CN105033275A - Preparing method for synthesizing flake cellulose nanocrystalline/nano-silver hybridization particles through assistant reducing agent - Google Patents
Preparing method for synthesizing flake cellulose nanocrystalline/nano-silver hybridization particles through assistant reducing agent Download PDFInfo
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- CN105033275A CN105033275A CN201510323487.1A CN201510323487A CN105033275A CN 105033275 A CN105033275 A CN 105033275A CN 201510323487 A CN201510323487 A CN 201510323487A CN 105033275 A CN105033275 A CN 105033275A
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Abstract
The invention relates to a preparing method for synthesizing flake cellulose nanocrystalline/nano-silver hybridization particles through an assistant reducing agent. The preparing method comprises the specific processes that firstly, cellulose nanocrystalline, the assistant reducing agent and an organic dispersing agent are weighed according to the mass ratio and dissolved in water to be sufficiently stirred, a silver-ammonia solution is added, and the solid-to-liquid ratio of a reaction system is controlled; and secondly, the solution is heated in a water bath, stirring continues to be carried out, after a reaction product is naturally cooled, the pH value of the solution is adjusted to 7 through centrifugal washing, finally, the solution is dried to the constant weight, and then the flake cellulose nanocrystalline/nano-silver hybridization particles are obtained. The adopted raw materials are low in cost and easy to obtain, the preparing technology is simple and fast, and preparing conditions are moderate and easy to control. The prepared flake cellulose nanocrystalline/nano-silver hybridization particles are controllable in appearance, small in size and large in specific surface area, good dispersibility is achieved in the water solution, combining between the cellulose nanocrystalline and the nano-silver is firm, the anti-bacterial effect is superior, and durable bacterial prevention can be achieved.
Description
Technical field
The invention belongs to the preparation field of Cellulose nanocrystal/nano-noble metal hybrid particle, particularly the preparation method of a kind of Cellulose nanocrystal/Nano Silver hybrid particle.
Background technology
The anti-microbial property of silver is just widely used in the world of medicine as far back as 16th century, fester as covered wound prevention with silver strip, gauze parcel skin trauma is made into filamentary silver, drip liquor argenti nitratis ophthalmicus during baby due and can prevent mucosa infection (Yuan Peng, He Hongping. the progress [J] of silver-based inorganic antibacterial agent. chemical industry mineral and processing, 2002,31 (10): 5-9.).Along with the fast development of nanometer technology, after argent is processed into Nano Silver, atomic arrangement shows as " Jie's state " between solid and molecule, its specific area is very big, demonstrate obvious skin effect, small-size effect and macroscopical tunnel-effect, the extremely strong Silver nanoparticles of this activity possesses superpower antibacterial ability.Chinese patent CN569366A discloses a kind of preparation method of nano-silver water solution, and this invention adds deionized water and is prepared into Nano Silver dilution after ultrasonic disperse.It should be noted that Nano Silver very easily agglomeration occurs, after reuniting, easily form large-sized nano-Ag particles, this will cause the decline of nanometer silver antimicrobial performance.And a large amount of activity hydroxies that Cellulose nanocrystal surface is contained can be had an effect with Nano Silver, play the effect of stabilized nanoscale silver solution, make it to have the possibility of the carrier becoming a kind of loading nano silvery.When nano-silver loaded is after Cellulose nanocrystal, utilize the template effect of Cellulose nanocrystal it can be considered as Nano Silver dispersant in aqueous.Cellulose nanocrystal has high length-diameter ratio, excellent mechanical performance, degradable and the characteristic such as renewable, through being developed and being widely used in preparing the Biocomposite material of novel cheapness.Now there are some researches show, Cellulose nanocrystal/Nano Silver the hybrid particle of corn shape and core-shell structure has good anti-microbial property (YuH, SunB, ZhangD, etal.Reinforcementofbiodegradablepoly (3-hydroxybutyrate-co-3-hydroxyvalerate) withcellulosenanocrystal/silvernanohybridsasbifunctional nanofillers [J] .JournalofMaterialsChemistryB, 2014,2 (48): 8479-8489).According to about showing the fragmentation effect of bacterium and the research of influence factor for Nano Silver, nano silver particles first produces little hole on cell membrane, enter periplasmic space by hole cell membrane component is leaked and destroys cell membrane, and then make the DNA of cell interior concentrated in nervous state, last combination with the cytoplasm of damaged bacterium is gathered, cause intracellular organic matter loss (Xie little Bao, Li Wenru, Zeng Haiyan, Deng. Nano Silver is to colibacillary antibacterial action and mechanism [J] thereof. material engineering, 2008 (10): 106-109.).But the Cellulose nanocrystal/Nano Silver hybrid particle size of corn shape and core-shell structure (wherein silver is in graininess) is comparatively large, and not easily permeate through cell membranes enters cell interior and kills bacterium.And sheet hybrid particle prepared by the present invention not only realizes combining firmly, and there is less size and larger specific area, hybrid particle has better antibacterial and bactericidal effect, and has broad-spectrum antibacterial action and superpower permeability, enables to realize durable antibiotic.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method that a kind of utilization helps reducing agent synthesizing flaky Cellulose nanocrystal/Nano Silver hybrid particle.The Cellulose nanocrystal that the present invention's raw material used is surface containing carbomethoxy or aldehyde radical, uses simple oxidation reduction reaction can prepare Cellulose nanocrystal/Nano Silver hybrid particle under water bath condition.Low cost of raw materials of the present invention is easy to get, and preparation technology is simple and quick, and the gentle easily control of preparation condition, is suitable for industrial-scale production; Obtained sheet-like fiber element is nanocrystalline/and Nano Silver hybrid particle not only can realize morphology controllable, also there is size little and compared with the characteristic of bigger serface, and it also has good dispersiveness in aqueous, Cellulose nanocrystal is combined with Nano Silver firmly, and antibacterial effect is excellent and can realize durable antibiotic.
A kind of utilization of the present invention helps the preparation method of reducing agent synthesizing flaky Cellulose nanocrystal/Nano Silver hybrid particle, comprising:
(1) Cellulose nanocrystal is taken according to mass ratio 10:1-5:1-5, help reducing agent and organic dispersing agent, fully stir in water-soluble for three solution, adding concentration is subsequently 0.01-0.05mol/L silver ammino solution, and to control solid-to-liquid ratio in reaction system be 1.625-2.85:150-200, its measurement unit is respectively g and ml.
(2) by above-mentioned solution in 70
oc-90
oheating water bath under C, Keep agitation 20-30min.After question response product cools naturally, through centrifugal washing, the pH value of solution is adjusted to 7, final drying to constant weight, obtain sheet-like fiber element nanocrystalline/Nano Silver nano-hybrid particle.
Cellulose nanocrystal in described step (1), its surface is with carbomethoxy or aldehyde radical.
The reducing agent that helps in described step (1) is one in glucose, sucrose and fructose.
Organic dispersing agent in described step (1) is the one in polyvinylpyrrolidone, triethyl group ethyl phosphonic acid, lauryl sodium sulfate, methyl anyl alcohol, polyacrylamide and fatty acid polyethylene glycol ester.
In described step (2), the diameter of gained sheet Cellulose nanocrystal/Nano Silver hybrid particle is 10-700nm.
beneficial effect
The present invention utilize help reducing agent by nano-silver loaded in Cellulose nanocrystal, and successfully prepared sheet-like fiber element nanocrystalline/Nano Silver hybrid particle.1) preparation technology described in is simple and easy to operate, the salt that needed raw material is with low cost and reducing agent and controllable obtain sheet-like fiber element nanocrystalline/Nano Silver hybrid particle, substantially reduce the manufacturing cycle of hybrid particle, and reduce production cost, be very suitable for industrial-scale production; 2) the sheet-like fiber element prepared of the present invention nanocrystalline/Nano Silver hybrid particle compares the granular hybrid material ratio of previously preparation, not only there is the features such as size is little, good dispersion, morphology controllable, specific area large, excellent antibacterial performance, and sheet-like fiber element prepared by the present invention is nanocrystalline/Nano Silver hybrid particle at Preen nono composite, there is application prospect more widely in the fields such as food, medicine, cosmetics, optics.
Accompanying drawing explanation
Fig. 1 be sheet-like fiber element nanocrystalline/scanning electron microscope (SEM) photograph of Nano Silver hybrid particle.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Take Cellulose nanocrystal according to mass ratio 10:1:1, glucose and polyvinylpyrrolidone (PVP) are prepared 100mL solution and are fully stirred, and add the silver ammino solution that 100mL concentration is 0.01mol/L subsequently, by above-mentioned solution in 70
oc heating water bath, Keep agitation 20min.After question response product cools naturally, the pH value of solution is adjusted to 7 by centrifugal washing, final drying to constant weight, obtain sheet-like fiber element nanocrystalline/Nano Silver hybrid particle.
Embodiment 2
Take Cellulose nanocrystal according to the ratio of mass ratio 10:1:2, glucose and polyvinylpyrrolidone (PVP) are prepared 100mL solution and are fully stirred, and add the silver ammino solution that 100mL concentration is 0.05mol/L subsequently, by above-mentioned solution in 80
oc heating water bath, Keep agitation 30min.After above-mentioned product cools naturally, the pH value of solution is adjusted to 7 by centrifugal washing, final drying to constant weight, obtain sheet-like fiber element nanocrystalline/Nano Silver hybrid particle.
Embodiment 3
Take Cellulose nanocrystal according to the ratio of mass ratio 10:1:1, sucrose and triethyl group ethyl phosphonic acid preparation 100mL solution fully stir, and add the silver ammino solution that 100mL concentration is 0.01mol/L subsequently, by above-mentioned solution in 80
oc heating water bath, Keep agitation 20min.After above-mentioned product cools naturally, the pH value of solution is adjusted to 7 by centrifugal washing, final drying to constant weight, obtain sheet-like fiber element nanocrystalline/Nano Silver hybrid particle.
Embodiment 4
Take Cellulose nanocrystal according to the ratio of mass ratio 10:2:1, sucrose and triethyl group ethyl phosphonic acid preparation 100mL solution fully stir, and add the silver ammino solution that 100mL concentration is 0.02mol/L subsequently, by above-mentioned solution in 90
oc heating water bath, Keep agitation 20min.After above-mentioned product cools naturally, the pH value of solution is adjusted to 7 by centrifugal washing, final drying to constant weight, obtain sheet-like fiber element nanocrystalline/Nano Silver hybrid particle.
Embodiment 5
Take Cellulose nanocrystal according to the ratio of mass ratio 10:2:2, fructose and triethyl group ethyl phosphonic acid preparation 100mL solution fully stir, and add the silver ammino solution that 100mL concentration is 0.03mol/L subsequently, by above-mentioned solution in 90
oc heating water bath, Keep agitation 25min.After above-mentioned product cools naturally, the pH value of solution is adjusted to 7 by centrifugal washing, final drying to constant weight, obtain sheet-like fiber element nanocrystalline/Nano Silver hybrid particle.
Embodiment 6
Take Cellulose nanocrystal according to the ratio of mass ratio 10:2:2, fructose and lauryl sodium sulfate preparation 100mL solution fully stir, and add the silver ammino solution that 100mL concentration is 0.04mol/L subsequently, by above-mentioned solution in 85
oc heating water bath, Keep agitation 25min.After above-mentioned product cools naturally, the pH value of solution is adjusted to 7 by centrifugal washing, final drying to constant weight, obtain sheet-like fiber element nanocrystalline/Nano Silver hybrid particle.
Embodiment 7
Take Cellulose nanocrystal according to the ratio of mass ratio 10:1:1, fructose and lauryl sodium sulfate preparation 100mL solution fully stir, and to add 100mL concentration be subsequently the concentration of 0.05mol/L is the silver ammino solution of 0.04mol/L, by above-mentioned solution in 90
oc heating water bath, Keep agitation 30min.After above-mentioned product cools naturally, the pH value of solution is adjusted to 7 by centrifugal washing, final drying to constant weight, obtain sheet-like fiber element nanocrystalline/Nano Silver hybrid particle.
Claims (5)
1. utilization helps a preparation method for reducing agent synthesizing flaky Cellulose nanocrystal/Nano Silver hybrid particle, comprising:
Take Cellulose nanocrystal according to mass ratio 10:1-5:1-5, help reducing agent and organic dispersing agent, by abundant stirring soluble in water for three, add the silver ammino solution that concentration is 0.01-0.05mol/L subsequently, and the solid-to-liquid ratio controlled in reaction system is 1.625-2.85:150-200, its measurement unit is respectively g and ml;
(2) by above-mentioned solution in 70
oc-90
oheating water bath under C, Keep agitation 20-30min; After question response product cools naturally, through centrifugal washing, the pH value of solution is adjusted to 7, final drying to constant weight, obtain sheet-like fiber element nanocrystalline/Nano Silver nano-hybrid particle.
2. utilization according to claim 1 helps the preparation method of reducing agent synthesizing flaky Cellulose nanocrystal/Nano Silver hybrid particle, it is characterized in that: the Cellulose nanocrystal in described step (1), its surface is with carbomethoxy or aldehyde radical.
3. utilization according to claim 1 helps the preparation method of reducing agent synthesizing flaky Cellulose nanocrystal/Nano Silver hybrid particle, it is characterized in that: the reducing agent that helps in described step (1) is one in glucose, sucrose and fructose.
4. utilization according to claim 1 helps the preparation method of reducing agent synthesizing flaky Cellulose nanocrystal/Nano Silver hybrid particle, it is characterized in that: the organic dispersing agent in described step (1) is the one in polyvinylpyrrolidone, triethyl group ethyl phosphonic acid, lauryl sodium sulfate, methyl anyl alcohol, polyacrylamide and fatty acid polyethylene glycol ester.
5. utilization according to claim 1 helps the preparation method of reducing agent synthesizing flaky Cellulose nanocrystal/Nano Silver hybrid particle, it is characterized in that: in described step (2), the diameter of gained sheet Cellulose nanocrystal/Nano Silver hybrid particle is 10-700nm.
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| CN201510323487.1A CN105033275B (en) | 2015-06-15 | 2015-06-15 | It is a kind of to utilize the preparation method for helping reducing agent synthesizing flaky Cellulose nanocrystal/Nano Silver hybrid particle |
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| CN201510323487.1A CN105033275B (en) | 2015-06-15 | 2015-06-15 | It is a kind of to utilize the preparation method for helping reducing agent synthesizing flaky Cellulose nanocrystal/Nano Silver hybrid particle |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116671515A (en) * | 2023-04-23 | 2023-09-01 | 合创(广州)科技研究有限公司 | Nano silver antibacterial liquid and application thereof |
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| JP2009138243A (en) * | 2007-12-07 | 2009-06-25 | Dowa Electronics Materials Co Ltd | Silver fine powder with excellent affinity for polar medium, silver ink, and method for producing silver particle |
| CN101811664A (en) * | 2010-04-15 | 2010-08-25 | 北京林业大学 | Cellulose/silver nano composite material and preparation method thereof |
| CN102775643A (en) * | 2012-07-10 | 2012-11-14 | 东华大学 | Preparation method for nano-sliver/cellulose nanocrystalline composite particle |
| CN103131030A (en) * | 2013-03-14 | 2013-06-05 | 北京林业大学 | Cellulose/sliver/silver chloride composite material and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20070027037A (en) * | 2005-08-29 | 2007-03-09 | 삼성전기주식회사 | Nano particle, conductive ink and wiring forming device |
| JP2009138243A (en) * | 2007-12-07 | 2009-06-25 | Dowa Electronics Materials Co Ltd | Silver fine powder with excellent affinity for polar medium, silver ink, and method for producing silver particle |
| CN101811664A (en) * | 2010-04-15 | 2010-08-25 | 北京林业大学 | Cellulose/silver nano composite material and preparation method thereof |
| CN102775643A (en) * | 2012-07-10 | 2012-11-14 | 东华大学 | Preparation method for nano-sliver/cellulose nanocrystalline composite particle |
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| CN116671515A (en) * | 2023-04-23 | 2023-09-01 | 合创(广州)科技研究有限公司 | Nano silver antibacterial liquid and application thereof |
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