CN102604141B - Method for preparing antibacterial film of quaternarized chitosan iodine complex - Google Patents
Method for preparing antibacterial film of quaternarized chitosan iodine complex Download PDFInfo
- Publication number
- CN102604141B CN102604141B CN 201210050268 CN201210050268A CN102604141B CN 102604141 B CN102604141 B CN 102604141B CN 201210050268 CN201210050268 CN 201210050268 CN 201210050268 A CN201210050268 A CN 201210050268A CN 102604141 B CN102604141 B CN 102604141B
- Authority
- CN
- China
- Prior art keywords
- iodine
- chitosan
- trimethyl
- film
- quaternary ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Materials For Medical Uses (AREA)
- Cosmetics (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a method for preparing an antibacterial film of a quaternarized chitosan iodine complex. The method comprises the following steps: inserting quaternary ammonium salt on the hydroxyl group or amino group of a chitosan structure unit to prepare a quaternarized chitosan derivative; soaking a blend film of the quaternarized chitosan derivative and gelatin or poval into a simple substance iodine solution for 4-6 hours to obtain the antibacterial film of the quaternarized chitosan/gelatin or poval iodine complex, or directly preparing a quaternary ammonium salt chitosan iodine complex from the quaternarized chitosan derivative and simple substance iodine, and then mixing the quaternary ammonium salt chitosan iodine complex with gelatin or poval to prepare the blend antibacterial film containing iodine. By using the method, the water solubility and the biological activity of chitosan can be improved; simple substance iodine is stabilized and complexed by utilizing the affinity of a quaternary ammonium salt group and an iodine molecule; according to the different positions of a human body, the prepared antibacterial film can be compounded with other materials; a chitosan base has hemostasis, antiphlogosis and tissue repair functions on human body wound, can reduce the stimulation of iodine on the wound and controls the release of iodine, and the double effects of the chitosan base and iodine provide an ideal curing environment for a wound surface.
Description
Technical field
The present invention relates to the quaternised modified of natural macromolecular material chitosan, prepare antibiotic, the anti-inflammatory medical films of corresponding chelated iodine.Belong to the biological medicine Material Field, especially relate to a kind of method for preparing the antibacterial film of n-trimethyl chitosan chloride chelated iodine.
Background technology
Chitosan has the functions such as antisepsis and anti-inflammation, hemostasis, analgesia and the growth of promotion body tissue, and the film made from the chitosan base polymer can be used as good wound coating material.Simultaneously it can also make artificial skin, is used for burning, making skin graft, cut the protecting wound surface of skin zone position, and effect is better than the nothing that Mierocrystalline cellulose makes and hinders cloth.China's medical dressing production technology is lower at present, and added value of product is not high, and especially high-tech medical dressing product is badly in need of exploitation.
The present invention utilizes chitosan to have good biocompatibility, hemostatic and promote wound healing and iodine that most bacteriums and virus are all had the extremely strong performance of killing.This class medical antibacterial film of developing had both embodied chitosan-based good biological activity, can fully represent again the broad-spectrum antimicrobial effect of iodine.This double effects provides desirable healing environment for the surface of a wound.
Iodine has as sterilization and antiviral material that high-efficiency low-toxicity, action effective are long, bacterium does not have the advantages such as resistance to it.Iodine clinically common formulation has solution and ointment.But solution is unstable, and the content, the action effective weak point that easily decompose, distil and make available iodine because of iodine in storage and use procedure do not reach quality standard.There is dose control difficulty in ointment, and is larger to surface of a wound pungency.Therefore on biomedicine how more good utilisation iodine have two subject matters: the one, the stability problem of iodine in iodine and the various base material compound; The 2nd, how to control the amount that discharges iodine.
Though there is the lot of documents chitosan that germ resistance is arranged, actual this anti-microbial effect is not obvious.Iodine molecule is non-polar molecule, with chitosan-based complexing mainly be Intermolecular Forces.Research finds no matter (iodine is with I in non-polar solvent
2The molecular form existence) and in the water (iodine is dissolved in potassiumiodide and generates I
3 -Ion) iodine and chitosan all can not generate stable complex compound, illustrate that Intermolecular Forces is less between them.
Summary of the invention
Purpose of the present invention is exactly the preparation method that a kind of medical antibacterial film of n-trimethyl chitosan chloride chelated iodine is provided for the defective that overcomes above-mentioned prior art existence; prepared product has certain physical strength, flexibility, good water absorption; while iodine energy Uniform Dispersion, good stability; the chitosan-based iodine controlled release that can make slowly discharges, and plays the hormesis that the protection surface of a wound reduces iodine.The iodine that discharges simultaneously is on the nano-scale, improves its antibacterial and antiviral efficacy.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of method for preparing the antibacterial film of n-trimethyl chitosan chloride chelated iodine may further comprise the steps:
(1) on the hydroxyl of chitosan structure unit or amino, accesses respectively quaternary ammonium salt, prepare the n-trimethyl chitosan chloride derivative;
(2) n-trimethyl chitosan chloride derivative, gelatin or polyvinyl alcohol blending film are soaked in the iodine solution, soak time is 4～6h, obtains the antibacterial film of the absorption of n-trimethyl chitosan chloride/gelatin or polyvinyl alcohol or chelated iodine.
Step (1) adopts following steps: chitosan is dissolved in acetum, add the dehydrated alcohol dilution that accounts for cumulative volume 50%, stir the lower aldehyde that adds, temperature of reaction is controlled at 35～45 ℃, reaction 3～4h, obtain even milky white liquid, drip NaOH solution in above-mentioned emulsion, stir until produce white flocks, filter and obtain white solid in apparatus,Soxhlet's dehydrated alcohol extraction 24h, 30～60 ℃ of vacuum-dryings get chitosan aldehyde schiff bases, with chitosan aldehyde schiff bases swelling 8～12h in organic solvent, add quaternary ammonium salt monomer, temperature of reaction is 40～60 ℃, reaction 3～6h, after hydrochloric acid/ethanolic soln suspension is processed, regulate pH=7.0, the solid ethanol that leaches with NaOH solution, washing with acetone prepares C6 hydroxyl n-trimethyl chitosan chloride derivative after 40～60 ℃ of vacuum-dryings.
Sticking all relative molecular masses of described chitosan are 30,000～300,000; Described aldehyde is glutaraldehyde or phenyl aldehyde, and the mol ratio of chitosan and aldehyde is 1: (2～4); Described organic solvent is hexanaphthene, the trimethyl carbinol, pyridine or chloroform; Described quaternary ammonium salt monomer is diethylin monochloroethane hydrochloride or trichlorine dihydroxypropyl trimethyl ammonium chloride, and the mol ratio of chitosan aldehyde schiff bases and quaternary ammonium salt monomer is 1: (2～6).
Step (1) can also adopt following steps: chitosan is added swelling 2～4h in the organic solvent, heat up 50～70 ℃ after adding NaOH solution alkalization 2～4h, add quaternary ammonium salt monomer, transfer pH=7.0 with hydrochloric acid behind reaction 3～6h, filter, solid extracts 10～12h with dehydrated alcohol in apparatus,Soxhlet's, prepares chitosan hydroxyl and the amino upper respectively n-trimethyl chitosan chloride derivative of grafting after 40～60 ℃ of vacuum-dryings.
Sticking all relative molecular masses of described chitosan are 30,000～300,000; Described organic solvent is propyl alcohol, Virahol or pyridine; Described quaternary ammonium salt monomer is diethylin monochloroethane hydrochloride or trichlorine dihydroxypropyl trimethyl ammonium chloride, and the mol ratio of chitosan and quaternary ammonium salt monomer is 1: (2～6).
Prepared n-trimethyl chitosan chloride derivative very easily forms quaternary ammonium salt under solutions of weak acidity, increase the biological activity of himself, and easy and iodine forms stable complex compound simultaneously, can further be processed as the core material of antibacterial film.Simultaneously since on chitosan the grafting ammonium salt, strengthened further that it is water-soluble, the easy water-sol of preparation with certain stickiness can prepare the network system of polymer gel chelated iodine with other soluble high-molecular material blend.
Step (2) adopts following steps:
In a, the KI solution that iodine is dissolved in, transfer pH between 3.5～5.5 with rare acetic acid or dilute hydrochloric acid, the adding volume fraction is 50% organic solvent, add tensio-active agent, emulsify at a high speed makes tensio-active agent and iodine Uniform Dispersion, adds the n-trimethyl chitosan chloride derivative in above-mentioned iodine liquid again, with 800～1000r/min rotating speed emulsification, 3～6h, make the mixture of n-trimethyl chitosan chloride chelated iodine, wherein the massfraction of iodine is 4～6%;
B, with mixture and polyvinyl alcohol or the gelatin cross-blend of above-mentioned n-trimethyl chitosan chloride chelated iodine, fully stir 2～4h in 30 ℃～60 ℃ temperature ranges, blended liquid is film forming in mould, can or naturally dry the antibacterial film for preparing the n-trimethyl chitosan chloride chelated iodine by lyophilize, infrared drying, wherein the massfraction of iodine is between 5%～15%.
Described organic solvent is ethanol, Virahol or the trimethyl carbinol; Described tensio-active agent is sodium laurylsulfonate, palmityl trimethyl ammonium chloride or lauryl alcohol polyoxyethylene ether, the mass ratio of tensio-active agent and iodine is 1: 0.1～1: 0.3, and the mass ratio of described n-trimethyl chitosan chloride derivative and iodine is 3.5: 1～5.5: 1; The volume ratio of the mixture of described n-trimethyl chitosan chloride chelated iodine and polyvinyl alcohol or gelatin is 0.2: 1～0.5: 1.
Step (2) can also adopt following steps:
A, the Quaternary Ammonium Salt of Chitosan derivative is dissolved in massfraction is in 2%～5% the acetic acid or hydrochloric acid soln, add polyvinyl alcohol or gelatin, fully stir 2～4h with 400～800r/min, inject the mould film forming, with distilled water flushing to neutral, infrared drying or naturally dry and obtain blend film then;
B, iodine is dissolved in obtains iodine liquid in the organic solvent, the blend film of above-mentioned preparation is immersed in 4～6h in the iodine liquid, can directly seal up for safekeeping after the taking-up, blend film is by Quaternary Ammonium Salt of Chitosan absorption or chelated iodine, prepare the antibacterial film of n-trimethyl chitosan chloride chelated iodine, the massfraction of iodine is between 5%～15% in the antibacterial film.
Described organic solvent is two or more mixed solvent in ethanol, propyl alcohol, Virahol or the sherwood oil; The mass ratio of Quaternary Ammonium Salt of Chitosan derivative and polyvinyl alcohol or gelatin is 1: 1～1: 4, and the massfraction of iodine liquid is 8%～10%.
It is water-soluble preferably that the preparation method of n-trimethyl chitosan chloride film is that the Quaternary Ammonium Salt of Chitosan derivative by modification has, and its biological activity has very large change than chitosan.Polyvinyl alcohol and gelatin all are the most frequently used biological medical polymer materials simultaneously, can be derivative blended with n-trimethyl chitosan chloride, help film forming, and easily machine-shaping.Its technical characterstic is that the film that availability is different is to satisfy the demand of various products by the massfraction that changes blend and control blending temperature.Because the Quaternary Ammonium Salt of Chitosan in the blend film is positively charged, has increased electrostatic repulsion between molecular chain, so that cross-linked network increases, the rate of liquid aspiration of film increases, and water regain also increases.Quaternary Ammonium Salt of Chitosan has weakened the hydrogen bond action between the molecule in the blend film simultaneously, and the film compactness of formation descends, so air transmission coefficient increases, water vapour permeability increases.
The antibacterial film technology of n-trimethyl chitosan chloride chelated iodine is to adsorb the preparation of (complexing) iodine by the blend film that the direct blend of the mixture of n-trimethyl chitosan chloride chelated iodine preparation contains the iodine film or prepares first the n-trimethyl chitosan chloride derivative to contain the iodine film again, its common ground is because the existence of quaternary ammonium salt is arranged, the iodine good dispersity, reach desirable stability, the massfraction of iodine all can be determined by the change of Quaternary Ammonium Salt of Chitosan derivative quality mark in the film.Owing to the adding of iodine, changed physicals and the mechanical property of film simultaneously, made the more convenient moulding of film-forming process.Observe by Optical microscope and SEM, this class contains that iodine antibacterial film surface is relatively coarse, and particle size dispersion is even, and iodine is arranged on the antibacterial film with the nanoparticle form.So that the antibacterial film of n-trimethyl chitosan chloride chelated iodine has stronger bacteriostatic action.
The mensuration of iodine content adopts iodimetry,iodometry in the antibacterial film, quantitatively takes by weighing the iodine film that shearing is good about 0.5000g and places the 250mL iodine flask, adds the 100mL Na that has demarcated
2S
2O
3Solution, magnetic agitation 2～4h, filter flask filter to get supernatant liquid, inject base buret, pipette 25mL standard substance KIO
3Solution adds 5mLKI and 5mL 0.5mol/L sulphuric acid soln in the 250mL iodine flask, take starch as indicator, be titrated to colourless.Consume Na according to titration
2S
2O
3Liquor capacity calculates the massfraction of iodine in the antibacterial film.
The biocidal property of the antibacterial film of n-trimethyl chitosan chloride chelated iodine is that the negative bacteria of taking is intestinal bacteria by inhibition zone method (MIC) test, and positive bacteria is streptococcus aureus.Concrete testing method shakes up for the bacterium liquid with intestinal bacteria or streptococcus aureus is distributed in the uncured substratum, and bacteria concentration is about 108Cells/mL (E1).Getting wherein, 30mL installs in the culture dish that diameter is 12cm the normal temperature cooling curing while hot.E1 dilution 10 times (E2) is made the required flat board of E2.Iodine film to be measured is made the disk that diameter is 10mm, ultraviolet-sterilization 30min.Respectively the iodine film is attached at dull and stereotyped different positions.Flat board is put into 37 ℃ of thermostat containers and is cultivated 24h, observes the growing state of bacterium, measures antibacterial circle diameter.
The antibacterial film water vapor transmission rate (WVTR) of n-trimethyl chitosan chloride chelated iodine, water-intake rate and mechanical mechanics property test are as follows: with loading onto a certain amount of distilled water in the wide-necked bottle, be encapsulated in bottleneck with the iodine film, the control bottle open-ended calculates air penetrability according to two bottles of fluid losses of 24h; The iodine film is put into the moisture eliminator of Calcium Chloride Powder Anhydrous, and interval 3h weighs until constant weight.Film sample with dry constant weight is immersed in the distilled water again, behind the 1min material is taken out, and weighs after with filter paper surface water being absorbed, and calculates water-intake rate; According to tensile strength and the elongation at break of GB1040-70 standard method in tension testing machine test antibacterial film.
Compared with prior art, the present invention is grafting quaternary ammonium salt on chitosan structure unit hydroxyl and amino, and the synthesis of quaternary ammonium chitosan derivatives is in weakly acidic solution, this derivative quaternary ammonium salt is positively charged, and iodine large to molecular volume, volatility has very strong sucking action.Because quaternary ammonium salt is dispersed on the polymer chitosan structural unit, can disperse iodine to the absorption (complexing) of iodine, make iodine can not form reunion, reduce the side effect that the surface of a wound is stimulated.Therefore iodine is loaded on the n-trimethyl chitosan chloride derivative, add certain proportion natural polymer dressing blend and prepare film forming, efficiently solve dispersiveness and the stable difficult problem of iodine.This class contains the iodine antibacterial film slow releasing function is played in the release of iodine, and the iodine that discharges is on the nano-scale, effect with good penetration cell wall, and then attack cells inwall target position make to contain the iodine antibacterial film and have the special functions such as antibacterial, antiviral and tissue reparation.
Because chitosan does not dissolve in water, and n-trimethyl chitosan chloride solubleness in water increases, the polymers such as used polyvinyl alcohol and gelatin all contain a large amount of free hydroxyl groups and carboxyl in film process, can form in the molecule and intermolecular hydrogen bonding, have stronger physical and chemical stability.These macromolecular compounds are colourless, nontoxic, good film-forming property, nonirritant, are the biological medical polymer materials of excellent property.The mixture energy of n-trimethyl chitosan chloride chelated iodine is good and these dressing are compound, it is prepared that to contain iodine antibacterial film handling property good, mechanics and ventilation property all are greatly improved, and store and easy to use, are the medical antibacterial film products of desirable antibiotic, the anti-inflammatory of a class and promotion wound healing.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
Get 1 part of chitosan (viscosity-average molecular weight 30,000～300,000 intervals) and be dissolved in the acetic acid or hydrochloric acid soln of massfraction 3%～5%, the adding volume ratio is 30%～50% dehydrated alcohol dilution.The glutaraldehyde or the phenyl aldehyde stirring reaction 3～6h that add 3～6 times of chitosan masses under the room temperature obtain the homogeneous milky white liquid.Add the sodium hydroxide solution of 5mol/L in above-mentioned emulsion, stir until produce white flocks, leave standstill and filter to get white solid, dehydrated alcohol extraction 24h in apparatus,Soxhlet's, 40～60 ℃ of vacuum-dryings get chitosan aldehyde schiff bases.With chitosan aldehyde schiff bases swelling 8～12h in the pyridine/chloroform mixed solvent, the quaternary ammonium salt monomer (diethylin monochloroethane hydrochloride, trichlorine dihydroxypropyl trimethyl ammonium chloride) that adds 1.5～3.0 times of chitosan aldehyde schiff bases quality, stirring reaction 12～24h filters to such an extent that solid product suspends in hydrochloric acid/ethanolic soln and processes 8～12h.Regulate pH to neutral with 1.0mol/L sodium hydroxide, suction filtration gets throw out dehydrated alcohol and acetone repetitive scrubbing, and 40～60 ℃ of vacuum-dryings get C6 position grafting n-trimethyl chitosan chloride derivative product (AS-CTS).
Embodiment 2
Get 1 part of chitosan (viscosity-average molecular weight 30,000～300,000 intervals) and put into ethanol/isopropyl alcohol mixed solvent swelling 2～4h, add 5.0mol/L sodium hydroxide solution alkalization 2～4h in chitosan mass than 1: 0.1 to 1: 0.3 ratio of sodium hydroxide quality.System is warmed up to the quaternary ammonium salt monomer (diethylin monochloroethane hydrochloride, trichlorine dihydroxypropyl trimethyl ammonium chloride) that adds 3～6 times of chitosan masses after 50～70 ℃.Stir 3～6h discharging, the slip massfraction is to leave standstill behind 10% the hydrochloric acid adjusting pH=7.0, and suction filtration gets the solids crude product.Thick product dehydrated alcohol extracting 8～12h on apparatus,Soxhlet's, 40～60 ℃ of vacuum-dryings obtain the Quaternary Ammonium Salt of Chitosan derivative product (AST-CTS) of difference grafting on chitosan C2 bit amino and the C6 position hydroxyl.
Embodiment 3
Being dissolved in 1 part of iodine with its amount ratio is in 0.9: 1 the liquor kalii iodide, is between 3%～5% the acetic acid adjust pH 4～5 with massfraction.The Virahol that the adding cumulative volume is 5～8 times/trimethyl carbinol mixed solvent, the mass ratio of adding and iodine is 1: 0.1～1: 0.3 palmityl trimethyl ammonium chloride, stirs 1～2h with the speed emulsification of 800～1000r/min and makes tensio-active agent and iodine Uniform Dispersion.With quaternized grafted chitosan derivative (AS-CTS) by with the iodine mass ratio be that 4: 1 amount takes by weighing in the above-mentioned dispersion system of rear adding, 3～6h is stirred in speed emulsification with 800～1000r/min, make the mixture of n-trimethyl chitosan chloride chelated iodine, be homogeneous solution, wherein the massfraction of iodine is about 4.5%～5.5%.The mixture of n-trimethyl chitosan chloride chelated iodine is designated as AS-CTS-I
2
Embodiment 4
Being dissolved in 1 part of iodine with its amount ratio is in 0.8: 1 the liquor kalii iodide, between 0.1mol/L dilute hydrochloric acid adjust pH 4～5.The propyl alcohol that the adding cumulative volume is 4～6 times/hexanaphthene mixed solvent, adding and iodine mass ratio are 1: 0.05～1: 0.1 sodium laurylsulfonate, stir 2h with the speed emulsification of 800r/min, make tensio-active agent and iodine molecule Uniform Dispersion.With n-trimethyl chitosan chloride derivative (AST-CTS) by taking by weighing in the dispersion system of rear adding iodine with 3.5: 1～5.5: 1 amount of iodine mass ratio, speed with 900r/min stirs 4～6h, make the mixture homogeneous solution of chitosan iodine, be designated as AST-CTS-I
2The massfraction of iodine is greater than 5.0% in this mixture.
Embodiment 5
Polyvinyl alcohol is made into massfraction under temperature 60 C be 5% the aqueous solution, added the complex solution (AS-CTS-I of n-trimethyl chitosan chloride chelated iodine in 1: 0.2 by volume～1: 0.5
2), stirring 1h in 60 ℃ with 600r/min, the adding volume ratio is 1%～3% linking agent glutaraldehyde, pours film forming in the mould into behind the stirring 2h.Dry antibacterial film, the content of iodine (10 ± 1) % in the film is (41 ± 1) mm to colibacillary antibacterial circle diameter, is (45 ± 1) mm to the antibacterial circle diameter of streptococcus aureus.The air penetrability of antibacterial film is 50%～60%; The water-intake rate of antibacterial film is 300%～400%; The tensile strength of antibacterial film is 46Mpa, and elongation at break is 26%.
Embodiment 6
Gelatin is made into massfraction under temperature 50 C be 8% the aqueous solution, added the mixture (AST-CTS-I of n-trimethyl chitosan chloride chelated iodine in 1: 0.2 by volume～1: 0.5
2) solution, stir 1h in 50 ℃ with 600r/min, add mass ratio with iodine and be 0.5: 1 tensio-active agent tween-80,600r/min stirs in the high-speed emulsifying machine, adds volume ratio and be 1%～3% linking agent glutaraldehyde, pours film forming in the mould into after stirring 2h.The dry antibacterial film that gets the n-trimethyl chitosan chloride chelated iodine, the massfraction of iodine is (10 ± 1) % in the film; Antibacterial film is (43 ± 1) mm to colibacillary antibacterial circle diameter, is (46 ± 1) mm to the antibacterial circle diameter of streptococcus aureus; The air penetrability of antibacterial film is 55%～65%; Water-intake rate is 250%～350%; The tensile strength of antibacterial film is 45.74Mpa, and elongation at break is 25.6%.
Embodiment 7
1 part of n-trimethyl chitosan chloride derivative (AS-CTS) is dissolved in the dilute hydrochloric acid solution of 0.1mol/L, and gelatin is made into massfraction under temperature 50 C be 8% the aqueous solution.Be that 1: 1～1: 3 ratio is mixed two solution than gelatin quality in the quality of quaternized chitosan derivatives, fully stir 1h in 50 ℃ with 600r/min.The adding volume fraction is 1%～3% linking agent glutaraldehyde, pours film forming in the mould into behind the stirring 2h.With distilled water film being washed into neutrality dries.
Iodine is dissolved in ethanol/isopropyl alcohol mixed solvent, and contained iodine massfraction is at 8%～10% solution.The blend film of above-mentioned preparation is immersed in 6h in the iodine solution, and taking-up is sealed up for safekeeping, obtains the antibacterial film of n-trimethyl chitosan chloride derivative absorption (complexing) iodine, and wherein the massfraction of iodine is at (10 ± 1) %; Antibacterial film is (45 ± 1) mm to colibacillary antibacterial circle diameter, is (48 ± 1) mm to the antibacterial circle diameter of streptococcus aureus; The air penetrability of antibacterial film is 54%～68%; Water-intake rate is 300%～400%; The tensile strength of antibacterial film is 46.38Mpa, and elongation at break is 26.7%.
Embodiment 8
Get 1 part of n-trimethyl chitosan chloride derivative (AST-CTS) and be dissolved in 5% the acetum, polyvinyl alcohol is made into massfraction under temperature 60 C be 5% the aqueous solution.Be that 1: 1～1: 4 ratio is mixed two solution in the quality of quaternized chitosan derivatives than the mass ratio of polyvinyl alcohol, under 60 ℃ with 800r/min high-speed stirring 1h, add volume fraction and be 1%～3% glutaraldehyde cross-linking agent and total mass mark and be 1% sodium laurylsulfonate, fully stir 2～4h, pour film forming in the mould into, take out film and dry with distilled water flushing to neutrality.
It is in 0.9: 1 the saturated solution of potassium iodide that iodine is dissolved in its amount ratio, adds the trimethyl carbinol/hexanaphthene mixed organic solvents, and the massfraction that is made into iodine is the solution between 8%～10%.AST-CTS and polyvinyl alcohol blending film are immersed 6h in the iodine solution, and taking-up is sealed up for safekeeping, obtains the antibacterial film of quaternary ammonium salt absorption (complexing) iodine.Wherein the massfraction of iodine is (10 ± 1) %; Antibacterial film is (47 ± 1) mm to colibacillary antibacterial circle diameter, is (49 ± 1) mm to the antibacterial circle diameter of streptococcus aureus; The air penetrability of antibacterial film is 50%～60%; Water-intake rate is 350%～450%; The tensile strength of antibacterial film is 47.3Mpa, and elongation at break is 25.5%.
Embodiment 9
A kind of method for preparing the antibacterial film of n-trimethyl chitosan chloride chelated iodine may further comprise the steps:
(1) will gluing all relatively, molecular mass is that 30,000 chitosans are dissolved in acetum, add the dehydrated alcohol dilution that accounts for cumulative volume 50%, stir the lower glutaraldehyde that adds, the mol ratio of chitosan and glutaraldehyde is 1: 2, temperature of reaction is controlled at 35 ℃, reaction 4h, obtain even milky white liquid, drip NaOH solution in above-mentioned emulsion, stir until produce white flocks, filtration obtains white solid in apparatus,Soxhlet's dehydrated alcohol extraction 24h, and 30 ℃ of vacuum-dryings get chitosan aldehyde schiff bases, with chitosan aldehyde schiff bases swelling 8～12h in hexanaphthene, add diethylin monochloroethane hydrochloride, the mol ratio of chitosan aldehyde schiff bases and diethylin monochloroethane hydrochloride is 1: 2, and temperature of reaction is 40 ℃, reaction 6h, after hydrochloric acid/ethanolic soln suspension is processed, regulate pH=7.0, the solid ethanol that leaches with NaOH solution, washing with acetone prepares C6 hydroxyl n-trimethyl chitosan chloride derivative after 40 ℃ of vacuum-dryings;
(2) in the KI solution that iodine is dissolved in, transfer pH 3.5 with rare acetic acid, the adding volume fraction is 50% ethanol, add the sodium laurylsulfonate tensio-active agent, the mass ratio of tensio-active agent and iodine is 1: 0.1, emulsify at a high speed makes tensio-active agent and iodine Uniform Dispersion, add again the n-trimethyl chitosan chloride derivative in above-mentioned iodine liquid, the mass ratio of n-trimethyl chitosan chloride derivative and iodine is 3.5: 1, with 800r/min rotating speed emulsification 6h, make the mixture of n-trimethyl chitosan chloride chelated iodine, wherein the massfraction of iodine is 4～6%;
Mixture and polyvinyl alcohol blending with above-mentioned n-trimethyl chitosan chloride chelated iodine, the volume ratio of the mixture of n-trimethyl chitosan chloride chelated iodine and polyvinyl alcohol or gelatin is 0.2: 1, fully stir 4h in 30 ℃, blended liquid is film forming in mould, can prepare by lyophilize the antibacterial film of n-trimethyl chitosan chloride chelated iodine, wherein the massfraction of iodine is between 5%～15%.
Embodiment 10
A kind of method for preparing the antibacterial film of n-trimethyl chitosan chloride chelated iodine may further comprise the steps:
(1) will gluing all relatively, the chitosan of molecular mass 100,000 is dissolved in acetum, add the dehydrated alcohol dilution that accounts for cumulative volume 50%, stir the lower phenyl aldehyde that adds, the mol ratio of chitosan and phenyl aldehyde is 1: 4, temperature of reaction is controlled at 45 ℃, reaction 3h, obtain even milky white liquid, drip NaOH solution in above-mentioned emulsion, stir until produce white flocks, filtration obtains white solid in apparatus,Soxhlet's dehydrated alcohol extraction 24h, and 60 ℃ of vacuum-dryings get chitosan aldehyde schiff bases, with chitosan aldehyde schiff bases swelling 12h in the trimethyl carbinol, add trichlorine dihydroxypropyl trimethyl ammonium chloride, the mol ratio of chitosan aldehyde schiff bases and trichlorine dihydroxypropyl trimethyl ammonium chloride is 1: 6, and temperature of reaction is 60 ℃, reaction 3h, after hydrochloric acid/ethanolic soln suspension is processed, regulate pH=7.0, the solid ethanol that leaches with NaOH solution, washing with acetone prepares C6 hydroxyl n-trimethyl chitosan chloride derivative after 60 ℃ of vacuum-dryings;
(2) iodine is dissolved in the solution of KI, transfer pH 5.5 with dilute hydrochloric acid, the adding volume fraction is 50% Virahol, add the tensio-active agent palmityl trimethyl ammonium chloride, the mass ratio of tensio-active agent and iodine is 1: 0.3, emulsify at a high speed makes tensio-active agent and iodine Uniform Dispersion, add again the n-trimethyl chitosan chloride derivative in above-mentioned iodine liquid, the mass ratio of n-trimethyl chitosan chloride derivative and iodine is 5.5: 1, with 1000r/min rotating speed emulsification 3h, make the mixture of n-trimethyl chitosan chloride chelated iodine, wherein the massfraction of iodine is 4～6%;
Mixture and gelatin cross-blend with above-mentioned n-trimethyl chitosan chloride chelated iodine, the volume ratio of the mixture of n-trimethyl chitosan chloride chelated iodine and polyvinyl alcohol or gelatin is 0.5: 1, fully stir 2h in 60 ℃, blended liquid is film forming in mould, can prepare by infrared drying the antibacterial film of n-trimethyl chitosan chloride chelated iodine, wherein the massfraction of iodine is between 5%～15%.
Embodiment 11
A kind of method for preparing the antibacterial film of n-trimethyl chitosan chloride chelated iodine may further comprise the steps:
(1) will gluing all relatively, the chitosan of molecular mass 150,000 adds swelling 2h in the propyl alcohol, heat up 50 ℃ after adding NaOH solution alkalization 2h, add diethylin monochloroethane hydrochloride, the mol ratio of chitosan and diethylin monochloroethane hydrochloride is 1: 2, transfer pH=7.0 with hydrochloric acid behind the reaction 3h, filter, solid extracts 10h with dehydrated alcohol in apparatus,Soxhlet's, prepares chitosan hydroxyl and the amino upper respectively n-trimethyl chitosan chloride derivative of grafting after 40 ℃ of vacuum-dryings;
(2) the Quaternary Ammonium Salt of Chitosan derivative being dissolved in massfraction is in 2% the acetum, add polyvinyl alcohol, the mass ratio of Quaternary Ammonium Salt of Chitosan derivative and polyvinyl alcohol is 1: 1, fully stir 4h with 400r/min, inject the mould film forming, to neutral, then infrared drying obtains blend film with distilled water flushing;
B, iodine is dissolved in the mixed organic solvents that ethanol and propyl alcohol consist of obtains iodine liquid, the massfraction of iodine liquid is 8%, the blend film of above-mentioned preparation is immersed in 4h in the iodine liquid, can directly seal up for safekeeping after the taking-up, blend film is by Quaternary Ammonium Salt of Chitosan absorption or chelated iodine, prepare the antibacterial film of n-trimethyl chitosan chloride chelated iodine, the massfraction of iodine is between 5%～15% in the antibacterial film.
Embodiment 12
A kind of method for preparing the antibacterial film of n-trimethyl chitosan chloride chelated iodine may further comprise the steps:
(1) will glue all relative molecular mass is that 300,000 chitosan adds swelling 4h in the organic solvent, heat up 70 ℃ after adding NaOH solution alkalization 4h, add trichlorine dihydroxypropyl trimethyl ammonium chloride, the mol ratio of chitosan and trichlorine dihydroxypropyl trimethyl ammonium chloride is 1: 6, transfer pH=7.0 with hydrochloric acid behind the reaction 6h, filter, solid extracts 12h with dehydrated alcohol in apparatus,Soxhlet's, prepares chitosan hydroxyl and the amino upper respectively n-trimethyl chitosan chloride derivative of grafting after 60 ℃ of vacuum-dryings;
(2) the Quaternary Ammonium Salt of Chitosan derivative being dissolved in massfraction is in 5% the hydrochloric acid soln, add gelatin, the mass ratio of Quaternary Ammonium Salt of Chitosan derivative and gelatin is 1: 4, fully stir 2h with 800r/min, inject the mould film forming,, then naturally dry and obtain blend film to neutral with distilled water flushing;
Iodine is dissolved in propyl alcohol, the sherwood oil mixed solvent obtains iodine liquid, the massfraction of iodine liquid is 10%, the blend film of above-mentioned preparation is immersed in 6h in the iodine liquid, can directly seal up for safekeeping after the taking-up, blend film is by Quaternary Ammonium Salt of Chitosan absorption or chelated iodine, prepare the antibacterial film of n-trimethyl chitosan chloride chelated iodine, the massfraction of iodine is between 5%～15% in the antibacterial film.
Prepared antibacterial film has the mechanical property of strong water-absorbent, flexibility, air penetrability and some strength, the antibacterial film of n-trimethyl chitosan chloride absorption (complexing) iodine, iodine is evenly distributed, good stability, utilize antibacterial around-France (MIC) to survey it to colibacillary antibacterial for extremely sensitive, be extremely sensitive to the antibacterial of streptococcus aureus, wherein the massfraction of iodine is between 5%～15%.Two classes contain the sealing of iodine antibacterial film preserved 6～12 months, and the massfraction of iodine does not have considerable change.
The massfraction of iodine can be controlled by the massfraction of regulating n-trimethyl chitosan chloride derivative in the film.Under differing temps, the rate of release of iodine is different in the film simultaneously, and temperature is higher, and the rate of release of iodine is faster.Therefore the antibacterial film of n-trimethyl chitosan chloride chelated iodine can be by the massfraction of regulating each material in the blend film and the release that temperature is controlled iodine molecule.The antibacterial film of the n-trimethyl chitosan chloride chelated iodine for preparing can prepare antibacterial, the anti-inflammatory medical films of various forms, can demonstrate fully chitosan-based and double effects iodine.
Claims (1)
1. method for preparing the antibacterial film of n-trimethyl chitosan chloride chelated iodine is characterized in that the method may further comprise the steps:
(1) on the hydroxyl of chitosan structure unit or amino, accesses respectively quaternary ammonium salt, prepare the n-trimethyl chitosan chloride derivative;
(2) blend film with n-trimethyl chitosan chloride derivative, gelatin or polyvinyl alcohol is soaked in the iodine solution, and soak time is 4～6h, obtains the antibacterial film of n-trimethyl chitosan chloride/gelatin or polyvinyl alcohol chelated iodine;
Step (1) adopts following steps: chitosan is dissolved in acetum, add the dehydrated alcohol dilution that accounts for cumulative volume 50%, stir the lower aldehyde that adds, temperature of reaction is controlled at 35～45 ℃, reaction 3～4h, obtain even milky white liquid, drip NaOH solution in above-mentioned emulsion, stir until produce white flocks, filter and obtain white solid in apparatus,Soxhlet's dehydrated alcohol extraction 24h, 30～60 ℃ of vacuum-dryings get chitosan aldehyde schiff bases, with chitosan aldehyde schiff bases swelling 8～12h in organic solvent, add quaternary ammonium salt monomer, temperature of reaction is 40～60 ℃, reaction 3～6h, after hydrochloric acid/ethanolic soln suspension is processed, regulate pH=7.0, the solid ethanol that leaches with NaOH solution, washing with acetone prepares C6 hydroxyl n-trimethyl chitosan chloride derivative after 40～60 ℃ of vacuum-dryings;
Sticking all relative molecular masses of described chitosan are 30,000～300,000; Described aldehyde is glutaraldehyde or phenyl aldehyde, and the mol ratio of chitosan and aldehyde is 1 ︰ (2～4); Described organic solvent is hexanaphthene, the trimethyl carbinol, pyridine or chloroform; Described quaternary ammonium salt monomer is diethylin monochloroethane hydrochloride or trichlorine dihydroxypropyl trimethyl ammonium chloride, and the mol ratio of chitosan aldehyde schiff bases and quaternary ammonium salt monomer is 1 ︰ (2～6);
Step (2) adopts following steps:
A, iodine is dissolved in the KI solution, transfer pH between 3.5～5.5 with rare acetic acid or dilute hydrochloric acid, the adding volume fraction is 50% organic solvent, add tensio-active agent, emulsify at a high speed makes tensio-active agent and iodine Uniform Dispersion, adds the n-trimethyl chitosan chloride derivative in above-mentioned iodine liquid again, with 800～1000r/min rotating speed emulsification, 3～6h, make the mixture of n-trimethyl chitosan chloride chelated iodine, wherein the massfraction of iodine is 4～6%;
B, with mixture and polyvinyl alcohol or the gelatin cross-blend of above-mentioned n-trimethyl chitosan chloride chelated iodine, fully stir 2～4h in 30 ℃～60 ℃ temperature ranges, blended liquid becomes blend film in mould, can or naturally dry the antibacterial film for preparing the n-trimethyl chitosan chloride chelated iodine by lyophilize, infrared drying, wherein the massfraction of iodine is between 5%～15%;
Described organic solvent is ethanol, Virahol or the trimethyl carbinol; Described tensio-active agent is the polyvinyl chloride-based ether of sodium laurylsulfonate, palmityl trimethyl ammonium chloride or lauryl alcohol, the mass ratio of tensio-active agent and iodine is 1: 0.1～1: 0.3, and the mass ratio of described n-trimethyl chitosan chloride derivative and iodine is 3.5: 1～5.5: 1; The volume ratio of the mixture of described n-trimethyl chitosan chloride chelated iodine and polyvinyl alcohol or gelatin is 0.2: 1～0.5: 1;
Step (2) can also adopt following steps:
A, the Quaternary Ammonium Salt of Chitosan derivative is dissolved in massfraction is in 2%～5% the acetic acid or hydrochloric acid soln, add polyvinyl alcohol or gelatin, fully stir 2～4h with 400～800r/min, inject the mould film forming, with distilled water flushing to neutral, infrared drying or naturally dry and obtain blend film then;
B, iodine is dissolved in obtains iodine liquid in the organic solvent, the blend film of above-mentioned preparation is immersed in 4～6h in the iodine liquid, can directly seal up for safekeeping after the taking-up, blend film is by the Quaternary Ammonium Salt of Chitosan chelated iodine, prepare the antibacterial film of n-trimethyl chitosan chloride chelated iodine, the massfraction of iodine is between 5%～15% in the antibacterial film;
Described organic solvent is two or more mixed solvent in ethanol, propyl alcohol, Virahol or the sherwood oil; The mass ratio of Quaternary Ammonium Salt of Chitosan derivative and polyvinyl alcohol or gelatin is 1: 1～1: 4, and the massfraction of iodine liquid is 8%～10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210050268 CN102604141B (en) | 2012-02-29 | 2012-02-29 | Method for preparing antibacterial film of quaternarized chitosan iodine complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210050268 CN102604141B (en) | 2012-02-29 | 2012-02-29 | Method for preparing antibacterial film of quaternarized chitosan iodine complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102604141A CN102604141A (en) | 2012-07-25 |
| CN102604141B true CN102604141B (en) | 2013-10-30 |
Family
ID=46521949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210050268 Expired - Fee Related CN102604141B (en) | 2012-02-29 | 2012-02-29 | Method for preparing antibacterial film of quaternarized chitosan iodine complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102604141B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103720712A (en) * | 2012-10-10 | 2014-04-16 | 上海工程技术大学 | Method for preparing quaternized chitosan nano iodine disinfectant |
| CN103083711B (en) * | 2013-01-11 | 2014-05-07 | 浙江三创生物科技有限公司 | Chitosan-iodine composite biological medical film and preparation method thereof |
| CN104163933B (en) * | 2013-05-17 | 2017-10-20 | 中国科学院海洋研究所 | A kind of polymer thin film and its methods and applications prepared based on Freeze Drying Technique |
| CN105506968B (en) * | 2014-10-14 | 2017-08-15 | 中国海洋大学 | A kind of preparation method of Quaternary Ammonium Salt of Chitosan fiber |
| CN104307030B (en) * | 2014-11-07 | 2016-07-27 | 广东泰宝医疗科技股份有限公司 | A kind of method that Quaternary Ammonium Salt of Chitosan medical hemostatic dressing is prepared in low temperature plasma catalysis |
| CN104672348B (en) * | 2015-02-14 | 2017-06-30 | 滨州医学院 | Chitosan quaternary ammonium salt derivatives with good aqueous solubility and antibacterial activity and preparation method thereof |
| CN105218702A (en) * | 2015-09-30 | 2016-01-06 | 苏州蔻美新材料有限公司 | A kind of water-solubility chitosan derivative and synthetic method thereof |
| CN105865883A (en) * | 2016-03-31 | 2016-08-17 | 常州大学 | Method for measuring content of elemental iodine complexed in povidone-iodine |
| CN106496357B (en) * | 2016-10-27 | 2019-02-19 | 山东师范大学 | A kind of O- quaternary ammonium salt-N- alkylated chitosan and the preparation method and application thereof |
| CN106727010A (en) * | 2017-01-05 | 2017-05-31 | 李美英 | A kind of special antibacterial film forming leaching hand liquid of milker |
| CN107417808A (en) * | 2017-05-15 | 2017-12-01 | 山东博创生物科技有限公司 | A kind of Water soluble oligo chitosan quaternary ammonium salt and preparation method thereof |
| CN108057425B (en) * | 2017-12-23 | 2021-04-30 | 杭州蟾拓环保新材料有限公司 | Sewage treatment adsorbent and preparation method thereof |
| CN108998285A (en) * | 2018-09-14 | 2018-12-14 | 太和县中科蓝海智能医疗设备有限公司 | A kind of medical instrument maintenance washes agent and preparation method thereof |
| CN110286009B (en) * | 2019-06-06 | 2021-09-24 | 强安医疗器械有限公司 | Rectal mucosa exfoliated cell sample pretreatment liquid and preparation method thereof |
| CN110772664B (en) * | 2019-11-25 | 2023-08-15 | 北京化工大学 | Preparation method of surface intelligent coating of orthopaedics temporary implant based on natural polysaccharide and product thereof |
| CN110760077B (en) * | 2019-11-26 | 2021-05-04 | 江南大学 | Polyvinyl alcohol-based antibacterial hydrogel and preparation method thereof |
| CN111593326B (en) * | 2020-06-05 | 2022-01-28 | 西北工业大学 | Method for preparing iodine fixing polymer coating by chemical vapor deposition method and application |
| CN112878045A (en) * | 2020-08-11 | 2021-06-01 | 西安力邦医药科技有限责任公司 | Air-permeable hydrophilic antibacterial antiviral medical cloth containing iodine compound |
| CN112915252B (en) * | 2021-01-29 | 2022-10-14 | 河南亚都实业有限公司 | Chitosan quaternary ammonium salt derivative wound dressing and preparation method thereof |
| CN113509490B (en) * | 2021-05-08 | 2022-08-12 | 维尼健康（深圳）股份有限公司 | Non-irritant medical disinfectant and preparation method thereof |
| CN113480764B (en) * | 2021-07-31 | 2021-12-24 | 贵州省材料产业技术研究院 | Preparation method of enhanced polyvinyl alcohol antibacterial film and product thereof |
| CN113996267B (en) * | 2021-11-23 | 2023-08-11 | 西南科技大学 | Preparation method of silicon-based fiber felt-bismuth-based composite material and application of silicon-based fiber felt-bismuth-based composite material in radioactive iodine adsorption |
| CN116726231A (en) * | 2023-08-10 | 2023-09-12 | 北京小鹿科技有限公司 | Dry antibacterial paper diaper and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235099B (en) * | 2007-01-29 | 2011-01-12 | 北京理工大学 | Carboxymethyl chitosan quaternary ammonium salt derivatives and preparation method thereof |
| CN101649007B (en) * | 2009-09-30 | 2011-06-01 | 上海交通大学 | Chitosan quaternary phosphonium salt derivative and preparation method thereof |
| CN101735339B (en) * | 2010-01-12 | 2011-09-07 | 浙江理工大学 | Reactive chitosan derivative and preparation method thereof |
-
2012
- 2012-02-29 CN CN 201210050268 patent/CN102604141B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102604141A (en) | 2012-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102604141B (en) | Method for preparing antibacterial film of quaternarized chitosan iodine complex | |
| Pang et al. | Cellulose based materials for controlled release formulations of agrochemicals: A review of modifications and applications | |
| CN102552966B (en) | Alginate antibacterial dressing and its preparation method | |
| CN105494430B (en) | One kind carries silver-colored low-molecular weight chitoglycan complex microsphere antiseptic and preparation method thereof | |
| CN103212106B (en) | Method for preparing bacterial cellulose slow-release analgesia dressing | |
| CN100411690C (en) | Bacteriostatic porous polyelectrolyte material and its prepn process | |
| CN102319448A (en) | Antibacterial aquagel material for preparing medical wound dressing and preparation method thereof | |
| CN107383283A (en) | A kind of structural type antimicrobial acrylic emulsion and its preparation method and application | |
| CN102406959A (en) | Liquid bandage containing povidone iodine and preparation method thereof | |
| CN104902954B (en) | Wound care products with superacid composite | |
| CN109432484A (en) | Medical super-hydrophobic antiseptic dressing of one kind and preparation method thereof | |
| CN106496357A (en) | A kind of O quaternary ammonium salts N alkylated chitosans and preparation method and application | |
| CN107899077A (en) | A kind of composite antibacterial coating of stability enhancing and its preparation method and application | |
| CN103638551B (en) | Preparation method for chitosan 6-OH immobilized cyclodextrin included tea tree oil thermo-sensitive hydrogel | |
| CN106719630A (en) | Optical Response controlled release nanometer pesticidal preparations and its preparation method and application | |
| CN103159972A (en) | Preparation method for chitosan and cellulose antibiosis application film of biotin coupling nano silver | |
| CN107998438A (en) | A kind of sustained anti-microbial bearing hydrocolloid dressing and preparation method thereof | |
| Long et al. | Microfibrillated cellulose-enhanced carboxymethyl chitosan/oxidized starch sponge for chronic diabetic wound repair | |
| CN107929232A (en) | A kind of multiple-effect restraining and sterilizing bacteria repairs gel and preparation method and application | |
| CN102493014A (en) | Epsilon-polylysine and polyvinyl alcohol composite biological antibacterial fiber and preparation method thereof | |
| Huang et al. | Modification of cellulose nanocrystals as antibacterial nanofillers to fabricate rechargeable nanocomposite films for active packaging | |
| CN107915787A (en) | A kind of preparation method of pH temperature dual-sensitivity chitosan nano particle | |
| Wei et al. | Sodium alginate-carboxymethyl chitosan hydrogels loaded with difenoconazole for pH-responsive release to control wheat crown rot | |
| CN111533613A (en) | Nano-cellulose gel-based water-retaining slow-release fertilizer and preparation method thereof | |
| CN105801870B (en) | The preparation method and products obtained therefrom of a kind of poly sialic acid-hyaluronic acid plural gel and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131030 Termination date: 20160229 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |