CN102228995A - Polysaccharide-nano silver sol and preparation method thereof - Google Patents
Polysaccharide-nano silver sol and preparation method thereof Download PDFInfo
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- CN102228995A CN102228995A CN 201110180946 CN201110180946A CN102228995A CN 102228995 A CN102228995 A CN 102228995A CN 201110180946 CN201110180946 CN 201110180946 CN 201110180946 A CN201110180946 A CN 201110180946A CN 102228995 A CN102228995 A CN 102228995A
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Abstract
The invention discloses polysaccharide-nano silver sol and a preparation method thereof. The polysaccharide-nano silver sol is carboxymethyl chitosan quaternary ammonium salt-nano silver sol; and the carboxymethyl chitosan quaternary ammonium salt-nano silver sol is prepared by converting AgNO3 into more active AgNO3, using carboxymethyl chitosan quaternary ammonium salt as a reducing agent and a stabilizing agent and adopting a microwave radiation heating method. The carboxymethyl chitosan quaternary ammonium salt is used as the reducing agent and the stabilizing agent for the first time, and the carboxymethyl chitosan quaternary ammonium salt-nano silver sol is quickly prepared in an aqueous phase under normal pressure by adopting the efficient microwave radiation heating method, so that the preparation process accords with 'green chemistry' advocated 'greenness' and 'environment friendliness' of reaction reagents, reducing agents and stabilizing agents in nano particle preparation; and because of the green preparation process and unique structure and properties of the carboxymethyl chitosan quaternary ammonium salt, the carboxymethyl chitosan quaternary ammonium salt-nano silver sol has huge application prospect in the fields of biology, medical treatment and the like.
Description
Technical field
The present invention relates to field of nanometer technology, relate in particular to polysaccharide-nano silver colloidal sol and preparation method thereof.
Background technology
Silver is a kind of common cheap noble metal, have characteristics such as good bactericidal properties, stability and electric conductivity, and Nano Silver has characteristics such as good bulk effect, skin effect, quantum size effect and macro quanta tunnel effect, in fields such as catalysis, superconduction, biomaterial, optical material or medical anti-biotic materials wide application space is arranged.
The preparation method of Nano Silver mainly contains chemical reduction method, photochemical method, microemulsion method and radiation method etc., and wherein simple low for equipment requirements being easy to of chemical reduction method technology produced in batches, is one of Nano Silver preparation method who has most using value.Traditional chemical reduction method need use reagent such as hydrazine hydrate, sodium borohydride as reducing agent, add natrium citricum, surfactant etc. again as stabilizing agent, in preparation process, often need to add number of chemical reagent, make that the Nano Silver product is difficult to thoroughly separate with stabilizing agent with reducing agent, limited the application of Nano Silver in fields such as biology, medical treatment.
Carboxymethyl chitosan quaternary ammonium salt is the amphoteric derivatives of shitosan, obtain by introducing carboxymethyl and quaternary ammonium group in chitosan structure, contain great amount of hydroxy group in its molecular structure, carboxyl and quaternary ammonium group can be used as the reducing agent and the stabilizing agent that prepare nano metal.
In addition, carboxymethyl chitosan quaternary ammonium salt has numerous excellent properties such as good water-solubility, antibiotic property, moisture absorbability and moisture retentivity and biocompatibility and biological degradability, has been applied to preparing cosmetic additive agent, antiseptic etc.
Microwave heating method is development in recent years one of green synthesis method rapidly, and programming rate is fast because of having, homogeneous heating, advantage such as easy to operate and safe receive much concern.
Have not yet to see useful carboxymethyl chitosan quaternary ammonium salt and prepare the relevant report of nano metal, the research that utilizes microwave heating method to prepare nano particle under condition of normal pressure is not also arranged as reducing agent and stabilizing agent.
Summary of the invention
The purpose of this invention is to provide a kind of be combined with carboxymethyl chitosan quaternary ammonium salt unique texture and character, at biomedicine field the polysaccharide-nano silver colloidal sol huge applications prospect, stable is arranged.
Another object of the present invention provides a kind of method of utilizing microwave heating method to prepare above-mentioned polysaccharide-nano silver colloidal sol.
Above-mentioned purpose of the present invention is achieved by following scheme:
A kind of polysaccharide-nano silver colloidal sol, this polysaccharide-nano silver colloidal sol are carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol, and described carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol is earlier with AgNO
3Be converted into more active
, use carboxymethyl chitosan quaternary ammonium salt as reducing agent and stabilizing agent again, adopt microwave heating method to prepare.
The preparation method of above-mentioned carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol specifically comprises the steps:
Step 1
With AgNO
3Be dissolved in the AgNO that is made into 0.17mg/mL～1.7mg/mL in the deionized water
3The aqueous solution adds NaOH aforementioned freshly prepared AgNO under stirring condition
3Form black Ag in the aqueous solution
2The O precipitation continues to drip NaOH to Ag
2The O precipitation no longer increases, and prepares Ag
2O suspension;
Immediately ammoniacal liquor is splashed into above-mentioned Ag then
2In the O suspension, to Ag
2The dissolving just of O precipitation obtains
Solution;
Step 2
Carboxymethyl chitosan quaternary ammonium salt is made into the carboxymethyl chitosan quaternary ammonium salt aqueous solution of 0.1mg/mL～40mg/mL earlier, and stirring is placed in the microwave reactor, and the adjusting microwave irradiation power is 100W～1000W, and radiation temperature is 30 ℃～100 ℃;
Step 3
With step 1 gained
Solution slowly splashes in the step 2 preparation gained carboxymethyl chitosan quaternary ammonium salt solution, promptly obtains required carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol behind reaction 1min～240min.
In the above-mentioned steps 1, NaOH adds with the form of the NaOH aqueous solution, and the concentration of the NaOH aqueous solution is 100mg/mL～250mg/mL.
In the above-mentioned steps 1, NaOH and AgNO
3Quality be 4:17～10:17.
In the above-mentioned steps 1, ammoniacal liquor is the form adding with the ammoniacal liquor dilute aqueous solution, and the concentration of ammoniacal liquor dilute aqueous solution adopts 50mg/mL～250mg/mL.
In the above-mentioned steps 2, the weight average molecular weight of carboxymethyl chitosan quaternary ammonium salt is 0.5 * 10
5～3.0 * 10
6, degree of substitution by carboxymethyl is 10%～100%, the substitution value of quaternary ammonium group is 5%～100%.
In the above-mentioned steps 3, the mass ratio of carboxymethyl chitosan quaternary ammonium salt and silver nitrate is 10mg:0.17mg～100mg:0.17mg.
Among the above-mentioned preparation method, carboxymethyl chitosan quaternary ammonium salt promptly as reducing agent again as stabilizing agent, need not to add any dispersant, reducing agent and stabilizing agent etc. in addition.
Adopt the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol of method for preparing, after measured, its stable placement under 4 ℃ of conditions was not reunited more than 3 months, illustrated that thus its character is highly stable.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention utilizes carboxymethyl chitosan quaternary ammonium salt as reducing agent and stabilizing agent first, adopting efficiently, microwave heating method aqueous phase under normal pressure prepares carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol apace, this preparation process meets reaction reagent in the nano particle preparation that " Green Chemistry " advocated, " greenization " and " environmental protectionization " of reducing agent and stabilizing agent, because of its green preparation process and carboxymethyl chitosan quaternary ammonium salt particular structure and character, carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol of the present invention is at biology, there is great application prospect in fields such as medical treatment;
2. carboxymethyl chitosan quaternary ammonium salt of the present invention-nano silver colloidal sol adopts amphoteric polysaccharide (carboxymethyl chitosan quaternary ammonium salt) to prepare nano silver colloidal sol as reducing agent and stabilizing agent at neutral aqueous phase, has avoided the use of organic solvent, dispersant, chemical reducing agent and stabilizing agent;
3. the present invention adopts microwave irradiation, obtains stable carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol under normal pressure in 1～240min, has greatly improved production efficiency, is a kind of extensively Nano Silver environment-friendly preparation method thereof of popularization that is suitable for;
4. the present invention provides new direction for the preparation of nano metal, and also the further research for nano metal provides good theory and practice basis with application.
Description of drawings
Fig. 1 is the UV-Vis absorption spectrum curve figure of the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol of embodiment 1～5;
Wherein, 1 is the UV-Vis absorption spectrum curve of embodiment 1 carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol, 2 is the UV-Vis absorption spectrum curve of embodiment 2 carboxymethyl chitosan quaternary ammonium salts-nano silver colloidal sol, 3 is the UV-Vis absorption spectrum curve of embodiment 3 carboxymethyl chitosan quaternary ammonium salts-nano silver colloidal sol, 4 is the UV-Vis absorption spectrum curve of embodiment 4 carboxymethyl chitosan quaternary ammonium salts-nano silver colloidal sol, and 5 is the UV-Vis absorption spectrum curve of embodiment 5 carboxymethyl chitosan quaternary ammonium salts-nano silver colloidal sol;
Fig. 2 is the transmission electron microscope picture of the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol of embodiment 1.
The specific embodiment
Below in conjunction with specific embodiment the present invention is done description further, but specific embodiment is not done any qualification to the present invention.
Embodiment 1
Carboxymethyl chitosan quaternary ammonium salt-the nano silver colloidal sol of present embodiment, its preparation method comprises the steps:
Step 1
With 0.00425g AgNO
3Be dissolved in the AgNO that is made into 0.17mg/mL in the 25mL deionized water
3The aqueous solution is added drop-wise to NaOH aforementioned freshly prepared AgNO under stirring condition
3Form black Ag in the aqueous solution
2The O precipitation continues to drip NaOH to Ag
2The O precipitation no longer increases, and prepares Ag
2O suspension;
Immediately ammoniacal liquor is splashed into above-mentioned Ag then
2In the O suspension,, obtain to precipitation dissolving just
Solution;
Step 2
(weight average molecular weight is 0.5 * 10 with the 0.005g carboxymethyl chitosan quaternary ammonium salt
5, degree of substitution by carboxymethyl is 10%, the quaternary ammonium group substitution value is 100%) and be made into the carboxymethyl chitosan quaternary ammonium salt aqueous solution of 0.1mg/mL earlier, stirring is placed in the microwave reactor, and the adjusting microwave irradiation power is 1000W, and radiation temperature is 100 ℃;
Step 3
With 0.2mL step 1 gained
Solution slowly splashes in the step 2 preparation gained carboxymethyl chitosan quaternary ammonium salt solution, promptly obtains required carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol behind the reaction 1min.
In the above-mentioned steps 1, NaOH is the form adding with the NaOH aqueous solution, and the concentration of the NaOH aqueous solution is 250mg/mL.
In the above-mentioned steps 1, NaOH and AgNO
3Mass ratio be 4:17.
In the above-mentioned steps 1, ammoniacal liquor adds with the form of ammoniacal liquor dilute aqueous solution, and the concentration of ammoniacal liquor dilute aqueous solution is 250mg/mL.
In the above-mentioned steps 3, the mass ratio of carboxymethyl chitosan quaternary ammonium salt and silver nitrate is 10mg:0.17mg.
With above-mentioned preparation and measure UV-Vis spectrum after 7 times of the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol dilutions, the result is as shown in Figure 1.
As can be seen from Figure 1, there is strong row ultraviolet and visible absorption peak in sample at 600～300nm place, and this absworption peak is belonged to the Nano Silver surface plasma resonance and absorbs generation, so there are a large amount of Nano Silvers to exist in the sample.
As can be seen from Figure 2, nano-Ag particles is the ball-type structure, and particle diameter is about 5～15nm, and the nothing that is uniformly dispersed is reunited.
After testing, the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol of present embodiment can be stablized placement more than 3 months under 4 ℃ of conditions.
Embodiment 2
Carboxymethyl chitosan quaternary ammonium salt-the nano silver colloidal sol of present embodiment, its preparation method comprises the steps:
Step 1
With 0.0425g AgNO
3Be dissolved in the AgNO that is made into 1.7mg/mL in the 25mL deionized water
3The aqueous solution is added drop-wise to NaOH aforementioned freshly prepared AgNO under stirring condition
3Form black Ag in the aqueous solution
2The O precipitation continues to drip NaOH to Ag
2The O precipitation no longer increases, and prepares Ag
2O suspension;
Immediately ammoniacal liquor is splashed into above-mentioned Ag then
2In the O suspension,, obtain to precipitation dissolving just
Solution;
Step 2
(weight average molecular weight is 3.0 * 10 with the 0.04g carboxymethyl chitosan quaternary ammonium salt
6, degree of substitution by carboxymethyl is 100%, the quaternary ammonium group substitution value is 5%) and be made into the carboxymethyl chitosan quaternary ammonium salt aqueous solution of 40mg/mL earlier, stirring is placed in the microwave reactor, and the adjusting microwave irradiation power is 100W, and radiation temperature is 30 ℃;
Step 3
With 0.04mL step 1 gained
Solution slowly splashes in the step 2 preparation gained carboxymethyl chitosan quaternary ammonium salt solution, promptly obtains required carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol behind the reaction 240min.
In the above-mentioned steps 1, NaOH is the form adding with the NaOH aqueous solution, and the concentration of the NaOH aqueous solution is 100mg/mL.
In the above-mentioned steps 1, NaOH and AgNO
3Mass ratio be 10:17.
In the above-mentioned steps 1, ammoniacal liquor is the form adding with the ammoniacal liquor dilute aqueous solution, and the concentration of ammoniacal liquor dilute aqueous solution is 50mg/mL.
In the above-mentioned steps 3, the ratio of carboxymethyl chitosan quaternary ammonium salt and silver nitrate is 100mg:0.17mg.
With above-mentioned preparation and measure UV-Vis spectrum after 7 times of the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol dilutions, the result is as shown in Figure 1.
As can be seen from Figure 1, there is strong row ultraviolet and visible absorption peak in sample at 600～300nm place, and this absworption peak is belonged to the Nano Silver surface plasma resonance and absorbs generation, so there are a large amount of Nano Silvers to exist in the sample.
After testing, the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol of present embodiment can be stablized placement more than 3 months under 4 ℃ of conditions.
Embodiment 3
Carboxymethyl chitosan quaternary ammonium salt-the nano silver colloidal sol of present embodiment, its preparation method comprises the steps:
Step 1
With 0.2125g AgNO
3Be dissolved in the AgNO that is made into 0.85mg/mL in the 250mL deionized water
3The aqueous solution is added drop-wise to NaOH aforementioned freshly prepared AgNO under stirring condition
3Form black Ag in the aqueous solution
2The O precipitation, continuing to drip NaOH increases to precipitating no longer, prepares Ag
2O suspension;
Immediately ammoniacal liquor is splashed into above-mentioned Ag then
2In the O suspension,, obtain to precipitation dissolving just
Solution;
Step 2
(weight average molecular weight is 3.0 * 10 with the 0.01g carboxymethyl chitosan quaternary ammonium salt
5, degree of substitution by carboxymethyl is 30%, the quaternary ammonium group substitution value is 50%) and be made into the carboxymethyl chitosan quaternary ammonium salt aqueous solution of 1mg/mL earlier, stirring is placed in the microwave reactor, and the adjusting microwave irradiation power is 600W, and radiation temperature is 70 ℃;
Step 3
With 0.1mL step 1 gained
Solution slowly splashes in the step 2 preparation gained carboxymethyl chitosan quaternary ammonium salt solution, promptly obtains required carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol behind the reaction 15min.
In the above-mentioned steps 1, NaOH is the form adding with the NaOH aqueous solution, and the concentration of the NaOH aqueous solution is 200mg/mL.
In the above-mentioned steps 1, NaOH and AgNO
3Mass ratio be 5:17.
In the above-mentioned steps 1, ammoniacal liquor is the form adding with the ammoniacal liquor dilute aqueous solution, and the concentration of ammoniacal liquor dilute aqueous solution is 150mg/mL.
Above-mentioned steps 3, the ratio of carboxymethyl chitosan quaternary ammonium salt and silver nitrate are 20mg:0.17mg.
With above-mentioned preparation and measure UV-Vis spectrum after 7 times of the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol dilutions, the result is as shown in Figure 1.
As can be seen from Figure 1, there is strong row ultraviolet and visible absorption peak in sample at 600～300nm place, and this absworption peak is belonged to the Nano Silver surface plasma resonance and absorbs generation, so there are a large amount of Nano Silvers to exist in the sample.
After testing, the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol of present embodiment can be stablized placement more than 3 months under 4 ℃ of conditions.
Embodiment 4
Carboxymethyl chitosan quaternary ammonium salt-the nano silver colloidal sol of present embodiment, its preparation method comprises the steps:
Step 1
With 0.068g AgNO
3Be dissolved in the AgNO that is made into 1.36mg/mL in the 50mL deionized water
3The aqueous solution is added drop-wise to NaOH aforementioned freshly prepared AgNO under stirring condition
3Form black Ag in the aqueous solution
2The O precipitation continues to drip NaOH to Ag
2The O precipitation no longer increases, and prepares Ag
2O suspension;
Immediately ammoniacal liquor is splashed into above-mentioned Ag then
2In the O suspension,, obtain to precipitation dissolving just
Solution;
Step 2
(weight average molecular weight is 1.0 * 10 with the 0.1g carboxymethyl chitosan quaternary ammonium salt
6, degree of substitution by carboxymethyl is 50%, the quaternary ammonium group substitution value is 60%) and be made into the carboxymethyl chitosan quaternary ammonium salt aqueous solution of 10mg/mL earlier, stirring is placed in the microwave reactor, and the adjusting microwave irradiation power is 700W, and radiation temperature is 80 ℃;
Step 3
With 1.25mL step 1 gained
Solution slowly splashes in the step 2 preparation gained carboxymethyl chitosan quaternary ammonium salt solution, promptly obtains required carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol behind the reaction 1min.
In the above-mentioned steps 1, NaOH is the form adding with the NaOH aqueous solution, and the concentration of the NaOH aqueous solution is 150mg/mL.
In the above-mentioned steps 1, NaOH and AgNO
3Mass ratio be 6:17.
In the above-mentioned steps 1, ammoniacal liquor is the form adding with the ammoniacal liquor dilute aqueous solution, and the concentration of ammoniacal liquor dilute aqueous solution is 200mg/mL.
In the above-mentioned steps 3, the ratio of carboxymethyl chitosan quaternary ammonium salt and silver nitrate is 10mg:0.17mg.
With above-mentioned preparation and measure UV-Vis spectrum after 7 times of the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol dilutions, the result is as shown in Figure 1.
As can be seen from Figure 1, there is strong row ultraviolet and visible absorption peak in sample at 600～300nm place, and this absworption peak is belonged to the Nano Silver surface plasma resonance and absorbs generation, so there are a large amount of Nano Silvers to exist in the sample.
After testing, the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol of present embodiment can be stablized placement more than 3 months under 4 ℃ of conditions.
Embodiment 5
Carboxymethyl chitosan quaternary ammonium salt-the nano silver colloidal sol of present embodiment, its preparation method comprises the steps:
Step 1
With 0.00425gAgNO
3Be dissolved in the AgNO that is made into 0.17mg/mL in the 25mL deionized water
3The aqueous solution is added drop-wise to NaOH aforementioned freshly prepared AgNO under stirring condition
3Form black Ag in the aqueous solution
2The O precipitation continues to drip NaOH to Ag
2The O precipitation no longer increases, and prepares Ag
2O suspension;
Immediately ammoniacal liquor is splashed into above-mentioned Ag then
2In the O suspension,, obtain to precipitation dissolving just
Solution;
Step 2
(weight average molecular weight is 4.8 * 10 with the 0.06g carboxymethyl chitosan quaternary ammonium salt
5, degree of substitution by carboxymethyl is 60%, the quaternary ammonium group substitution value is 70%) and be made into the carboxymethyl chitosan quaternary ammonium salt aqueous solution of 6mg/mL, stirring is placed in the microwave reactor, and the adjusting microwave irradiation power is 500W, and radiation temperature is 60 ℃;
Step 3
With 2mL step 1 gained
Solution slowly splashes in the step 2 preparation gained carboxymethyl chitosan quaternary ammonium salt solution, promptly obtains required carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol behind the reaction 30min.
In the above-mentioned steps 1, NaOH is the form adding with the NaOH aqueous solution, and the concentration of the NaOH aqueous solution is 150mg/mL.
In the above-mentioned steps 1, NaOH and AgNO
3Mass ratio be 6:17.
In the above-mentioned steps 1, ammoniacal liquor is the form adding with the ammoniacal liquor dilute aqueous solution, and the concentration of ammoniacal liquor dilute aqueous solution is 100mg/mL.
In the above-mentioned steps 3, the ratio of carboxymethyl chitosan quaternary ammonium salt and silver nitrate is 30mg:0.17mg.
With above-mentioned preparation and measure UV-Vis spectrum after 7 times of the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol dilutions, the result is as shown in Figure 1.
As can be seen from Figure 1, there is strong row ultraviolet and visible absorption peak in sample at 600～300nm place, and this absworption peak is belonged to the Nano Silver surface plasma resonance and absorbs generation, so there are a large amount of Nano Silvers to exist in the sample.
After testing, the carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol of present embodiment can be stablized placement more than 3 months under 4 ℃ of conditions.
Claims (7)
1. a polysaccharide-nano silver colloidal sol is characterized in that described polysaccharide-nano silver colloidal sol is carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol, and described carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol is earlier with AgNO
3Be converted into more active
, use carboxymethyl chitosan quaternary ammonium salt as reducing agent and stabilizing agent again, adopt microwave heating method to prepare.
2. the preparation method of the described polysaccharide-nano silver colloidal sol of claim 1 is characterized in that this preparation method comprises the steps:
Step 1
With AgNO
3Be dissolved in the AgNO that is made into 0.17mg/mL～1.7mg/mL in the deionized water
3The aqueous solution adds NaOH aforementioned freshly prepared AgNO under stirring condition
3Form black Ag in the aqueous solution
2The O precipitation continues to drip NaOH to Ag
2The O precipitation no longer increases, and prepares Ag
2O suspension;
Immediately ammoniacal liquor is splashed into above-mentioned Ag then
2In the O suspension, to Ag
2The dissolving just of O precipitation obtains
Solution;
Step 2
Carboxymethyl chitosan quaternary ammonium salt is made into the carboxymethyl chitosan quaternary ammonium salt aqueous solution of 0.1mg/mL～40mg/mL earlier, and stirring is placed in the microwave reactor, and the adjusting microwave irradiation power is 100W～1000W, and radiation temperature is 30 ℃～100 ℃;
Step 3
With step 1 gained
Solution slowly splashes in the step 2 preparation gained carboxymethyl chitosan quaternary ammonium salt solution, promptly obtains required carboxymethyl chitosan quaternary ammonium salt-nano silver colloidal sol behind reaction 1min～240min.
3. according to the preparation method of the described polysaccharide-nano silver colloidal sol of claim 2, it is characterized in that in the described step 1 that NaOH adds with the form of the NaOH aqueous solution, the concentration of the NaOH aqueous solution is 100mg/mL～250mg/mL.
4. according to the preparation method of the described polysaccharide-nano silver colloidal sol of claim 2, it is characterized in that in the described step 1 NaOH and AgNO
3Quality be 4:17～10:17.
5. according to the preparation method of the described polysaccharide-nano silver colloidal sol of claim 2, it is characterized in that in the described step 1 that ammoniacal liquor is the form adding with the ammoniacal liquor dilute aqueous solution, the concentration of ammoniacal liquor dilute aqueous solution is 50mg/mL～250mg/mL.
6. according to the preparation method of the described polysaccharide-nano silver colloidal sol of claim 2, it is characterized in that in the described step 2 that the weight average molecular weight of carboxymethyl chitosan quaternary ammonium salt is 0.5 * 10
5～3.0 * 10
6, degree of substitution by carboxymethyl is 10%～100%, the substitution value of quaternary ammonium group is 5%～100%.
7. according to the preparation method of the described polysaccharide-nano silver colloidal sol of claim 2, it is characterized in that in the described step 3 that the mass ratio of carboxymethyl chitosan quaternary ammonium salt and silver nitrate is 10mg:0.17mg～100mg:0.17mg.
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