CN104153120A - Antibacterial medical dressing film carrying nano-silver and cellulose nanocrystalline hybrid materials and preparation method thereof - Google Patents

Antibacterial medical dressing film carrying nano-silver and cellulose nanocrystalline hybrid materials and preparation method thereof Download PDF

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CN104153120A
CN104153120A CN201410291338.7A CN201410291338A CN104153120A CN 104153120 A CN104153120 A CN 104153120A CN 201410291338 A CN201410291338 A CN 201410291338A CN 104153120 A CN104153120 A CN 104153120A
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nano
cellulose
silver
hybrid material
preparation method
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CN201410291338.7A
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余厚咏
张冬子
李志刚
陈国印
杨兴远
陈旺平
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浙江理工大学
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Abstract

The invention relates to an antibacterial medical dressing film carrying nano-silver and cellulose nanocrystalline hybrid materials and a preparation method thereof. The film comprises biodegradable polymers and the nano-silver and cellulose nanocrystalline hybrid materials with the mass ratio of 3-99 : 1. The preparation method comprises the steps that (1) cellulose raw materials are added to a mixed acid water solution of formic acid and hydrochloric acid, aldehyde group cellulose nanocrystalline is obtained through reaction, the aldehyde group cellulose nanocrystalline is then added to silver salt solutions with the content of 0.01-3 mol/L, and the nano-silver and cellulose nanocrystalline hybrid materials are obtained through reaction; (2) after the hybrid materials and the biodegradable polymers are added to organic solvents, transparent uniform electrostatic spinning solutions are obtained through reaction; (3) electrostatic spinning is carried out on the electrostatic spinning solutions to obtain the antibacterial medical dressing film. The preparation method is simple in preparation technology and suitable for industrial large-scale production, the multifunctional composite film is biodegradable and good in mechanical and thermal property, breathability, antibacterial effect, biocompatibility and cytocompatibility.

Description

Antibacterial medical dressing film of a kind of loading nano silvery-cellulose nano-crystal hybrid material and preparation method thereof

 

Technical field

The invention belongs to Multifunction complete biodegradable composite membrane and preparation field thereof, particularly relate to antibacterial medical dressing film of a kind of loading nano silvery-cellulose nano-crystal hybrid material and preparation method thereof.

 

Background technology

Along with global warming, and the increase of the movement of population that brings of urbanization and globalization, various forms of bacteriums being infected and become more and more serious, the increase of anti-bacteria and breeding also become more and more important.Clinically, in order to control the bacterium on wound, protect from infection, many medical materials add antibiotic or various anti-biotic material in using.Although antibiotic onset is rapid, antibiotic and anti-biotic material antibacterial action are limited, and bacterium is of a great variety, therefore limited containing the effect of the dressing of antibiotic or anti-biotic material.And long-term use can make bacterium produce drug resistance.Make people be busy with developing more anti-biotic material.Even to this day, some bacteriums have been difficult to kill.

Because the use of antibiotic and anti-biotic material has entered bottleneck, people are familiar with well known antiseptic elements silver for a long time again.Traditional silver and some other oxide material have certain sterilizing ability, are a kind of heavy metals with broad spectrum antibacterial.Be prepared into after nano level particle, bactericidal activity can significantly improve, and nano level particle is more convenient for being attached on cellulose surface, for the surface of a wound provides stable dynamic activity silver, there is the slow releasing function of medicine, act on incessantly regenerated bacteria, thereby there is the effect of lasting sterilization.

Taking bone surgery Acticoat(Ai Yinkang used) silver ion dressing is as example, the artificial polyester of normal employing is intermediate layer, then by evaporation coating technique, nanometer Ag is deposited on polyester material, but evaporation coating technique has defects such as cost is high, polyester material is not biodegradable.Meanwhile, on market, degradation rate is slow under field conditions (factors) for this type of anti-biotic material, and nowadays this type of anti-biotic material causes certain pollution to environment, a kind of biodegradable substitute of active demand.

In recent years, biodegradable polyesters (as PHBV (PHBV), PLA (PLA) etc.) and fibre thereof have wide application potential at aspects such as bio-medical material, thin-film material, disposable product, packaging material and dressing materials thereof.But pure biodegradable polyesters is because drafting rate is compared with the low macromolecular orientation imperfection that causes, and fracture strength and Young's modulus reduce.This just makes this class material be restricted in the application of the occasion that mechanics and thermal property are had higher requirements, as for bone or ligament tissue timbering material CN102493021A; CN101927033A).At present existing researcher is by Nano Silver with cellulose is nanocrystalline is added in Biodegradable polyester, result shows: the nanocrystalline mechanical strength that can strengthen matrix of cellulose, Nano Silver can be given antibiotic property (the Fortunati E of composite, Armentano I, Zhou Q, Iannonia A, Saino E, Visai L, Berglund LA, Kenny JM. Multifunctional bionanocomposite films of poly (lactic acid), cellulose nanocrystals and silver nanoparticles. Carbohydrate Polymers 2012, 87:1596 – 1605).But Nano Silver is directly to add polymeric matrix to, caused the effective combination of the nanocrystalline shortage of Nano Silver and cellulose, and the composite film material of solution casting is difficult to intercept the subinfection again of bacterium.Micro/nano fibrous membrane material not only has controlled gap structure (intercepting bacterium or virus), and has and organize good compatibility.

The people such as Stevens find, cell can be well at nano-material surface growth (Stevens M M, George J H. Exploring and engineering the cell surface interface. Science, 2005,310 (5751): 1135-1138).Loading nano silvery-cellulose nano-crystal hybrid material of the present invention is a kind of multi-functional filler of antibacterial enhancing, it is taking biodegradable polymer as matrix, pass through electrostatic spinning technique, prepare mechanical strength good, heat resistance is good, good biocompatibility, the antibacterial medical dressing dimension film that cell compatibility is good.The nanoscale strong point that effectively provides Growth of Cells to need more, in addition, the present invention can be placed in wound surface effectively, for Growth of Cells provides fulcrum, the environment that can regenerate with the three-dimensional tissue that coaches.

 

Summary of the invention

Technical problem to be solved by this invention is to provide antibacterial medical dressing film of a kind of loading nano silvery-cellulose nano-crystal hybrid material and preparation method thereof, this tunica fibrosa is complete biodegradable product, mechanics and thermal property excellence, and permeability is good, good anti-bacterial effect, has a extensive future; The method simple and fast, Cheap highly effective, be suitable for industrialized mass production; In Nano Silver-cellulose nano-crystal hybrid material used, cellulose is nanocrystalline is combined firmly with Nano Silver, and surface is beneficial to polyester compound with ester group.

The preparation method of the antibacterial medical dressing film of a kind of loading nano silvery-cellulose nano-crystal hybrid material of the present invention, comprising:

(1) cellulosic material is joined in the nitration mixture aqueous solution of formic acid-hydrochloric acid, in 40-90 DEG C of reaction 3-15 h, after question response finishes, with deionized water washed reaction product, to neutral, the cellulose that obtains aldehyde radical is nanocrystalline; Then by nanocrystalline the cellulose of this aldehyde radical silver salt solution that joins 0.01-3 mol/L, in 50 ~ 95 DEG C of reaction 10 ~ 60 min, after naturally cooling, with deionized water diluting reaction product, centrifugal postlyophilization or vacuumize, obtain Nano Silver-cellulose nano-crystal hybrid material.

(2) above-mentioned hybrid material and biological degradation polyalcohol are joined after organic solvent, be warming up to 80 DEG C of 30 –, fully stir, obtain the electrostatic spinning liquid of transparent homogeneous, wherein biological degradation polyalcohol and the mass fraction sum of Nano Silver-cellulose nano-crystal hybrid material in electrostatic spinning liquid are 5 – 20%, and the mass ratio of biological degradation polyalcohol and Nano Silver-cellulose nano-crystal hybrid material is 3 – 99:1.

(3) extract above-mentioned spinning solution with syringe and carry out electrostatic spinning, spinning parameter is that operating voltage 5-30KV, receiving range are that 5 – 50cm, spinning speed are 0.1 – 3ml/h, the spinning time is 1 – 12h, then at room temperature vacuumize 2 – 24h, can obtain the antibacterial medical dressing film of loading nano silvery-cellulose nano-crystal hybrid material.

Cellulosic material in described step (1) is one or more in flax fibre, microcrystalline cellulose, cotton, bamboo fibre, wood pulp.

In formic acid-hydrochloric acid nitration mixture aqueous solution in described step (1), the volume ratio of formic acid and hydrochloric acid is 2 – 9:1, and before configuration, the concentration of formic acid is 3 – 10 mol/L, and before configuration, the concentration of hydrochloric acid is 1 – 10 mol/L.

In described step (1), the solid-to-liquid ratio of cellulosic material and formic acid-hydrochloric acid nitration mixture aqueous solution is 1:10 – 80 g/mL.

In described step (1), described silver salt solution is liquor argenti nitratis ophthalmicus, silver ammino solution or nitrogenize silver solution.

In described step (1) cellulose of aldehyde radical nanocrystalline with solid-to-liquid ratio silver salt solution be 1:20 – 500 g/mL.

In Nano Silver-cellulose nano-crystal hybrid material in described step (1), cellulose is nanocrystalline is bar-shaped or ellipticity, and its particle diameter is 10 – 300 nm, and the particle diameter of Nano Silver is 8 – 45 nm.

Biological degradation polyalcohol in described step (2) is PHBV (PHBV), PLA (PLA), polycaprolactone (PCL) or poly-(Ru Suan – glycolic acid) copolymer (PLGA).

Organic solvent in described step (2) is N, N – dimethyl formamide, N, one or more in N – dimethylacetylamide, oxolane, carrene, 1,2 – chloroethanes, chloroform, acetone, diethylene glycol dimethyl ether or ethyl acetate.

Composite cellulosic membrane fibre diameter in described step (3) is 20 nm – 800 nm, and thickness is 100nm – 2000 μ m.

 

The present invention introduces Nano Silver-cellulose nano-crystal hybrid material in biodegradable polyesters, because hybrid material surface ester group can make it be dispersed in equably in polymeric matrix, not only can significantly improve its mechanics and thermal property, and its antibacterial effect is lasting, the composite membrane of gained has shown charming prospect in antibacterial non-returnable container material, wound dressing.

 

Beneficial effect

The present invention compared with prior art has following distinguishing feature:

(1) the nanocrystalline Biodegradable material that is of raw polymer of the present invention and cellulose, the preparation process of Nano Silver-cellulose nano-crystal hybrid particle and antibacterial medical dressing film thereof is simple, controlled, quick, efficient, without special expensive equipment, be suitable for the production in enormous quantities of this composite membrane.

(2) in the prepared Nano Silver-cellulose of the present invention nano-crystal hybrid material, Nano Silver and the nanocrystalline combination of cellulose are firm, and surface is with ester group, be conducive to hydrophobicity biodegradable polyesters compound, effectively improve the nanocrystalline synergistic enhancing effect of Nano Silver and cellulose, a little less than having avoided the nanocrystalline combination of previous Nano Silver and cellulose, the performance of composite is difficult to obtain the defects such as raising comprehensively.The antibacterial medical dressing film product of gained has good mechanical property and heat endurance, there is good biocompatibility and cell compatibility, and to the antibiotic rate of Escherichia coli and staphylococcus aureus all up to 100%, cell growth provides three dimensions, can improve the reproduction speed of cell.This polyfunctional full biodegradable composite membrane has broad application prospects in fields such as multi-functional packaging material, the moist wound dressings of novel sanitation articles for use.

 

Brief description of the drawings

The surface topography map of the antibacterial medical dressing film of Fig. 1 loading nano silvery-cellulose nano-crystal hybrid material;

The inhibition zone picture of the antibacterial medical dressing film of Fig. 2 control sample (cellulose is nanocrystalline) and loading nano silvery-cellulose nano-crystal hybrid material to Escherichia coli (a) and staphylococcus aureus (b).

Detailed description of the invention

Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.

Embodiment 1

Flax fibre is added in formic acid-hydrochloric acid solution, at 48 DEG C of reaction 12h, wherein the solid-to-liquid ratio of microcrystalline cellulose and the nitration mixture aqueous solution is 1:60 g/mL, formic acid in the nitration mixture aqueous solution (9 mol/L) is 6:1 with the volume ratio of hydrochloric acid (5 mol/L), after question response finishes, deionized water washed reaction product is to neutral, and the cellulose that can obtain aldehyde radical is nanocrystalline; Again by nanocrystalline the cellulose of this aldehyde radical liquor argenti nitratis ophthalmicus that adds 0.03 mol/L, at 85 DEG C of reaction 20 min, wherein the cellulose of aldehyde radical nanocrystalline with solid-to-liquid ratio liquor argenti nitratis ophthalmicus be 1:100 g/mL, after question response finishes, with deionized water diluting reaction product, the repeatedly centrifugal inorganic ions that removes, then by dispersion liquid vacuumize, obtain Nano Silver-cellulose nano-crystal hybrid material;

Nano Silver-cellulose nano-crystal hybrid material and PHBV (PHBV) are joined in chloroform, be warming up to 70 DEG C, fully stir, obtain the electrostatic spinning liquid of transparent homogeneous, wherein PHBV and the mass fraction sum of Nano Silver-cellulose nano-crystal hybrid material in mixed liquor are 9 %, and the mass ratio of PHBV and Nano Silver-cellulose nano-crystal hybrid material is 9:1;

Extract above-mentioned spinning solution with syringe and carry out electrostatic spinning, spinning parameter is that operating voltage 18KV, receiving range are that 20cm, spinning speed are 0.8ml/h, the spinning time is 4h, then vacuumize 10h at room temperature, can obtain the antibacterial medical dressing film of loading nano silvery-cellulose nano-crystal hybrid material.

The surface topography of antibacterial medical dressing film is observed (see figure 1) through ESEM (SEM), finds good being dispersed in PHBV matrix of Nano Silver-cellulose nano-crystal hybrid material, and fibre diameter is 650nm; Material records the purer PHBV ratio of its tensile strength through micro-control electronic universal tester again and has improved 90%, material is again after thermogravimetric analyzer test, the purer PHBV ratio of its maximum heat degradation temperature has improved 10 DEG C, product again after antibacterial experiment, find its to the antibiotic rate of Escherichia coli and staphylococcus aureus respectively up to 99.5% and 99.9%(see Fig. 2).

Embodiment 2

Microcrystalline cellulose is added in formic acid-hydrochloric acid solution, at 70 DEG C of reaction 2 h, wherein the solid-to-liquid ratio of flax fibre and the nitration mixture aqueous solution is 1:50 g/mL, formic acid in the nitration mixture aqueous solution (5 mol/L) is 8:1 with the volume ratio of hydrochloric acid (7 mol/L), after question response finishes, deionized water washed reaction product is to neutral, and the cellulose that can obtain aldehyde radical is nanocrystalline; Again by nanocrystalline the cellulose of this aldehyde radical liquor argenti nitratis ophthalmicus that adds 0.3 mol/L, at 80 DEG C of reaction 35 min, wherein the cellulose of aldehyde radical nanocrystalline with solid-to-liquid ratio silver ammino solution be 1:220 g/mL, after question response finishes, with deionized water diluting reaction product, the repeatedly centrifugal inorganic ions that removes, then by dispersion liquid vacuumize, obtain Nano Silver-cellulose nano-crystal hybrid material;

Nano Silver-cellulose nano-crystal hybrid material is joined to the N of PHBV (PHBV), in N – dimethyl formamide solution, be warming up to 48 DEG C, fully stir, obtain the electrostatic spinning liquid of transparent homogeneous, wherein PHBV and the mass fraction sum of Nano Silver-cellulose nano-crystal hybrid material in mixed liquor are that the mass ratio of 10%, PHBV and Nano Silver-cellulose nano-crystal hybrid material is 5:1;

Extract above-mentioned spinning solution with syringe and carry out electrostatic spinning, spinning parameter is that operating voltage 16KV, receiving range are that 18cm, spinning speed are 1.0ml/h, the spinning time is 4h, then vacuumize 20h at room temperature, can obtain the antibacterial medical dressing film of loading nano silvery-cellulose nano-crystal hybrid material.

The surface topography of antibacterial medical dressing film is observed through ESEM (SEM), finds that it is 420nm that Nano Silver-cellulose nano-crystal hybrid material is dispersed in fibre diameter in PHBV matrix preferably; Material records the purer PHBV ratio of its tensile strength through micro-control electronic universal tester again and has improved 98%, and material is again after thermogravimetric analyzer test, and the purer PHBV ratio of its maximum heat degradation temperature has improved 18 oc, product again after antibacterial experiment, find its to the antibiotic rate of Escherichia coli and staphylococcus aureus respectively up to 99.6% and 99.8%.

Embodiment 3

Flax fibre is added in formic acid-hydrochloric acid solution, at 40 DEG C of reaction 8 h, wherein the solid-to-liquid ratio of bamboo fibre and the nitration mixture aqueous solution is 1:60 g/mL, formic acid in the nitration mixture aqueous solution (6 mol/L) is 8:1 with the volume ratio of hydrochloric acid (4 mol/L), after question response finishes, deionized water washed reaction product is to neutral, and the cellulose that can obtain aldehyde radical is nanocrystalline; Again by nanocrystalline the cellulose of this aldehyde radical silver ammino solution that adds 0.08 mol/L, at 78 DEG C of reaction 51 min, wherein the cellulose of aldehyde radical nanocrystalline with solid-to-liquid ratio silver ammino solution be 1:150 g/mL, after question response finishes, with deionized water diluting reaction product, the repeatedly centrifugal inorganic ions that removes, then by dispersion liquid vacuumize, obtain Nano Silver-cellulose nano-crystal hybrid material;

Nano Silver-cellulose nano-crystal hybrid material is joined in the ethyl acetate solution of polycaprolactone (PCL), be warming up to 48 DEG C, fully stir, obtain the electrostatic spinning liquid of transparent homogeneous, wherein PCL and the mass fraction sum of Nano Silver-cellulose nano-crystal hybrid material in mixed liquor are that the mass ratio of 20%, PCL and Nano Silver-cellulose nano-crystal hybrid material is 99:1;

Extract above-mentioned spinning solution with syringe and carry out electrostatic spinning, spinning parameter is that operating voltage 22KV, receiving range are that 25cm, spinning speed are 0.6ml/h, the spinning time is 5h, then vacuumize 16h at room temperature, can obtain the antibacterial medical dressing film of loading nano silvery-cellulose nano-crystal hybrid material.

The surface topography of antibacterial medical dressing film is observed through ESEM (SEM), finds that Nano Silver-cellulose nano-crystal hybrid material is dispersed in PCL matrix preferably, and fibre diameter is 340nm; Material records the purer PCL ratio of its tensile strength through micro-control electronic universal tester again and has improved 83%, and material is again after thermogravimetric analyzer test, and the purer PCL ratio of its maximum heat degradation temperature has improved 24 oc, product again after antibacterial experiment, find its to the antibiotic rate of Escherichia coli and staphylococcus aureus respectively up to 99.5% and 99.8%.

Embodiment 4

Cotton is added in formic acid-hydrochloric acid solution, at 45 DEG C of reaction 6 h, wherein the solid-to-liquid ratio of cotton and the nitration mixture aqueous solution is 1:60 g/mL, formic acid in the nitration mixture aqueous solution (7 mol/L) is 5:1 with the volume ratio of hydrochloric acid (4 mol/L), after question response finishes, deionized water washed reaction product is to neutral, and the cellulose that can obtain aldehyde radical is nanocrystalline; Again by nanocrystalline the cellulose of this aldehyde radical liquor argenti nitratis ophthalmicus that adds 3 mol/L, at 92 DEG C of reaction 15 min, wherein the cellulose of aldehyde radical nanocrystalline with solid-to-liquid ratio liquor argenti nitratis ophthalmicus be 1:350 g/mL, after question response finishes, with deionized water diluting reaction product, the repeatedly centrifugal inorganic ions that removes, then by dispersion liquid vacuumize, obtain Nano Silver-cellulose nano-crystal hybrid material;

Nano Silver-cellulose nano-crystal hybrid material is joined in the dichloromethane solution of polycaprolactone (PCL), be warming up to 45 DEG C, fully stir, obtain the electrostatic spinning liquid of transparent homogeneous, wherein PCL and the mass fraction sum of Nano Silver-cellulose nano-crystal hybrid material in mixed liquor are that the mass ratio of 12%, PCL and Nano Silver-cellulose nano-crystal hybrid material is 18:1;

Extract above-mentioned spinning solution with syringe and carry out electrostatic spinning, spinning parameter is that operating voltage 28KV, receiving range are that 35cm, spinning speed are 0.4ml/h, the spinning time is 6h, then vacuumize 18h at room temperature, can obtain the antibacterial medical dressing film of loading nano silvery-cellulose nano-crystal hybrid material.

The surface topography of antibacterial medical dressing film is observed through ESEM (SEM), finds good being dispersed in PCL matrix of Nano Silver-cellulose nano-crystal hybrid material, and fibre diameter is 300nm; Material records the purer PCL ratio of its tensile strength through micro-control electronic universal tester again and has improved 93%, material is again after thermogravimetric analyzer test, the purer PCL ratio of its maximum heat degradation temperature has improved 21 DEG C, product again after antibacterial experiment, find its to the antibiotic rate of Escherichia coli and staphylococcus aureus respectively up to 99.9% and 99.8%.

Embodiment 5

Bamboo fibre is added in formic acid-hydrochloric acid solution, at 70 DEG C of reaction 8 h, wherein the solid-to-liquid ratio of bamboo fibre and the nitration mixture aqueous solution is 1:60 g/mL, formic acid in the nitration mixture aqueous solution (3 mol/L) is 4:1 with the volume ratio of hydrochloric acid (8 mol/L), after question response finishes, deionized water washed reaction product is to neutral, and the cellulose that can obtain aldehyde radical is nanocrystalline; Again by nanocrystalline the cellulose of this aldehyde radical silver ammino solution that adds 2 mol/L, at 80 DEG C of reaction 45 min, wherein the cellulose of aldehyde radical nanocrystalline with solid-to-liquid ratio silver ammino solution be 1:300 g/mL, after question response finishes, with deionized water diluting reaction product, the repeatedly centrifugal inorganic ions that removes, then by dispersion liquid vacuumize, obtain Nano Silver-cellulose nano-crystal hybrid material;

Nano Silver-cellulose nano-crystal hybrid material is joined to poly-(Ru Suan – glycolic acid) in the acetone soln of copolymer (PLGA), be warming up to 65 DEG C, fully stir, obtain the electrostatic spinning liquid of transparent homogeneous, wherein PLGA and the mass fraction sum of Nano Silver-cellulose nano-crystal hybrid material in mixed liquor are that the mass ratio of 7%, PLGA and Nano Silver-cellulose nano-crystal hybrid material is 49:1;

Extract above-mentioned spinning solution with syringe and carry out electrostatic spinning, spinning parameter is that operating voltage 25KV, receiving range are that 24cm, spinning speed are 1.2ml/h, the spinning time is 2.5h, then vacuumize 18h at room temperature, can obtain the antibacterial medical dressing film of loading nano silvery-cellulose nano-crystal hybrid material.

The surface topography of antibacterial medical dressing film is observed through ESEM (SEM), finds good being dispersed in PLGA matrix of Nano Silver-cellulose nano-crystal hybrid material, and fibre diameter is 540nm; Material records the purer PLGA ratio of its tensile strength through micro-control electronic universal tester again and has improved 54%, and material is again after thermogravimetric analyzer test, and the purer PLGA ratio of its maximum heat degradation temperature has improved 13 oc, product again after antibacterial experiment, find its to the antibiotic rate of Escherichia coli and staphylococcus aureus respectively up to 99.0% and 99.2%.

Embodiment 6

Wood pulp is added in formic acid-hydrochloric acid solution, at 55 DEG C of reaction 15 h, wherein the solid-to-liquid ratio of wood pulp and the nitration mixture aqueous solution is 1:80 g/mL, formic acid in the nitration mixture aqueous solution (8 mol/L) is 9:1 with the volume ratio of hydrochloric acid (6 mol/L), after question response finishes, deionized water washed reaction product is to neutral, and the cellulose that can obtain aldehyde radical is nanocrystalline; Again by nanocrystalline the cellulose of this aldehyde radical liquor argenti nitratis ophthalmicus that adds 0.5 mol/L, at 60 DEG C of reaction 40 min, wherein the cellulose of aldehyde radical nanocrystalline with solid-to-liquid ratio liquor argenti nitratis ophthalmicus be 1:180 g/mL, after naturally cooling, with deionized water diluting reaction product, the repeatedly centrifugal inorganic ions that removes, then by dispersion liquid vacuumize, obtain Nano Silver-cellulose nano-crystal hybrid material;

Nano Silver-cellulose nano-crystal hybrid material is joined to chloroform-N of PLA (PLA), in N – dimethyl formamide solution, be warming up to 65 DEG C, fully stir, obtain the electrostatic spinning liquid of transparent homogeneous, wherein PLA and the mass fraction sum of Nano Silver-cellulose nano-crystal hybrid material in mixed liquor are that the mass ratio of 16%, PLA and Nano Silver-cellulose nano-crystal hybrid material is 5:1, chloroform and N, the mass ratio of N – dimethyl formamide is 3:1;

Extract above-mentioned spinning solution with syringe and carry out electrostatic spinning, spinning parameter is that operating voltage 30KV, receiving range are that 30cm, spinning speed are 1.2ml/h, the spinning time is 3h, then vacuumize 12h at room temperature, can obtain the antibacterial medical dressing film of loading nano silvery-cellulose nano-crystal hybrid material.

The surface topography of antibacterial medical dressing film is observed through ESEM (SEM), finds good being dispersed in PLA matrix of Nano Silver-cellulose nano-crystal hybrid material, and fibre diameter is 400nm; Material records the purer PLA ratio of its tensile strength through micro-control electronic universal tester again and has improved 89%, and material is again after thermogravimetric analyzer test, and the purer PLA ratio of its maximum heat degradation temperature has improved 28 oc, product again after antibacterial experiment, find its to the antibiotic rate of Escherichia coli and staphylococcus aureus respectively up to 100% and 100%.

Claims (10)

1. the antibacterial medical dressing film of loading nano silvery-cellulose nano-crystal hybrid material, its composition comprises: biological degradation polyalcohol and Nano Silver-cellulose nano-crystal hybrid material, wherein the mass ratio of biological degradation polyalcohol and Nano Silver-cellulose nano-crystal hybrid material is 3 – 99:1.
2. the antibacterial medical dressing film of a kind of loading nano silvery-cellulose nano-crystal hybrid material according to claim 1, is characterized in that: described biological degradation polyalcohol is PHBV, PLA, polycaprolactone or poly-(Ru Suan – glycolic acid) copolymer.
3. the antibacterial medical dressing film of a kind of loading nano silvery-cellulose nano-crystal hybrid material according to claim 1, it is characterized in that: in described Nano Silver-cellulose nano-crystal hybrid material, cellulose is nanocrystalline is bar-shaped or ellipticity, its particle diameter is 10 – 300 nm, and the particle diameter of Nano Silver is 8 – 45 nm.
4. a preparation method for the antibacterial medical dressing film of loading nano silvery-cellulose nano-crystal hybrid material as claimed in claim 1, comprising:
(1) cellulosic material is joined in the nitration mixture aqueous solution of formic acid-hydrochloric acid, in 90 DEG C of reaction 2 – 15 h of 40 –, after question response finishes, with deionized water washed reaction product, to neutral, the cellulose that obtains aldehyde radical is nanocrystalline; Then by nanocrystalline the cellulose of this aldehyde radical silver salt solution that joins 0.01 – 3 mol/L, in 95 DEG C of reaction 10 – 60 min of 50 –, after naturally cooling, with deionized water diluting reaction product, centrifugal postlyophilization or vacuumize, obtain Nano Silver-cellulose nano-crystal hybrid material;
(2) above-mentioned hybrid material and biological degradation polyalcohol are joined after organic solvent, be warming up to 80 DEG C of 30 –, fully stir, obtain the electrostatic spinning liquid of transparent homogeneous, wherein biological degradation polyalcohol and the mass fraction sum of Nano Silver-cellulose nano-crystal hybrid material in electrostatic spinning liquid are 5 – 20%, and the mass ratio of biological degradation polyalcohol and Nano Silver-cellulose nano-crystal hybrid material is 3 – 99:1;
(3) extract above-mentioned spinning solution with syringe and carry out electrostatic spinning, spinning parameter is that operating voltage 5 – 30KV, receiving range are that 5 – 50cm, spinning speed are 0.1 – 3ml/h, the spinning time is 1 – 12h, then at room temperature vacuumize 2 – 24h, obtain the antibacterial medical dressing film of loading nano silvery-cellulose nano-crystal hybrid material.
5. preparation method according to claim 4, is characterized in that: in step (1), described cellulosic material is one or more in flax fibre, microcrystalline cellulose, cotton, bamboo fibre, wood pulp.
6. preparation method according to claim 4, is characterized in that: in step (1), the solid-to-liquid ratio of cellulosic material and described formic acid-hydrochloric acid nitration mixture aqueous solution is 1:10 – 80 g/mL; In the formic acid-hydrochloric acid nitration mixture aqueous solution adopting, the volume ratio of formic acid and hydrochloric acid is 2 – 9:1, and before configuration, the concentration of formic acid is 3 – 10 mol/L, and before configuration, the concentration of hydrochloric acid is 1 – 10 mol/L.
7. preparation method according to claim 4, is characterized in that: in step (1), described silver salt solution is liquor argenti nitratis ophthalmicus, silver ammino solution or nitrogenize silver solution.
8. preparation method according to claim 4, is characterized in that: in step (1), the cellulose of described aldehyde radical nanocrystalline with solid-to-liquid ratio silver salt solution be 1:20 – 500 g/mL.
9. preparation method according to claim 4, it is characterized in that: in step (2), described organic solvent is N, N – dimethyl formamide, N, one or more in N – dimethylacetylamide, oxolane, carrene, 1,2 – chloroethanes, chloroform, acetone, diethylene glycol dimethyl ether or ethyl acetate.
10. preparation method according to claim 4, is characterized in that: in step (3), the fibre diameter of described antibacterial medical dressing film is 20 nm – 800 nm, and thickness is 100nm – 2000 μ m.
CN201410291338.7A 2014-06-26 2014-06-26 Antibacterial medical dressing film carrying nano-silver and cellulose nanocrystalline hybrid materials and preparation method thereof CN104153120A (en)

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CN105821659A (en) * 2016-04-28 2016-08-03 东华大学 Antibacterial finishing agent and preparation method and antibacterial application thereof
WO2017122224A1 (en) * 2016-01-12 2017-07-20 Council Of Scientific & Industrial Research A nanobiocomposite formulation for wound healing and a process for the preparation thereof
CN107412881A (en) * 2017-08-01 2017-12-01 浙江理工大学 A kind of preparation method of composite strengthening artificial skin receptor
CN108893871A (en) * 2018-06-20 2018-11-27 北京服装学院 A kind of high-performance biology group compound film and preparation method thereof

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Application publication date: 20141119