectant, wherein the mass fraction of iodine is 0.5%.The average-size of chitosan-based nanometer Surgidine is 10nm.Minimum inhibitory concentration (MIC) is 0.3g/L.
Embodiment 5
A method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant, the method comprises the following steps:
(1) chitosan being added to mass fraction is 5% hydrogenperoxide steam generator, at 80 ℃ of stirring reaction 2h, reacted rear filtration, filtrate rotary evaporation is to 1/3 of original volume, the ethanol that is 95% to the volume fraction that adds 3 times of volumes in filtrate, standing 12h, sucking filtration, vacuum drying obtain low-molecular weight chitoglycan, the low-molecular weight chitoglycan that is 90,000 by glutinous equal relative molecular mass is dissolved in water, adding mass fraction is that 25% sodium hydroxide solution is in 60 ℃ of alkalization 2h, slowly drip trichlorine dihydroxypropyl trimethyl ammonium chloride solution, wherein the mol ratio of low-molecular weight chitoglycan and trichlorine dihydroxypropyl trimethyl ammonium chloride is 1: 4, 60 ℃ of stirring reaction 3h, reacted rear filtration, the salt acid for adjusting pH to 7.0 that filtrate is 10% with mass fraction, the acetone that the volume ratio that adds 3 times of volumes is 1: 2 and the mixed liquor of petroleum ether, standing 12h, precipitation sucking filtration, obtain low-molecular-weight n-trimethyl chitosan chloride derivant,
(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 1% with mass fraction regulates pH between 5～7, and adding gross mass mark is 1.0% dodecyl sodium sulfate, with 300r/min stirring and emulsifying 1.0h; Add and be equivalent to 6 times of low-molecular-weight n-trimethyl chitosan chloride derivant aqueous solutions of iodine quality in above-mentioned iodine liquid, generate low-molecular weight chitoglycan Ji Na meter Surgidine, add total volume fraction is propanol/petroleum ether mixed solvent (volume ratio is 1: 0.1～0.3) of 50% simultaneously, with 1000r/min stirring and emulsifying 3h, obtain low-molecular weight chitoglycan Ji Na meter iodine disinfectant, wherein the mass fraction of iodine is 1.5%.Minimum inhibitory concentration (MIC) is 0.3g/L.The average-size of chitosan-based nanometer Surgidine is 40nm.
Embodiment 6
A method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant, the method comprises the following steps:
(1) chitosan being added to mass fraction is 5% hydrogenperoxide steam generator, at 60 ℃ of stirring reaction 3h, reacted rear filtration, filtrate rotary evaporation is to 1/3 of original volume, the ethanol that is 95% to the volume fraction that adds 3 times of volumes in filtrate, standing 10h, sucking filtration, vacuum drying obtain the low-molecular weight chitoglycan that glutinous equal relative molecular mass is 50,000; Low-molecular weight chitoglycan is dissolved in water, adding mass fraction is that 20% sodium hydroxide solution is in 50 ℃ of alkalization 2.5h, slowly drip trichlorine dihydroxypropyl trimethyl ammonium chloride solution, wherein the mol ratio of low-molecular weight chitoglycan and trichlorine dihydroxypropyl trimethyl ammonium chloride is 1: 3,50 ℃ of stirring reaction 4h, reacted rear filtration, the salt acid for adjusting pH to 7.0 that filtrate is 10% with mass fraction, the acetone that the volume ratio that adds 3 times of volumes is 1: 2 and the mixed liquor of petroleum ether, standing 10h, precipitation sucking filtration, obtains low-molecular-weight n-trimethyl chitosan chloride derivant;
(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% with mass fraction regulates pH between 5～7, and adding gross mass mark is 0.8% hexadecyltrimethylammonium chloride, with 300r/min stirring and emulsifying 0.8h; Add and be equivalent to 5 times of low-molecular-weight n-trimethyl chitosan chloride derivant aqueous solutions of iodine quality in above-mentioned iodine liquid, generate low-molecular weight chitoglycan Ji Na meter Surgidine, add total volume fraction is ethanol/tert-butyl alcohol mixed solvent (volume ratio is 1: 0.3～0.5) of 40% simultaneously, with 900r/min stirring and emulsifying 4h, obtain low-molecular weight chitoglycan Ji Na meter iodine disinfectant, wherein the mass fraction of iodine is 1.2%.The average-size of chitosan-based nanometer Surgidine is 30nm.Minimum inhibitory concentration is 0.35g/L.
Claims (10)
1. a method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant, is characterized in that, the method comprises the following steps:
(1) on the hydroxyl of chitosan or low-molecular weight chitoglycan or amino, access respectively quaternary ammonium salt monomer, prepare n-trimethyl chitosan chloride derivant or low-molecular-weight n-trimethyl chitosan chloride derivant;
(2) n-trimethyl chitosan chloride derivant or low-molecular-weight n-trimethyl chitosan chloride derivant are reacted to generation n-trimethyl chitosan chloride nanometer Surgidine or low-molecular-weight n-trimethyl chitosan chloride nanometer Surgidine with iodine, and in solvent, prepare n-trimethyl chitosan chloride nanometer iodine disinfectant or low-molecular-weight n-trimethyl chitosan chloride nanometer iodine disinfectant.
2. a kind of method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant according to claim 1, is characterized in that, the concrete grammar of step (1) is as follows:
Chitosan is added in organic solvent or by low-molecular weight chitoglycan and is dissolved in water, add the sodium hydroxide solution 2～3h that alkalizes at 40 ℃～60 ℃, slowly drip again the aqueous solution of quaternary ammonium salt monomer, at 40 ℃～60 ℃, react 3～6h, reacted rear filtration, the salt acid for adjusting pH to 7.0 that filtrate is 10% with mass fraction, the mixed solvent that adds 3 times of filtrate volumes, standing 8～12h, precipitation sucking filtration, obtains n-trimethyl chitosan chloride derivant or low-molecular-weight n-trimethyl chitosan chloride derivant.
3. a kind of method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant according to claim 2, it is characterized in that, described organic solvent is the tert-butyl alcohol, isopropyl alcohol, cyclohexane or chloroform, and described quaternary ammonium salt monomer is trichlorine dihydroxypropyl trimethyl ammonium chloride or lignocaine ethyl chloride hydrochlorate.
4. a kind of method of preparing n-trimethyl chitosan chloride nanometer 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 chitosan and the mol ratio of quaternary ammonium salt monomer are 1: (3～5), the glutinous equal relative molecular mass of described low-molecular weight chitoglycan is 1～90,000, and described low-molecular weight chitoglycan and the mol ratio of quaternary ammonium salt monomer are 1: (2～4).
5. a kind of method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant according to claim 2, it is characterized in that, when chitosan carries out quaterisation, the mass fraction of the sodium hydroxide solution adding is 20～40%, and required mixed solvent is that volume ratio is the ethanol of 2: 1 and the mixed liquor of ether; When low-molecular weight chitoglycan carries out quaterisation, the mass fraction of the sodium hydroxide solution adding is 15～25%, and required mixed solvent is that volume ratio is the acetone of 1: 2 and the mixed liquor of petroleum ether.
6. according to the arbitrary a kind of described method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant of claim 1～5, it is characterized in that, the preparation method of low-molecular weight chitoglycan is as follows:
It is in 5% hydrogenperoxide steam generator that chitosan is added to mass fraction, stirring reaction 2～4h at 50 ℃～80 ℃, reacted rear filtration, filtrate rotary evaporation is to 1/3 of original volume, the ethanol that is 95% to the volume fraction that adds 3 times of volumes in filtrate, standing 8～12h, sucking filtration, vacuum drying obtain low-molecular weight chitoglycan.
7. a kind of method of preparing n-trimethyl chitosan chloride nanometer 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 acetic acid that is 5% with mass fraction or 1% dilute hydrochloric acid regulate pH between 3.5～7, adding gross mass mark is 0.5～1.5% surfactant, with 300r/min stirring and emulsifying 0.5～1.0h; Add the aqueous solution of n-trimethyl chitosan chloride derivant or low-molecular-weight n-trimethyl chitosan chloride derivant in above-mentioned solution, generate n-trimethyl chitosan chloride nanometer Surgidine or low-molecular-weight n-trimethyl chitosan chloride nanometer Surgidine, add total volume fraction is 30～50% organic solvent simultaneously, with 800～1000r/min rotating speed emulsifying, 3～6h, obtain n-trimethyl chitosan chloride nanometer iodine disinfectant or low-molecular-weight n-trimethyl chitosan chloride nanometer iodine disinfectant.
8. a kind of method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant according to claim 7, 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; Described organic solvent is one or more in ethanol, ether, petroleum ether, propanol, isopropyl alcohol or the tert-butyl alcohol.
9. a kind of method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant according to claim 7, it is characterized in that, the quality of the n-trimethyl chitosan chloride derivant adding is iodine quality 5～8 times, the quality of the low-molecular-weight n-trimethyl chitosan chloride derivant adding is iodine quality 4～6 times, in n-trimethyl chitosan chloride nanometer iodine disinfectant, the mass fraction of iodine is 0.5～1.5%, and in low-molecular-weight n-trimethyl chitosan chloride nanometer iodine disinfectant, the mass fraction of iodine is 0.5～1.5%.
10. a kind of method of preparing n-trimethyl chitosan chloride nanometer iodine disinfectant according to claim 1, is characterized in that, the average-size of n-trimethyl chitosan chloride nanometer Surgidine or low-molecular-weight n-trimethyl chitosan chloride nanometer Surgidine is 10～40nm.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103975949A (en) * | 2014-05-23 | 2014-08-13 | 青岛科技大学 | Chitosan iodine solution and preparation method thereof |
| CN104434994A (en) * | 2014-11-28 | 2015-03-25 | 成都顺发消洗科技有限公司 | Mucocutaneous disinfectant |
| CN104434995A (en) * | 2014-11-28 | 2015-03-25 | 成都顺发消洗科技有限公司 | Preparation method of mucocutaneous disinfectant |
| CN108715621A (en) * | 2018-07-24 | 2018-10-30 | 上海融澈水性材料有限公司 | A kind of amine oxide type n-trimethyl chitosan chloride iodine and the preparation method and application thereof |
| CN111803705A (en) * | 2020-07-24 | 2020-10-23 | 上海济国医疗科技有限公司 | Hydroxyapatite composite material with antibacterial function and preparation method and application thereof |
| WO2022119322A1 (en) * | 2020-12-04 | 2022-06-09 | 단국대학교 천안캠퍼스 산학협력단 | Hemostatic composition comprising novel compound |
| CN115627207A (en) * | 2022-09-08 | 2023-01-20 | 荆州阳豪大酒店管理有限公司 | Delicious black vinegar |
| WO2023128597A1 (en) * | 2021-12-28 | 2023-07-06 | 단국대학교 천안캠퍼스 산학협력단 | Physiological saline including novel compound |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103975949A (en) * | 2014-05-23 | 2014-08-13 | 青岛科技大学 | Chitosan iodine solution and preparation method thereof |
| CN104434994A (en) * | 2014-11-28 | 2015-03-25 | 成都顺发消洗科技有限公司 | Mucocutaneous disinfectant |
| CN104434995A (en) * | 2014-11-28 | 2015-03-25 | 成都顺发消洗科技有限公司 | Preparation method of mucocutaneous disinfectant |
| CN108715621A (en) * | 2018-07-24 | 2018-10-30 | 上海融澈水性材料有限公司 | A kind of amine oxide type n-trimethyl chitosan chloride iodine and the preparation method and application thereof |
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| WO2022119322A1 (en) * | 2020-12-04 | 2022-06-09 | 단국대학교 천안캠퍼스 산학협력단 | Hemostatic composition comprising novel compound |
| WO2023128597A1 (en) * | 2021-12-28 | 2023-07-06 | 단국대학교 천안캠퍼스 산학협력단 | Physiological saline including novel compound |
| CN115627207A (en) * | 2022-09-08 | 2023-01-20 | 荆州阳豪大酒店管理有限公司 | Delicious black vinegar |
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Application publication date: 20140416 |