CN106561711A - Nanometer silver aqueous solution with stable macromolecules in closed network structure and preparation method thereof - Google Patents
Nanometer silver aqueous solution with stable macromolecules in closed network structure and preparation method thereof Download PDFInfo
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- CN106561711A CN106561711A CN201611034679.1A CN201611034679A CN106561711A CN 106561711 A CN106561711 A CN 106561711A CN 201611034679 A CN201611034679 A CN 201611034679A CN 106561711 A CN106561711 A CN 106561711A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
- C08G83/004—After treatment of dendrimers
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Abstract
The invention provides a nanometer silver aqueous solution with stable macromolecules in a closed network structure and a preparation method thereof. The preparation method comprises the following steps: cooling a multi-amino monomer to 5 to 10 DEG C in an ice-water bath; then dropwise adding an ethylene monomer and a solvent into the multi-amino monomer through a funnel under the protection of nitrogen gas, after the completion of dropwise addition, carrying out a reaction at normal temperature for 4 hours so as to generate a light-yellow intermediate, placing the intermediate on a rotary evaporator, reducing pressure so as to remove the solvent, carrying out heating to 120 DEG C to 140 DEG C, and carrying out a pressure-reducing reaction for 2 to 4 hours so as to obtain a multi-amino hyperbranched polymer; adding a modifying agent into the multi-amino hyperbranched polymer, carrying out heating to 140 to 150 DEG C, continuing the pressure-reducing reaction for 1 to 4 hours so as to obtain a polyamide dendrimer polymer with the closed space network structure; and adding a silver ion compound solution into the polyamide dendrimer polymer with the closed space network structure, and carrying out complex-reduction so as to obtain a stable nanometer silver solution with a particle size of 5 to 15 nm.
Description
Technical field
The present invention relates to the disinfectant that uses of medicine and hygiene fieldses or bactericide, particularly a kind of to have polyamide tree-shaped big
The preparation method of molecular structure nano-silver water solution.
Background technology
Nano silver material, with performances such as unique light, electricity, magnetic, heat, antibacterials, is being changed because size is little, specific surface area big
Learn the aspects such as detection, bio-imaging and antibiotic preparation to be all widely used, in addition, there is Nano Silver extremely strong nanometer to live
Property, the antibacterial ability of overlength is shown, common bacterium, fungi, mycoplasma etc. can be killed under extremely low concentration pathogenic micro-
It is biological.Compare with antibiotic, there is Nano Silver bactericidal action not affected by PH values, broad-spectrum antiseptic, have no drug resistance, effect is held
Long, the features such as meeting higher water sterilizing power, safety and environmental protection, is preferable anti-biotic material, can be widely applied to numerous industries.At present
For products such as antibiotic fabric, gel, antibacterial stoste, micro mists, and can be widely applied to gynecological infection, mycotic infection of superficial part, wound
The fields such as wound nursing, water process, hygienic material, daily necessities.Because it does not have the replacement that drug resistance is splendid antibiotic
Product, are a kind of natural non-antibiotic class efficient germicides of safety.
Chemical reduction method is to prepare one of Nano Silver most common method, simple to operate because of its, is easily controlled, low cost and
It is widely used, its principle is the silver salt such as silver nitrate, silver acetate and for example new powder of appropriate reducing agent, hydrazine hydrate, boric acid, citric acid
Sodium etc. is reacted Ag in the liquid phase+It is grown to simple substance Argent grain.But the impurity content for preparing Nano Silver with chemical reduction method is higher,
Size distribution width, easily reunites.
Although Nano Silver is a kind of efficient, lasting, nontoxic inorganic antibacterial material, it is intrinsic that Nano Silver there is also some
Defect, it is such as unstable in exposure air, it is oxidizable, be long placed in easily discoloration；The preparation method of Nano Silver dispersion is complicated, surely
Qualitative difference, will often add the auxiliary agents such as suitable crosslinking agent, adhesive, stabilizer；Reunion of the Nano Silver in preparation process is still
It is difficult to control to.
In the case of more, nano silver dispersion as target product, with more wide industry and business application.
But, because Nano Silver particle diameter is less, surface energy is higher, is inclined to extremely strong reunion.In the preparation of nano silver dispersion
Cheng Zhong, the metachromatism for preventing agglomeration, deposited phenomenon and the solution of nano-Ag particles is even more important.Thus it is guaranteed that nanometer
The stability of nano-Ag particles, monodispersity in silver-colored dispersion liquid, become the key problem in technology in nano-silver water solution preparation process.
The substantial amounts of primary amino radical of ultrabranching polyamide periphery distribution, primary amino radical has higher compared with its internal secondary amino group and tertiary amino
Complexing, the ability of reduction silver ion, so ultrabranching polyamide is occurred mostly in the seizure of silver ion and reduction
The outside of dissaving polymer, therefore can not effectively control to generate the particle diameter and its stability of Nano Silver；Secondly it is hyperbranched
Polymer-supported chain is different in size, and regularity is poor, dissaving polymer does not have the such compound with regular structure of dendrimer, so internal empty
Between not strict protective layer, the nano material of generation is easily transferred to outside cavity structure, therefore stability is poor.
The content of the invention
The technical problem to be solved is, for generally existing nanometer in current nano-silver water solution preparation process
Silver granuel footpath is widely distributed so that nano-silver water solution stability is poor, oxidizable, is long placed in the allochroic problem of appearance, there is provided a kind of nanometer
The little narrowly distributing in silver granuel footpath and high water-soluble with the tree-shaped macromolecular structure Nano Silver of closing space network structure polyamide of stability
The preparation method of liquid.
To solve above-mentioned technical problem, the technical solution adopted in the present invention is：One kind has polyamide dendrimer
The preparation method of the structure nano silver aqueous solution, it comprises the following steps：
1）Polyamino monomer is cooled to into 5-10 DEG C with ice-water bath；
2）With constant pressure funnel under nitrogen protection to step 1）Vinyl monomer and solvent, drop are added dropwise in the polyamino monomer for obtaining
Plus finish under rear normal temperature reaction and generate faint yellow intermediate in 4 hours, intermediate is placed on Rotary Evaporators be removed under reduced pressure it is molten
Agent, then be warmed up to 120 DEG C of -140 DEG C of Depressor response 2-4 hours and obtain polyamino dissaving polymer；
3）Addition modifying agent is warmed up to 140-150 DEG C of continuation Depressor response 1-4 hour and obtains in polyamino dissaving polymer
To the tree-shaped macromolecule polyalcohol of closing space network structure polyamide；
4）Silver iron compound is added to make its complexing reduction in the tree-shaped macromolecule polyalcohol of closing space network structure polyamide
Particle diameter is obtained for 5-15nm stable Nano silver solution.
The polyamino monomer is diethylenetriamine, triethylene tetramine, TEPA or pentaethylene hexamine.
The vinyl monomer is acrylic acid, methyl acrylate, methyl methacrylate or ethyl acrylate.
The solvent is methyl alcohol, chloroform or N,N-dimethylformamide.
The modifying agent is succinic anhydride, maleic anhydride.
The silver iron compound is silver nitrate, silver acetate.
The step 2）The mol ratio 1 of middle polyamino monomer and vinyl monomer:1-1:3, the step 3）Middle polyamino
The mol ratio 1 of monomer and modifying agent:0.1-1:1.
To solve above-mentioned technical problem, present invention also offers close network structure prepared by a kind of utilization said method is big
The stable nano-silver water solution of molecule.
The present invention has synthesized the polyamide dendrimer with closing space network structure and has gathered by change synthesis technique
Compound, is complexed silver ion and is reduced into it and received using the secondary amino group inside its dendrimer spacial framework and tertiary amino
Meter Yin, the generation of the size in its internal network space to Nano Silver plays effective control effect, and the sealing effect of network structure can make
The nano-Ag particles of generation are limited in inside it, keep its stability.
Compared with prior art, present invention process is simple, the little narrowly distributing of gained Nano Silver particle diameter, good antimicrobial effect and stable
Property high, aqueous solution impurity it is few, biocompatibility, security are good.
Specific embodiment
Embodiment 1：
Weigh 103.2g diethylenetriamines and be placed in ice-water bath cooling in 500ml there-necked flasks；With constant pressure funnel under nitrogen protection
The mixed solution of 87.0g methyl acrylates and 200ml methyl alcohol is slowly added dropwise, generation in 4 hours is reacted after completion of dropping under normal temperature light
Yellow intermediate, above-mentioned intermediate is transferred in eggplant-shape bottle methyl alcohol is removed under reduced pressure on a rotary evaporator, then is warmed up to 120 DEG C
Depressor response obtains polyamino dissaving polymer for 4 hours, and the succinic anhydride for adding 10g is warmed up to 140 DEG C of continuation Depressor responses 4
Hour obtains the tree-shaped macromolecule polyalcohol of closing space network structure polyamide.
It is the above-mentioned polyamide that 1% silver nitrate solution is slowly dropped to that 500ml mass fractions are 1% by 500ml mass fractions
In dendrimer aqueous solutions of polymers, under agitation solution is heated to into 90 DEG C after completion of dropping and is cooled to room temperature,
Particle diameter is obtained for 5-15nm stable Nano silver solution.
Embodiment 2：
Weigh 51.6g diethylenetriamines and be placed in ice-water bath cooling in 250ml there-necked flasks；Delayed under nitrogen protection with constant pressure funnel
The slow mixed solution that 43.0g methyl acrylates and 100ml methyl alcohol is added dropwise, reacts generation in 4 hours yellowish under normal temperature after completion of dropping
Color intermediate, above-mentioned intermediate is transferred in eggplant-shape bottle methyl alcohol is removed under reduced pressure on a rotary evaporator, then is warmed up to 140 DEG C and is subtracted
Pressure reaction obtains polyamino dissaving polymer for 2 hours, and the maleic anhydride for adding 2.5g is warmed up to 150 DEG C of continuation Depressor responses 2
Hour obtains the tree-shaped macromolecule polyalcohol of closing space network structure polyamide.
By 500ml mass fractions be 0.5% silver acetate solution be slowly dropped to 500ml mass fractions be 0.5% it is above-mentioned poly-
In acid amides dendrimer aqueous solutions of polymers, under agitation solution is heated to into boiling after completion of dropping and is cooled to room
Temperature, that is, obtain particle diameter for 5-15nm stable Nano silver solution.
Embodiment 3：
Weigh 122.6g TEPAs and be placed in ice-water bath cooling in 500ml there-necked flasks；With constant pressure funnel under nitrogen protection
The mixed solution of 57.5g methyl acrylates and 200ml chloroforms is slowly added dropwise, life in 4 hours is reacted after completion of dropping under normal temperature
Into faint yellow intermediate, above-mentioned intermediate is transferred in eggplant-shape bottle chloroform is removed under reduced pressure on a rotary evaporator, then risen
Temperature to 140 DEG C of Depressor responses obtain polyamino dissaving polymer for 2 hours, add 13.4g succinic anhydride be warmed up to 150 DEG C after
Continuous Depressor response obtains the tree-shaped macromolecule polyalcohol of closing space network structure polyamide for 1 hour.
It is the above-mentioned polyamide that 1% silver nitrate solution is slowly dropped to that 500ml mass fractions are 1% by 500ml mass fractions
In dendrimer aqueous solutions of polymers, by solution normal-temperature reaction 48 hours after completion of dropping, that is, obtain particle diameter for 5-15nm it is steady
Fixed Nano silver solution.
Claims (8)
1. a kind of close network structural macromolecules stablize the preparation method of nano-silver water solution, it is characterised in that including following step
Suddenly：
1）Polyamino monomer is cooled to into 5-10 DEG C with ice-water bath；
2）With funnel under nitrogen protection to step 1）Vinyl monomer and solvent are added dropwise in the polyamino monomer for obtaining, are dripped
Reaction generates faint yellow intermediate in 4 hours under normal temperature after finishing, and intermediate is placed into into removal of solvent under reduced pressure on Rotary Evaporators, then
It is warmed up to 120 DEG C of -140 DEG C of Depressor response 2-4 hours and obtains polyamino dissaving polymer；
3）Addition modifying agent is warmed up to 140-150 DEG C of continuation Depressor response 1-4 hour and obtains in polyamino dissaving polymer
To the tree-shaped macromolecule polyalcohol of closing space network structure polyamide；
4）Silver iron compound is added to make its complexing reduction in the tree-shaped macromolecule polyalcohol of closing space network structure polyamide
Particle diameter is obtained for 5-15nm stable Nano silver solution.
2. a kind of close network structural macromolecules according to claim 1 stablize the preparation method of nano-silver water solution, its
It is characterised by, the polyamino monomer is diethylenetriamine, triethylene tetramine, TEPA or pentaethylene hexamine.
3. a kind of close network structural macromolecules according to claim 1 stablize the preparation method of nano-silver water solution, its
It is characterised by, the vinyl monomer is acrylic acid, methyl acrylate, methyl methacrylate or ethyl acrylate.
4. a kind of close network structural macromolecules according to claim 1 stablize the preparation method of nano-silver water solution, its
It is characterised by, the solvent is methyl alcohol, chloroform or DMF.
5. a kind of close network structural macromolecules according to claim 1 stablize the preparation method of nano-silver water solution, its
It is characterised by, the silver iron compound is silver nitrate, silver acetate.
6., according to a kind of preparation method of the stable nano-silver water solution of close network structural macromolecules described in claim 1, it is special
Levy and be, the modifying agent is succinic anhydride, maleic anhydride.
7. a kind of close network structural macromolecules according to claim 1 stablize the preparation method of nano-silver water solution, its
It is characterised by, the step 2）The mol ratio 1 of middle polyamino monomer and vinyl monomer:1-1:3, the step 3）Middle polyamino
The mol ratio 1 of monomer and modifying agent:0.1-1:1.
8. a kind of stable nano-silver water solution of the close network structural macromolecules that prepared by claim 1 methods described.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611034679.1A CN106561711A (en) | 2016-11-23 | 2016-11-23 | Nanometer silver aqueous solution with stable macromolecules in closed network structure and preparation method thereof |
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| CN201611034679.1A CN106561711A (en) | 2016-11-23 | 2016-11-23 | Nanometer silver aqueous solution with stable macromolecules in closed network structure and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912812A (en) * | 2019-01-28 | 2019-06-21 | 狄小龙 | A kind of preparation method of the Ag-containing solution of controllable Argent grain size |
| CN111940755A (en) * | 2020-07-27 | 2020-11-17 | 武汉勿幕科技有限公司 | Preparation method of gold nanoparticles |
| CN112913854A (en) * | 2019-12-05 | 2021-06-08 | 上海沪正实业有限公司 | Preparation method of targeted nano silver particles |
| CN113026367A (en) * | 2021-02-26 | 2021-06-25 | 长沙海润生物技术有限公司 | Medical silver-carrying gauze and preparation method thereof |
| CN113024825A (en) * | 2021-02-26 | 2021-06-25 | 长沙海润生物技术有限公司 | Modified polyamide complex silver and preparation method thereof |
-
2016
- 2016-11-23 CN CN201611034679.1A patent/CN106561711A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 张德锁 等: "纳米银的可控制备及对棉织物的抗菌整理", 《纺织学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912812A (en) * | 2019-01-28 | 2019-06-21 | 狄小龙 | A kind of preparation method of the Ag-containing solution of controllable Argent grain size |
| CN112913854A (en) * | 2019-12-05 | 2021-06-08 | 上海沪正实业有限公司 | Preparation method of targeted nano silver particles |
| CN112913854B (en) * | 2019-12-05 | 2022-04-01 | 上海沪正实业有限公司 | Preparation method of targeted nano silver particles |
| CN111940755A (en) * | 2020-07-27 | 2020-11-17 | 武汉勿幕科技有限公司 | Preparation method of gold nanoparticles |
| CN113026367A (en) * | 2021-02-26 | 2021-06-25 | 长沙海润生物技术有限公司 | Medical silver-carrying gauze and preparation method thereof |
| CN113024825A (en) * | 2021-02-26 | 2021-06-25 | 长沙海润生物技术有限公司 | Modified polyamide complex silver and preparation method thereof |
| CN113026367B (en) * | 2021-02-26 | 2022-07-26 | 长沙海润生物技术有限公司 | Medical silver-carrying gauze and preparation method thereof |
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