CN105646923B - A kind of preparation method of the nano-cellulose antibacterial film of loading nano silvery particle - Google Patents
A kind of preparation method of the nano-cellulose antibacterial film of loading nano silvery particle Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of the nano-cellulose antibacterial film of loading nano silvery particle, in the method with 2,2,6,6 tetramethyl piperidine, 1 oxygen radical, sodium bromide and sodium hypochlorite handle cellulosic material, and then reaction prepares the nano-cellulose for loading silver particles under water bath condition.Solve the problems, such as that silver particles disperse uneven in nano-cellulose and easily reunite according to the method for the present invention, and unused any specific apparatus and toxic reagent, the nano-cellulose antibacterial film of gained loading nano silvery particle have broad application prospects in the fresh-keeping equal industrial fields of antibacterial wound dressing and food storage.
Description
Technical field
The present invention relates to organic/inorganic composite material fields, in particular to a kind of nanometer of loading nano silvery particle
The preparation method of cellulose antibacterial film.
Background technology
Cellulose is the recyclability natural polymers that content is most abundant on the earth, is widely present in timber, bamboo
In the natural plant materials such as material, linen-cotton class.Due to the crisis of resource and environment, the development and utilizations of cellulose and its derivates by
The extensive concern of domestic and foreign scholars is arrived.Nano-cellulose refers to cellulose products of the diameter between 1~100nm, due to it
Have the characteristics that good biocompatibility, biodegradable, intensity is high, rigidity is big, excellent optical performance, light weight and by extensive
Concern.There is a large amount of hydroxyl on nano-cellulose surface, can combinations such as inorganic, organic material with other, obtain different properties
Functional composite material, such as magnetism, antibiotic property, electric conductivity material.
Nano-cellulose thin-film material has good mechanical property.Mainly there are two aspect reasons, first, cellulose surface
There is great amount of hydroxy group, when cellulose becomes nano-cellulose by vertical peeling, has more hydroxyls and be exposed, between hydroxyl
Interact to form a large amount of hydrogen bonds；Secondly, for the diameter of nano-cellulose between 1~100nm, length is several microns, is had greatly
Draw ratio, during forming nano-cellulose film, nano-cellulose can mutually wind, interweave, therefore Nanowire
The plain film of dimension has good mechanical property.
Nano silver particles are that a kind of grain size is nano level metal simple-substance silver, have stable physicochemical property and potent
Sterilizing ability.Have to pathogenic microorganisms such as staphylococcus aureus, Escherichia coli and streptococcus albus and inhibits and kills
Effect, and nano silver particles are not easy that microorganism is made to develop immunity to drugs it, can form the anti-biotic material of physicochemical property stabilization.
Antibacterial based on the good biocompatibility of nano-cellulose, excellent mechanical property and nano silver particles is lived
Property, the two can be combined and prepare bio-medical and food fresh keeping material with antibiotic property.How to prepare equably to divide
The nano silver particles being dispersed in nano-cellulose network are one of correlative study urgent problems.Nano silver particles at present
Preparation method mainly has photoreduction met hod, electrochemical process and chemical reduction method etc..Photoreduction met hod is usually using ultraviolet light as sharp
Send out Ag+The wavelength of the light source of reduction, incident light source determines the pattern of silver particles；Electrochemical process generally use electrochemistry sacrifices sun
Pole method makes deposition of silver prepare nano silver particles in cathode by raw material of metallic silver；Chemical reduction method be typically be added sodium borohydride,
The reducing agents such as sodium citrate, ascorbic acid make Ag+It is reduced into nano silver particles.
However in the preparation method of the above-mentioned prior art, often there are following problems：Gained nano silver particles exist
It is unevenly distributed in nano-cellulose, easily reunites；Photoreduction met hod and electrochemical process operation are more complex, need to use special instrument
Device, chemical reduction method need to use toxic reagent as reducing agent, not only of high cost and can cause to endanger to the health of operating personnel
Evil.Therefore it needs to develop a kind of new preparation method, with efficiently against the above-mentioned problems of the prior art.
Invention content
In view of this, the present invention provides a kind of preparation sides of the nano-cellulose antibacterial film of loading nano silvery particle
Method solves the problems, such as that silver particles disperse uneven in nano-cellulose and easily reunite, and the preparation method is not used
Any specific apparatus and toxic reagent, the nano-cellulose antibacterial film of gained loading nano silvery particle antibacterial wound dressing with
And the fresh-keeping equal industrial fields of food storage have broad application prospects.
In order to achieve the above objectives, according to an aspect of the invention, there is provided a kind of Nanowire of loading nano silvery particle
The preparation method of the plain antibacterial film of dimension, the preparation method include the following steps：
(1) cellulosic material is crushed with pulverizer；
(2) comminuted fibres element raw material is immersed containing 2,2,6,6- tetramethyl piperidine -1- oxygen radicals (TEMPO), bromine
In the distilled water for changing sodium and sodium hypochlorite, oxidation processes are carried out, wherein the comminuted fibres element raw material based on 100 parts by weight,
Use the distilled water of 9000 parts by weight, the sodium bromide of 10 parts by weight, the concentration of the parts by weight of TEMPO and 5 to 10 of 0.8 parts by weight
For the liquor natrii hypochloritis of 1mol/L, the oxidation processes reaction is stirred at room temperature 6 to 10h, stir speed (S.S.) be 400 to
The pH of reaction system in reaction process, is adjusted to every half an hour with the sodium hydroxide solution of a concentration of 1mol/L by 800rpm
About 10；
(3) it is above-mentioned after reaction, by being centrifugally separating to obtain the cellulose of oxidation, and be added water prepare mass fraction be
0.5%~1.0% oxycellulose water slurry；
(4) above-mentioned gained oxycellulose water slurry is subjected to high-speed stirred and supersonic cell pulverization process, obtained
To nano-cellulose water slurry,
(5) silver nitrate aqueous solution of a concentration of 0.5mol/L is added in above-mentioned gained nano-cellulose water slurry, mixes
1h is stirred under dark conditions after closing uniformly, heats 0.5~1h, cellulose aqueous suspension under 60~100 DEG C of water bath conditions later
Liquid color becomes light brown from white, obtains the nano-cellulose water slurry of load silver particles；
(6) the nano-cellulose water slurry that above-mentioned gained loads to silver particles is filtered, is rinsed, to obtain thickness equal for drying
The nano-cellulose antibacterial film of even, smooth surface loading nano silvery particle.
Wherein, the preparation method of oxycellulose can be in the step (2)：
Will 1g cellulosic materials immerse 90ml distilled water in, sequentially add 0.1g sodium bromides, 0.008gTEMPO and 5~
The liquor natrii hypochloritis of a concentration of 1mol/L of 10ml, is stirred at room temperature 6~10h, and stir speed (S.S.) is 400~800rpm, reaction
In the process, the pH of reaction system is adjusted to 10 with the sodium hydroxide solution of a concentration of 1mol/L every half an hour, reaction is completed
Afterwards by being centrifugally separating to obtain oxycellulose.
Preferably, the rotating speed of step (4) the high speed blender be 12000~15000rpm, processing time be 10~
15min；The power of ultrasonication is 600~1000W, and sonication treatment time is 20~30min.
Preferably, in the step (5), based on the nano-cellulose of 100 parts by weight, the addition of silver nitrate aqueous solution is
30 to 50 parts by weight.
Preferably, Suction filtration device used is solvent filter in the step (6), filter membrane is the vinegar that aperture is 0.45 μm
Acid cellulose film filters into film under conditions of vacuum degree is -0.096~-0.098MPa, distilled water flushing is used in combination three times,
Since film has good wet strength, it can directly take off from filter membrane, be dried in 105 DEG C of baking ovens later.
According to another aspect of the present invention, a kind of nano-cellulose antibacterial film of loading nano silvery particle is provided,
The nano-cellulose antibacterial film of the loading nano silvery particle is prepared by method made above.
Advantageous effect
Compared with prior art, beneficial outcomes of the invention are：Nanofiber prepared by the preparation method invented at all
Simple substance silver particles are formed in plain network, the nano-cellulose that loading nano silvery particle has been obtained finally by the method for suction filtration is anti-
Bacterium film solves the problems, such as that nano silver particles are unevenly distributed in cellulose network and easily reunite；In preparation process not
Using any specific apparatus and toxic reagent, cost is reduced, and is good for the environment and the health of operating personnel.
Description of the drawings
TEMPO oxidation reaction schematic diagrams in the step of Fig. 1 is the preparation method according to the present invention (2)；
Fig. 2 is the transmission electron microscope of the nano-cellulose film of the loading nano silvery particle prepared according to the embodiment of the present invention 1
Figure；
Fig. 3 be according to the nano-celluloses of unsupported nano silver particles in the embodiment of the present invention 1 (under) and loaded nanometer
Silver particles nano-cellulose (on) film X-ray diffractogram；
Fig. 4 is the EDS power spectrums point of the nano-cellulose film of the loading nano silvery particle prepared according to the embodiment of the present invention 1
Analyse spectrogram；
Fig. 5 is antibacterial activity result of the film to staphylococcus aureus of the nano-cellulose of unsupported nano silver particles
Photo；
Fig. 6 is photograph of the film to the antibacterial activity results of Escherichia coli of the nano-cellulose of unsupported nano silver particles
Piece；
Fig. 7 is antibacterial activity result of the film to staphylococcus aureus of the nano-cellulose of loading nano silvery particle
Photo；
Fig. 8 is photo of the film to the antibacterial activity results of Escherichia coli of the nano-cellulose of loading nano silvery particle；
Fig. 9 is the transmission electron microscope picture of the nano-cellulose of the loading nano silvery particle obtained by comparative example 4 of the present invention.
Specific implementation mode
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims in the term that uses should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to meaning corresponding with the technical aspect of the present invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
2,2,6,6- tetramethyl piperidine -1- oxygen radicals (TEMPO), bromination are used in preparation in accordance with the present invention
Sodium and sodium hypochlorite handle cellulosic material.The wherein possible mechanism of TEMPO oxidation reactions is as shown in Fig. 1,
Hydroxyl on six carbon of cellulose is oxidized to carboxyl and/or aldehyde radical by TEMPO oxidation systems, this reaction makes cellulose surface part
Hydroxyl is aoxidized, and hydrogen bond content is reduced, and the binding force between fiber reduces, and the in addition generation of carboxyl improves the water-soluble of cellulose
Property, be conducive to the nanosizing of cellulose.
- COONa can be obtained by the reaction in the carboxyl of formation with sodium hydroxide, wherein the sodium hydroxide can regard bromine as
Change the product that sodium strong acid weak base salt dissolves in water.Then, Na is utilized+With Ag+Ion exchange in nano-cellulose six
Generation-COOAg on carbon, and the aldehyde radical formed is due to reproducibility, it can be by Ag+Reduction becomes Ag.But reaction temperature
The generation of Ag simple substance is also had a major impact, when reaction temperature be less than 60 DEG C when, reaction be not susceptible to or relatively slowly；When temperature height
When 100 DEG C, Ag is easy to happen reunion.
The addition of liquor natrii hypochloritis and reaction time are to carboxyl and aldehyde in gained oxycellulose in reaction process
The content of base has larger impact, and the addition of sodium hypochlorite is very few or the reaction time is too short can make aldehyde group content in product excessively high,
And carboxyl-content is very few, but the addition of sodium hypochlorite is excessive or the reaction time is long that aldehyde group content in product can be made very few, and
Carboxyl-content is excessive, can be impacted to subsequent reactions.Therefore adjusting the addition of liquor natrii hypochloritis can effectively control
The reactivity of nano-cellulose processed.
The mass fraction of oxycellulose water slurry is preferred in (3) the preparation method according to the present invention the step of
It is 0.5%~1.0%.When oxycellulose water slurry excessive concentration or it is too low can influence subsequent mechanical processing effect,
Excessive concentration, such as higher than 1.0%, the mechanical strength for acting on unit mass cellulose can be made to reduce, and concentration is too low, such as
Less than 0.5%, mutual friction between fiber, collision can be reduced, treatment effect can be equally influenced.
Obtained oxycellulose water slurry carried out in (4) the preparation method according to the present invention the step of high
Speed stirring and supersonic cell pulverization process, obtain nano-cellulose water slurry, thin by high-speed stirred and ultrasonic wave
After born of the same parents' pulverization process, make fiber vertical peeling, obtain nano-cellulose of the diameter within 100nm, nano-cellulose can be equal
Even is dispersed in water, almost without precipitation；
It is added in gained nano-cellulose water slurry in (5) the preparation method according to the present invention the step of suitable
The silver nitrate aqueous solution of a concentration of 0.5mol/L is measured, stirs 1h under dark conditions after mixing, later in 60~100 DEG C of water
0.5~1h is heated under the conditions of bath, cellulose color becomes light brown from white, and the nano-cellulose water for obtaining load silver particles is outstanding
Supernatant liquid.The very few anti-microbial property that can lead to gained sample of the addition of wherein silver nitrate is weaker, and addition is excessively easily caused and received
The reunion of rice silver particles.
Embodiment
Following embodiment is enumerated only as the example of embodiment of the present invention, does not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that modification in the range of without departing from essence of the invention and design each falls within the present invention
Protection domain.
Embodiment 1
(1) 2g cotton linter pulpboards are crushed, immerses in 180ml distilled water, sequentially adds 0.2g sodium bromides, 0.016g
10h, stir speed (S.S.) 400rpm is stirred at room temperature in the liquor natrii hypochloritis of a concentration of 1mol/L of TEMPO and 10ml, reaction
In the process, the pH of reaction system is adjusted to about 10 with the sodium hydroxide solution of a concentration of 1mol/L every half an hour, reaction
After the completion by being centrifugally separating to obtain oxycellulose, it is respectively 0.59mmol g to measure its carboxyl and aldehyde group content-1With
0.33mmol g-1.Then the oxycellulose of preparation is dispersed in water, it is fine prepares the oxidation that 200ml mass fractions are 0.5%
The plain water slurry of dimension；
(2) above-mentioned gained oxycellulose water slurry is stirred into 10min, Zhi Houfang under the conditions of rotating speed is 15000rpm
Enter in ultrasonic cell disruptor, processing 20min obtains nano-cellulose water slurry under conditions of power is 1000W；
(3) silver nitrate of a concentration of 0.5mol/L of 1ml is added in nano-cellulose water slurry obtained by above-mentioned steps (2)
Aqueous solution stirs 1h under dark conditions after mixing, heats 1.0h in 60 DEG C of water-baths later, by Ag+It is reduced to Ag, is obtained
To the nano-cellulose water slurry of load silver particles；
(4) above-mentioned gained suspension is taken out with solvent filter under conditions of vacuum degree is -0.096~-0.098MPa
Film is filtered into, three times with distilled water flushing, and is taken off from filter membrane, is dried in 105 DEG C of baking ovens later, it is equal to obtain thickness
The nano-cellulose antibacterial film of even, smooth surface loading nano silvery particle.
In addition, as a comparison, the present embodiment also obtains the nanometer of unsupported silver particles by way of without step (3)
Cellophane.
The nano-cellulose water slurry prepared according to the method for the present embodiment does not precipitate, and illustrates the nanometer being prepared
Cellulose is evenly dispersed in water, and granularity is minimum, and in addition solution becomes shallow palm fibre from white after the processing of overload silver particles
Color illustrates that silver particles are supported on nano-cellulose while the granularity of silver particles itself is minimum.
Attached drawing 2 is the transmission electron microscope picture according to the nano-cellulose film of loading nano silvery particle manufactured in the present embodiment.
It can be seen from the figure that the diameter of obtained silver particles is about tens nanometers, particle diameter distribution is more uniform.Nanometer silver granuel simultaneously
Son can be evenly distributed in nano-cellulose network, almost without agglomeration, it was demonstrated that preparation in accordance with the present invention
It can effectively solve the problems, such as that nano silver particles are unevenly distributed in nano-cellulose and easily reunite.
Attached drawing 3 be unsupported nano silver particles in the present embodiment nano-cellulose (under) and loaded nano silver particles
Nano-cellulose (on) film X-ray diffractogram.It can be seen that the nanometer with unsupported nano silver particles from XRD diagram
Cellophane is compared, and has been loaded to have more in the XRD spectrum of the antibacterial film of the nano-cellulose of nano silver particles and has been showed 5 and spread out
Penetrate peak, respectively 38.14 °, 44.33 °, 64.51 °, 77.46 °, the data of silver particles on 81.62 °, with JCPDS cards 04-0783
Unanimously, it was demonstrated that be successfully prepared nano silver particles.
Attached drawing 4 is to be composed according to the EDS energy spectrum analysis of the nano-cellulose film of loading nano silvery particle manufactured in the present embodiment
Figure.Occur the energy spectral peak of apparent silver particles in spectrogram, further demonstrates the formation of silver particles.
Using the film of the antibacterial around-France nano-cellulose to the unsupported nano silver particles prepared in the present embodiment and negative
The film for having carried the nano-cellulose of nano silver particles carries out antibacterial activity survey to staphylococcus aureus and Escherichia coli respectively
Examination.Attached drawing 5 is antibacterial activity result of the film to staphylococcus aureus of the nano-cellulose of unsupported nano silver particles
Photo；Attached drawing 6 is photo of the film to the antibacterial activity results of Escherichia coli of the nano-cellulose of unsupported nano silver particles；
Attached drawing 7 is photo of the film to the antibacterial activity result of staphylococcus aureus of the nano-cellulose of loading nano silvery particle；
Attached drawing 8 is photo of the film to the antibacterial activity results of Escherichia coli of the nano-cellulose of loading nano silvery particle.From attached drawing 5
And it can be seen that there is not antibacterial ring size around the film of the nano-cellulose of unsupported nano silver particles in 6, it was demonstrated that it does not have
There is antibacterial activity；Opposite, it can be seen that around the film of the nano-cellulose of loading nano silvery particle from attached drawing 7 and 8
There is apparent antibacterial ring size, it was demonstrated that its antibacterial activity can obtain it to staphylococcus aureus and Escherichia coli by measuring
Antibacterial ring width be respectively 3.8mm and 2.9mm.
Embodiment 2
(1) 2g cotton linter pulpboards are crushed, immerses in 180ml distilled water, sequentially adds 0.2g sodium bromides, 0.016g
8h, stir speed (S.S.) 600rpm is stirred at room temperature in the liquor natrii hypochloritis of a concentration of 1mol/L of TEMPO and 15ml, reaction
In the process, the pH of reaction system is adjusted to about 10 with the sodium hydroxide solution of a concentration of 1mol/L every half an hour, reaction
After the completion by being centrifugally separating to obtain oxycellulose, carboxyl and aldehyde group content are respectively 0.66mmol g-1And 0.23mmol
g-1.Then the oxycellulose of preparation is dispersed in water, it is outstanding prepares the oxycellulose water that 125ml mass fractions are 0.8%
Supernatant liquid；
(2) above-mentioned oxycellulose water slurry is stirred into 15min under the conditions of rotating speed is 12000rpm, be put into later super
In sound wave cell disruptor, processing 30min obtains nano-cellulose water slurry under conditions of power is 800W；
(3) nitric acid of a concentration of 0.5mol/L of 0.8ml is added in nano-cellulose water slurry obtained by above-mentioned steps (2)
Silver-colored aqueous solution stirs 1h under dark conditions after mixing, heats 0.5h in 80 DEG C of water-baths later, by Ag+Ag is reduced to,
Obtain the nano-cellulose water slurry of load silver particles；
(4) by suspension solvent filter obtained by above-mentioned steps in the condition that vacuum degree is -0.096~-0.098MPa
Lower suction filtration is used in combination distilled water flushing to be taken off from filter membrane three times, is dried in 105 DEG C of baking ovens later, obtain thickness at film
Uniformly, the nano-cellulose antibacterial film of the loading nano silvery particle of smooth surface.
According to same antibacterial around-France test antibacterial activity in embodiment 1.As a result the load nanometer obtained in the present embodiment
The nano-cellulose antibacterial film of silver particles to the antibacterial ring width of staphylococcus aureus and Escherichia coli be respectively 3.6mm and
2.7mm。
Embodiment 3
(1) 2g cotton linter pulpboards are crushed, immerses in 180ml distilled water, sequentially adds 0.2g sodium bromides, 0.016g
6h, stir speed (S.S.) 800rpm is stirred at room temperature in the liquor natrii hypochloritis of a concentration of 1mol/L of TEMPO and 20ml, reaction
In the process, the pH of reaction system is adjusted to 10 with the sodium hydroxide solution of a concentration of 1mol/L every half an hour, reaction is completed
Afterwards by being centrifugally separating to obtain oxycellulose, carboxyl and aldehyde group content are respectively 0.70mmol g-1With 0.20mmol g-1。
Then the oxycellulose of preparation is dispersed in water, prepares the oxycellulose aqueous suspension that 100ml mass fractions are 1.0%
Liquid；
(2) above-mentioned oxycellulose water slurry is stirred into 10min under the conditions of rotating speed is 15000rpm, be put into later super
In sound wave cell disruptor, processing 25min obtains nano-cellulose water slurry under conditions of power is 1000W；
(3) nitric acid of a concentration of 0.5mol/L of 0.6ml is added in nano-cellulose water slurry obtained by above-mentioned steps (2)
Silver-colored aqueous solution stirs 1h under dark conditions after mixing, heats 0.5h in 100 DEG C of water-baths later, by Ag+It is reduced to
Ag obtains the nano-cellulose water slurry of load silver particles；
(4) by suspension solvent filter obtained by above-mentioned steps in the condition that vacuum degree is -0.096~-0.098MPa
Lower suction filtration three times with distilled water flushing, and is taken off from filter membrane at film, is dried in 105 DEG C of baking ovens later, obtain thickness
Uniformly, the nano-cellulose antibacterial film of the loading nano silvery particle of smooth surface.
According to same antibacterial around-France test antibacterial activity in embodiment 1.As a result the load nanometer obtained in the present embodiment
The nano-cellulose antibacterial film of silver particles to the antibacterial ring width of staphylococcus aureus and Escherichia coli be respectively 3.3mm and
2.4mm。
Embodiment 4
(1) by 2g bleached sulphate needlebush pulpboards crush, immerse 180ml distilled water in, sequentially add 0.2g sodium bromides,
The liquor natrii hypochloritis of a concentration of 1mol/L of 0.016g TEMPO and 10ml, is stirred at room temperature 8h, and stir speed (S.S.) is
The pH of reaction system in reaction process, is adjusted to every half an hour with the sodium hydroxide solution of a concentration of 1mol/L by 600rpm
10, by being centrifugally separating to obtain oxycellulose after the completion of reaction, it is respectively 0.50mmol g to measure its carboxyl and aldehyde group content-1
With 0.28mmol g-1.Then the oxycellulose of preparation is dispersed in water, prepares the oxidation that 200ml mass fractions are 0.5%
Aqueous cellulosic suspension；
(2) above-mentioned oxycellulose water slurry is stirred into 15min under the conditions of rotating speed is 10000rpm, be put into later super
In sound wave cell disruptor, processing 30min obtains nano-cellulose water slurry under conditions of power is 600W；
(3) nitre of a concentration of 0.5mol/L of 1ml is added in nano-cellulose water slurry obtained by above-mentioned steps step (2)
Sour silver aqueous solution, 1h is stirred under dark conditions, heats 0.5h in 90 DEG C of water-baths later, after mixing by Ag+It is reduced to
Ag obtains the nano-cellulose water slurry of load silver particles；
(4) by suspension solvent filter obtained by above-mentioned steps in the condition that vacuum degree is -0.096~-0.098MPa
Lower suction filtration three times with distilled water flushing, and is taken off from filter membrane at film, is dried in 105 DEG C of baking ovens later, obtain thickness
Uniformly, the nano-cellulose antibacterial film of the loading nano silvery particle of smooth surface.
According to same antibacterial around-France test antibacterial activity in embodiment 1.As a result the load nanometer obtained in the present embodiment
The nano-cellulose antibacterial film of silver particles to the antibacterial ring width of staphylococcus aureus and Escherichia coli be respectively 3.7mm and
2.9mm。
Embodiment 5
(1) by 2g bleached sulphate needlebush pulpboards crush, immerse 180ml distilled water in, sequentially add 0.2g sodium bromides,
The liquor natrii hypochloritis of a concentration of 1mol/L of 0.016g TEMPO and 15ml, is stirred at room temperature 5h, and stir speed (S.S.) is
The pH of reaction system in reaction process, is adjusted to every half an hour with the sodium hydroxide solution of a concentration of 1mol/L by 800rpm
10, by being centrifugally separating to obtain oxycellulose after the completion of reaction, it is respectively 0.63mmol g to measure its carboxyl and aldehyde group content-1
With 0.24mmol g-1.Then the oxycellulose of preparation is dispersed in water, prepares the oxidation that 125ml mass fractions are 0.8%
Aqueous cellulosic suspension；
(2) above-mentioned oxycellulose water slurry is stirred into 15min under the conditions of rotating speed is 12000rpm, be put into later super
In sound wave cell disruptor, processing 25min obtains nano-cellulose water slurry under conditions of power is 800W；
(3) it is added a concentration of 0.5mol/L's of 0.8ml in nano-cellulose water slurry obtained by above-mentioned steps step (2)
Silver nitrate aqueous solution stirs 1h under dark conditions after mixing, heats 0.5h in 100 DEG C of water-baths later, by Ag+Reduction
For Ag, the nano-cellulose water slurry of load silver particles is obtained；
(4) by suspension solvent filter obtained by above-mentioned steps in the condition that vacuum degree is -0.096~-0.098MPa
Lower suction filtration three times with distilled water flushing, and is taken off from filter membrane at film, is dried in 105 DEG C of baking ovens later, obtain thickness
Uniformly, the nano-cellulose antibacterial film of the loading nano silvery particle of smooth surface.
According to same antibacterial around-France test antibacterial activity in embodiment 1.As a result the load nanometer obtained in the present embodiment
The nano-cellulose antibacterial film of silver particles to the antibacterial ring width of staphylococcus aureus and Escherichia coli be respectively 3.6mm and
2.8mm。
Embodiment 6
(1) by 2g bleached sulphate needlebush pulpboards crush, immerse 180ml distilled water in, sequentially add 0.2g sodium bromides,
The liquor natrii hypochloritis of a concentration of 1mol/L of 0.016g TEMPO and 20ml, is stirred at room temperature 6h, and stir speed (S.S.) is
The pH of reaction system in reaction process, is adjusted to every half an hour with the sodium hydroxide solution of a concentration of 1mol/L by 800rpm
10, by being centrifugally separating to obtain oxycellulose after the completion of reaction, carboxyl and aldehyde group content are respectively 0.75mmol g-1With
0.20mmol g-1.Then the oxycellulose of preparation is dispersed in water, it is fine prepares the oxidation that 100ml mass fractions are 1.0%
The plain water slurry of dimension；
(2) above-mentioned oxycellulose water slurry is stirred into 10min under the conditions of rotating speed is 15000rpm, be put into later super
In sound wave cell disruptor, processing 20min obtains nano-cellulose water slurry under conditions of power is 1000W；
(3) nitric acid of a concentration of 0.5mol/L of 0.6ml is added in nano-cellulose water slurry obtained by above-mentioned steps (2)
Silver-colored aqueous solution stirs 1h under dark conditions after mixing, heats 0.5h in 100 DEG C of water-baths later, by Ag+It is reduced to
Ag obtains the nano-cellulose water slurry of load silver particles；
(4) by suspension solvent filter obtained by above-mentioned steps in the condition that vacuum degree is -0.096~-0.098MPa
Lower suction filtration three times with distilled water flushing, and is taken off from filter membrane at film, is dried in 105 DEG C of baking ovens later, obtain thickness
Uniformly, the nano-cellulose antibacterial film of the loading nano silvery particle of smooth surface.
According to same antibacterial around-France test antibacterial activity in embodiment 1.As a result the load nanometer obtained in the present embodiment
The nano-cellulose antibacterial film of silver particles to the antibacterial ring width of staphylococcus aureus and Escherichia coli be respectively 3.2mm and
2.1mm。
Comparative example 1 (does not carry out TEMPO oxidation reactions)
1g bleached sulphate needlebush pulpboards are crushed, immerses in 99ml distilled water, 6h, stir speed (S.S.) is stirred at room temperature
For 800rpm；Above-mentioned aqueous cellulosic suspension is stirred into 15min under the conditions of rotating speed is 15000rpm, it is thin to be put into ultrasonic wave later
In born of the same parents' pulverizer, 20min is handled under conditions of power is 1000W.Due to not carrying out TEMPO oxidation processes, only at machinery
Reason cannot obtain nano-cellulose, therefore only obtain aqueous cellulosic suspension, and carboxyl and aldehyde group content are 0mmol g-1；
The silver nitrate aqueous solution of a concentration of 0.5mol/L of 1ml is added in above-mentioned gained aqueous cellulosic suspension, is hiding after mixing
1h is stirred under the conditions of light, heats 1.0h at 100 DEG C later, and cellulose does not become light brown from white, this is because fiber
Hydroxyl and carboxyl are not contained in element, therefore can not be by Ag+It is reduced to Ag.
Comparative example 2 (does not carry out mechanical treatment)
(1) 2g cotton linter pulpboards are crushed, immerses in 180ml distilled water, sequentially adds 0.2g sodium bromides, 0.016g
8h, stir speed (S.S.) 600rpm is stirred at room temperature in the liquor natrii hypochloritis of a concentration of 1mol/L of TEMPO and 15ml, reaction
In the process, the pH of reaction system is adjusted to 10 with the sodium hydroxide solution of a concentration of 1mol/L every half an hour, reaction is completed
Afterwards by being centrifugally separating to obtain oxycellulose, it is respectively 0.66mmol g to measure its carboxyl and aldehyde group content-1And 0.24mmol
g-1.Then the oxycellulose of preparation is dispersed in water, it is outstanding prepares the oxycellulose water that 125ml mass fractions are 0.8%
Supernatant liquid；
(2) silver nitrate of a concentration of 0.5mol/L of 0.8ml is added in the oxycellulose water slurry obtained by above-mentioned steps
Aqueous solution stirs 1h under dark conditions after mixing, heats 0.5h at 80 DEG C later, by Ag+It is reduced to Ag, is born
Carry the aqueous cellulosic suspension of silver particles.
Since the diameter of oxycellulose is other in the micron-scale, and the aperture for filtering cellulose acetate film used is 0.45 μm,
Therefore oxycellulose can block the hole of filter membrane in filter process, and moisture can not remove, and in order to solve the problems, such as this, be leaked with Bu Shi
The filter paper that bucket and aperture are 10~15 μm is filtered suspension, after the completion of filtering, three times with distilled water flushing, due to fiber
The wet strength of element is poor, cannot directly be taken off from filter paper, but the material obtained after drying is bonded together with filter paper, Bu Nengjin
Row subsequent experimental.
Comparative example 3 (reaction temperature is too low)
(1) 2g cotton linter pulpboards are crushed, immerses in 180ml distilled water, sequentially adds 0.2g sodium bromides, 0.016g
10h, stir speed (S.S.) 400rpm is stirred at room temperature in the liquor natrii hypochloritis of a concentration of 1mol/L of TEMPO and 10ml, reaction
In the process, the pH of reaction system is adjusted to 10 with the sodium hydroxide solution of a concentration of 1mol/L every half an hour, reaction is completed
Afterwards by being centrifugally separating to obtain oxycellulose, it is respectively 0.59mmol g to measure its carboxyl and aldehyde group content-1And 0.33mmol
g-1.Then the oxycellulose of preparation is dispersed in water, it is outstanding prepares the oxycellulose water that 200ml mass fractions are 0.5%
Supernatant liquid；
(2) above-mentioned gained oxycellulose water slurry is stirred into 10min, Zhi Houfang under the conditions of rotating speed is 15000rpm
Enter in ultrasonic cell disruptor, processing 20min obtains nano-cellulose water slurry under conditions of power is 1000W；
(3) silver nitrate of a concentration of 0.5mol/L of 1ml is added in nano-cellulose water slurry obtained by above-mentioned steps (2)
Aqueous solution stirs 1h under dark conditions after mixing, heats 1.0h in 40 DEG C of water-baths later, and acquired results are similar to pair
Ratio 1, cellulose does not become light brown from white, this may be since temperature is too low, be unfavorable for redox reaction into
Row.
Comparative example 4 (reaction temperature is excessively high)
(1) 2g cotton linter pulpboards are crushed, immerses in 180ml distilled water, sequentially adds 0.2g sodium bromides, 0.016g
10h, stir speed (S.S.) 400rpm is stirred at room temperature in the liquor natrii hypochloritis of a concentration of 1mol/L of TEMPO and 10ml, reaction
In the process, the pH of reaction system is adjusted to 10 with the sodium hydroxide solution of a concentration of 1mol/L every half an hour, reaction is completed
Afterwards by being centrifugally separating to obtain oxycellulose, it is respectively 0.59mmol g to measure its carboxyl and aldehyde group content-1And 0.33mmol
g-1.Then the oxycellulose of preparation is dispersed in water, it is outstanding prepares the oxycellulose water that 200ml mass fractions are 0.5%
Supernatant liquid；
(2) above-mentioned gained oxycellulose water slurry is stirred into 10min, Zhi Houfang under the conditions of rotating speed is 15000rpm
Enter in ultrasonic cell disruptor, processing 20min obtains nano-cellulose water slurry under conditions of power is 1000W；
(3) silver nitrate of a concentration of 0.5mol/L of 1ml is added in nano-cellulose water slurry obtained by above-mentioned steps (2)
Aqueous solution stirs 1h under dark conditions after mixing, heats 1.0h in 120 DEG C of oil baths later, by Ag+It is reduced to Ag.
Attached drawing 9 be gained load silver particles nano-cellulose water slurry TEM figure, as can be seen from the figure silver granuel molecular dispersivity compared with
Difference, and agglomeration has occurred.In vacuum degree it is -0.096~-0.098MPa by above-mentioned gained suspension solvent filter
Under the conditions of filter at film, three times with distilled water flushing, and taken off from filter membrane, dry, obtain in 105 DEG C of baking ovens later
The nano-cellulose antibacterial film of uniform, smooth surface the loading nano silvery particle of thickness.
According to same antibacterial around-France test antibacterial activity in embodiment 1.As a result the load nanometer obtained in the present embodiment
The nano-cellulose antibacterial film of silver particles only has 2.0mm respectively to the antibacterial ring width of staphylococcus aureus and Escherichia coli
And 1.3mm.
5 (AgNO of comparative example3Solution addition is very few)
By 2g bleached sulphate needlebush pulpboards crush, immerse 180ml distilled water in, sequentially add 0.2g sodium bromides,
The liquor natrii hypochloritis of a concentration of 1mol/L of 0.016g TEMPO and 20ml, is stirred at room temperature 6h, and stir speed (S.S.) is
The pH of reaction system in reaction process, is adjusted to every half an hour with the sodium hydroxide solution of a concentration of 1mol/L by 800rpm
10, by being centrifugally separating to obtain oxycellulose after the completion of reaction, carboxyl and aldehyde group content are respectively 0.75mmol g-1With
0.20mmol g-1.Then the oxycellulose of preparation is dispersed in water, it is fine prepares the oxidation that 100ml mass fractions are 1.0%
The plain water slurry of dimension；Above-mentioned oxycellulose water slurry is stirred into 15min under the conditions of rotating speed is 15000rpm, is put into later
In ultrasonic cell disruptor, processing 20min obtains nano-cellulose water slurry under conditions of power is 1000W；
The silver nitrate that a concentration of 0.5mol/L of 0.1ml are added in the nano-cellulose water slurry obtained by above-mentioned steps is water-soluble
Liquid stirs 1h under dark conditions after mixing, heats 0.5h at 100 DEG C later, by Ag+It is reduced to Ag, is loaded
The nano-cellulose water slurry of silver particles；In vacuum degree it is -0.096 by suspension solvent filter obtained by above-mentioned steps
It filters into film under conditions of~-0.098MPa, three times with distilled water flushing, and is taken off from filter membrane, dried later at 105 DEG C
It is dried in case, obtains the nano-cellulose antibacterial film of uniform, smooth surface the loading nano silvery particle of thickness.
According to same antibacterial around-France test antibacterial activity in embodiment 1.As a result due to AgNO3Addition is very few, causes
The nano-cellulose antibacterial film of the loading nano silvery particle obtained in the present embodiment is to staphylococcus aureus and Escherichia coli
Antibacterial ring width respectively only have 1.5mm and 0.6mm.
6 (AgNO of comparative example3Solution addition is excessive)
2g cotton linter pulpboards are crushed, immerses in 180ml distilled water, sequentially adds 0.2g sodium bromides, 0.016g TEMPO
And the liquor natrii hypochloritis of a concentration of 1mol/L of 10ml, 10h, stir speed (S.S.) 400rpm, reaction process is stirred at room temperature
In, the pH of reaction system is adjusted to 10 with the sodium hydroxide solution of a concentration of 1mol/L every half an hour, is led to after the completion of reaction
It crosses and is centrifugally separating to obtain oxycellulose, carboxyl and aldehyde group content are respectively 0.59mmol g-1With 0.33mmol g-1, prepare
The oxycellulose water slurry that 200ml mass fractions are 0.5%；It is in rotating speed by above-mentioned gained oxycellulose water slurry
10min is stirred under the conditions of 15000rpm, is put into ultrasonic cell disruptor later, is handled under conditions of power is 1000W
20min obtains nano-cellulose water slurry；It is a concentration of that 3ml is added in above-mentioned gained nano-cellulose water slurry
The silver nitrate aqueous solution of 0.5mol/L stirs 1h under dark conditions after mixing, heats 1.0h at 60 DEG C later, by Ag+It is reduced to Ag, the TEM figures of gained suspension are similar to comparative example 4；By above-mentioned gained suspension solvent filter in vacuum degree
To be filtered into film under conditions of -0.096~-0.098MPa, three times with distilled water flushing, and taken off from filter membrane, later
It is dried in 105 DEG C of baking ovens, obtains the nano-cellulose antibacterial film of uniform, smooth surface the loading nano silvery particle of thickness.
Although AgNO3Addition is more, but since silver particles are reunited and disperse unevenness, gained loads nanometer
The anti-microbial property of the nano-cellulose antibacterial film of silver particles there is no and AgNO3Addition is directly proportional.
According to same antibacterial around-France test antibacterial activity in embodiment 1.As a result the load nanometer obtained in the present embodiment
The nano-cellulose antibacterial film of silver particles only has 2.6mm respectively to the antibacterial ring width of staphylococcus aureus and Escherichia coli
And 1.9mm.
Claims (3)
1. a kind of preparation method of the nano-cellulose antibacterial film of loading nano silvery particle, the preparation method includes following step
Suddenly：
（1）Cellulosic material is crushed with pulverizer；
（2）Comminuted fibres element raw material is immersed and contains 2,2,6,6- tetramethyl piperidine -1- oxygen radicals, sodium bromide and secondary chlorine
In the distilled water of sour sodium, oxidation processes are carried out, wherein the comminuted fibres element raw material based on 100 parts by weight, uses 9000 weight
The distilled water of part, the sodium bromide of 10 parts by weight, the 2 of 0.8 parts by weight, 2,6,6- tetramethyl piperidine -1- oxygen radicals and 5 to 10
The liquor natrii hypochloritis of a concentration of 1 mol/L of parts by weight, the oxidation processes reaction are stirred at room temperature 6 to 10 h, stir
Rate is 400 to 800 rpm, in reaction process, every half an hour with the sodium hydroxide solution of a concentration of 1 mol/L by reactant
The pH of system is adjusted to 10；
（3）It is above-mentioned after reaction, by being centrifugally separating to obtain the cellulose of oxidation, and be added water prepare mass fraction be 0.5
The oxycellulose water slurry of the % of %~1.0；
（4）Above-mentioned gained oxycellulose water slurry is subjected to high-speed stirred and supersonic cell pulverization process, is received
Rice aqueous cellulosic suspension, the wherein rotating speed of high speed agitator are 12000~15000 rpm, and processing time is 10~15 min；
The power of ultrasonication is 600~1000 W, and sonication treatment time is 20~30 min；
（5）The silver nitrate aqueous solution of a concentration of 0.5 mol/L is added in above-mentioned gained nano-cellulose water slurry, is uniformly mixed
1 h is stirred under dark conditions afterwards, heats 0.5~1 h, aqueous cellulosic suspension face under 60~100 DEG C of water bath conditions later
Color becomes light brown from white, the nano-cellulose water slurry of load silver particles is obtained, wherein the nanometer based on 100 parts by weight
The addition of cellulose, the silver nitrate aqueous solution is 30 to 50 parts by weight；
（6）By above-mentioned gained load silver particles nano-cellulose water slurry filter, rinse, drying obtain thickness uniformly, table
The nano-cellulose antibacterial film of the smooth loading nano silvery particle in face.
2. preparation method according to claim 1, which is characterized in that the step（6）In Suction filtration device used be solvent
Filter, filter membrane are the cellulose acetate films that aperture is 0.45 μm, in the condition that vacuum degree is -0.096~-0.098 MPa
Distilled water flushing is used in combination three times at film in lower suction filtration, can be directly from filter membrane since film has good wet strength
On take off, dried in 105 DEG C of baking ovens later.
3. the nano-cellulose of a kind of nano-cellulose antibacterial film of loading nano silvery particle, the loading nano silvery particle is anti-
Bacterium film is prepared by preparation method as claimed in any of claims 1 to 2.
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| CN108951106B (en) * | 2018-06-13 | 2021-02-26 | 浙江工业大学之江学院 | Antibacterial nanofiber and preparation method thereof |
| CN109778537A (en) * | 2018-12-25 | 2019-05-21 | 华南理工大学 | The nano cellulose material and its preparation method of the uniform and stable load of nano-Ag particles and application |
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| CN114008124B (en) * | 2019-04-25 | 2023-09-29 | 东洋制罐集团控股株式会社 | Cellulose nanocrystal complex and method for producing same |
| CN111253624A (en) * | 2020-01-20 | 2020-06-09 | 华南农业大学 | Organic/inorganic hybrid material for environment-friendly cysteine detection and preparation method and application thereof |
| CN111519475A (en) * | 2020-03-02 | 2020-08-11 | 中科如米(北京)生态农业科技发展有限公司 | Method for extracting cellulose nanofibers from xylose residues and using cellulose nanofibers for preparing antibacterial composite membrane |
| CN111471312B (en) * | 2020-03-09 | 2022-02-25 | 内蒙古农业大学 | Silver-loaded nanocellulose, preparation method thereof and antibacterial composite material |
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| CN112176725A (en) * | 2020-10-28 | 2021-01-05 | 上海威露美生物科技有限公司 | Carboxyl esterification complex antibacterial fiber, preparation method and application |
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