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CN1653907A - Preparation method of nano-silver solution and nano-silver powder with high polymer as stabilizer - Google Patents

Preparation method of nano-silver solution and nano-silver powder with high polymer as stabilizer Download PDF

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CN1653907A
CN1653907A CN 200510049258 CN200510049258A CN1653907A CN 1653907 A CN1653907 A CN 1653907A CN 200510049258 CN200510049258 CN 200510049258 CN 200510049258 A CN200510049258 A CN 200510049258A CN 1653907 A CN1653907 A CN 1653907A
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CN1277476C (en
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计剑
付金红
沈家骢
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Zhejiang University ZJU
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Abstract

The present invention discloses the preparation process of nanometer silver solution and nanometer silver powder with polymer as stabilizer. Water soluble polymer as stabilizer in solution of 0.001-0.05 g/ml solution and silver nitrate in solution of 0.001-0.1 mol/L are compounded and reduced with water soluble reductant in solution of 0.001-0.2 mol/L to obtain nanometer silver particle of 5-100 nm size. The nanometer silver particle in solution may be further deposited and washed with sodium hydroxide solution, dried and crushed to obtain nanometer silver particle of 5-100 nm size. The prepared solution may be used in medical article, and prepared nanometer silver powder may be used widely in household appliance, plastic product, paint, etc. The present invention is environment friendly, low in cost and simple in operation, and the prepared nanometer silver particle has extremely powerful antibiotic capacity and wide antibiotic spectrum.

Description

以高聚物为稳定剂的纳米银溶液和纳米银粉体制备方法Preparation method of nano-silver solution and nano-silver powder with high polymer as stabilizer

技术领域technical field

本发明涉及一种广谱抗菌纳米银溶液及纳米银粉体制备方法,特别涉及一种以高聚物为稳定剂的纳米银溶液和纳米银粉体的制备方法。The invention relates to a preparation method of a broad-spectrum antibacterial nano-silver solution and a nano-silver powder, in particular to a preparation method of a nano-silver solution and a nano-silver powder with a high polymer as a stabilizer.

背景技术Background technique

目前市场上应用的抗菌材料还是以有机抗菌剂为多,但是有机抗菌剂一般抗菌效果较差,仅防霉菌作用较强,对二者均有优良抑制的有机抗菌剂较少。而且有机抗菌剂的耐热性、稳定性较差,其分解产物和挥发物可能对人体有害;因而对细菌抑制作用较强的无机抗菌剂,特别银系抗菌剂,脱颖而出。与有机抗菌剂相比,无机抗菌材料具有持续性、持久性、广谱性,不易产生耐药性,耐热性好,安全性高等特点。At present, most of the antibacterial materials used in the market are organic antibacterial agents, but organic antibacterial agents generally have poor antibacterial effects, and only have a strong anti-mold effect, and there are few organic antibacterial agents that have excellent inhibition on both. Moreover, organic antibacterial agents have poor heat resistance and stability, and their decomposition products and volatiles may be harmful to the human body; thus, inorganic antibacterial agents with strong inhibitory effects on bacteria, especially silver-based antibacterial agents, stand out. Compared with organic antibacterial agents, inorganic antibacterial materials have the characteristics of persistence, persistence, broad spectrum, resistance to drug resistance, good heat resistance, and high safety.

银具有广谱抗菌性。早在远古时代就被用来治疗刀伤、剑伤,古代三国名医华佗就用银刀为关公刮骨疗伤,《本草纲目》对银的杀菌功能已有记载。《基础元素化学》对银这样描述:银作为杀菌剂具有奇特功效,1%的硝酸银溶液是治疗眼结膜炎的常用药。金属银具有强烈的杀菌作用。Silver has broad-spectrum antimicrobial properties. As early as ancient times, it was used to treat knife wounds and sword wounds. Hua Tuo, a famous doctor of the Three Kingdoms in ancient times, used silver knives to scrape the bones of Guan Gong to heal wounds. "Compendium of Materia Medica" has recorded the bactericidal function of silver. "Basic Element Chemistry" describes silver in this way: silver has a unique effect as a bactericide, and 1% silver nitrate solution is a common drug for treating conjunctivitis. Metallic silver has a strong bactericidal effect.

纳米技术是以1~100nm尺寸的物质为研究对象的前沿学科。纳米银由于其较高的比表面积,具有快速、持久释放的特性。近年来,我国纳米银技术进步较大,纳米银产业也得到较快的发展。中国发明专利01110767《防聚集广谱抗菌纳米银微粉及产业化制作工艺》公开了一种防聚集广谱抗菌纳米银微粉及产业化制作工艺,将纳米银微粉牢固地吸附在一些天然多空隙植物材料上。中国发明专利02138891以藻类的空腔或空胞来吸附纳米银微粉。以上专利都是以多孔材料为载体制备纳米银粉体,未涉及以高聚物为稳定剂制备纳米银溶液及纳米银粉体方法。Nanotechnology is a frontier discipline that takes materials with a size of 1 to 100nm as the research object. Due to its high specific surface area, nano silver has the characteristics of fast and long-lasting release. In recent years, my country's nano-silver technology has made great progress, and the nano-silver industry has also developed rapidly. Chinese invention patent 01110767 "anti-aggregation broad-spectrum antibacterial nano-silver powder and industrial production process" discloses an anti-aggregation broad-spectrum antibacterial nano-silver powder and an industrial production process, which firmly adsorbs nano-silver powder on some natural porous plants material. Chinese invention patent 02138891 uses algal cavities or empty cells to adsorb nano-silver powder. The above patents all use porous materials as carriers to prepare nano-silver powders, and do not involve the preparation of nano-silver solutions and nano-silver powders with high polymers as stabilizers.

银离子的抗菌机理有以下两种观点:The antibacterial mechanism of silver ions has the following two views:

1.Ag+接触反应,认为Ag+通过接触反应造成微生物活性成分破坏或者产生阻碍。当微量Ag+到达微生物细胞膜时,因后者带有负电荷,依靠库仑引力,使二者牢固吸附,Ag+与菌体蛋白酶的-SH基结合,使以此为必要的酶丧失活性而无法生存,从而实现杀灭病菌的作用。1. Ag + contact reaction, it is considered that Ag + causes the destruction or hindrance of the active components of microorganisms through the contact reaction. When a small amount of Ag + reaches the microbial cell membrane, because the latter is negatively charged, the two are firmly adsorbed by Coulomb gravity, and Ag + combines with the -SH group of the bacterial protease, so that the necessary enzyme loses its activity and cannot Survive, so as to realize the effect of killing germs.

其抗菌机理为:Its antibacterial mechanism is:

Figure A20051004925800041
Figure A20051004925800041

2.催化假说,认为物质表面分布的微量Ag+能起到催化活性中心的作用,银能激活空气中或水中的氧,产生羟基自由基机活性氧离子。它们能破坏微生物细胞的增殖能力,抑制或杀灭细菌。2. Catalytic hypothesis, it is believed that the trace amount of Ag + distributed on the surface of the substance can act as a catalytic active center, and silver can activate oxygen in the air or water to generate hydroxyl radicals and active oxygen ions. They can destroy the proliferation ability of microbial cells, inhibit or kill bacteria.

发明内容Contents of the invention

本发明的目的是提供一种以高聚物为稳定剂的纳米银溶液和纳米银粉体的制备方法。The purpose of the present invention is to provide a preparation method of nano-silver solution and nano-silver powder with high polymer as stabilizer.

以高聚物为稳定剂的纳米银溶液制备方法:浓度为0.001~0.05g/ml水溶性高聚物稳定剂与浓度为0.001~0.1mol/L硝酸银复合,再使用浓度为0.001~0.2mol/L水溶性还原剂将硝酸银还原为纳米银,纳米银的粒径为5~100nm。Preparation method of nano-silver solution with polymer as stabilizer: the concentration is 0.001-0.05g/ml water-soluble polymer stabilizer and the concentration is 0.001-0.1mol/L silver nitrate composite, and then the concentration is 0.001-0.2mol The /L water-soluble reducing agent reduces silver nitrate to nano-silver, and the particle size of nano-silver is 5-100nm.

以高聚物为稳定剂的纳米银粉体制备方法:浓度为0.001~0.05g/ml壳聚糖稳定剂与浓度为0.001~0.1mol/L硝酸银复合,使用浓度为0.001~0.2mol/L水溶性还原剂将硝酸银还原为纳米银,再使用氢氧化钠溶液将纳米银沉积、洗涤、干燥、粉碎,获得粒径为5~100nm的纳米银。Preparation method of nano-silver powder with high polymer as stabilizer: chitosan stabilizer with a concentration of 0.001-0.05g/ml is compounded with silver nitrate with a concentration of 0.001-0.1mol/L, and the concentration used is 0.001-0.2mol/L to dissolve in water The silver nitrate is reduced to nano-silver by the active reducing agent, and then the nano-silver is deposited, washed, dried and pulverized by sodium hydroxide solution to obtain the nano-silver with a particle diameter of 5-100nm.

本发明不仅具有成本低、操作简单等优点,而且制备的纳米银颗粒具有极强的抗菌能力和广谱抗菌性。在本发明中,没有使用任何有机溶剂,符合绿色环保的要求。本发明的纳米银溶液纳米银溶液无毒副作用,在3个月内无沉淀,具有较好的稳定性。The invention not only has the advantages of low cost, simple operation and the like, but also the prepared nano-silver particle has extremely strong antibacterial ability and broad-spectrum antibacterial property. In the present invention, no organic solvent is used, which meets the requirements of environmental protection. The nano-silver solution of the present invention has no toxic and side effects, no precipitation within 3 months, and has good stability.

本发明所述的纳米银溶液可以对袜子、毛巾、鞋垫、内衣、纱线、抗菌袜、和口罩等织物进行处理,处理后的织物具有广谱长效抗菌功能。本发明所述的纳米银溶液可对商场、医院、电梯、车站等公共场所及厨房等家庭场所进行处理,预防传染病的发生。本发明所述的纳米银溶液可通过与其它添加剂或赋形剂结合制成面膜、洗手液、洗面液、沐浴液等,也可以用于烧烫伤、手术切口创面感染的预防与消毒。本发明所述的纳米银溶液也可以用于治疗细菌性阴道炎、男性前列腺炎等。本发明所述的纳米银溶液也可直接用于治理水污染。本发明所述的纳米银溶液和骨生长因子分别与骨载体进行复合,形成缓释膜,该抗感染植骨材料具有广谱、无耐药性等多种性能。本发明的高聚物稳定的广谱抗菌纳米银微粉可以用于制备抗菌型塑料用品、家电制品、涂料等。The nano-silver solution of the present invention can treat fabrics such as socks, towels, insoles, underwear, yarns, antibacterial socks, and masks, and the treated fabrics have broad-spectrum and long-lasting antibacterial functions. The nano-silver solution of the present invention can treat public places such as shopping malls, hospitals, elevators, stations, and household places such as kitchens to prevent the occurrence of infectious diseases. The nano-silver solution of the present invention can be combined with other additives or excipients to make facial masks, hand sanitizers, facial cleansers, body washes, etc., and can also be used for the prevention and disinfection of burns and surgical incision wound infections. The nano-silver solution of the present invention can also be used to treat bacterial vaginosis, male prostatitis and the like. The nano-silver solution of the present invention can also be directly used for controlling water pollution. The nano-silver solution and the bone growth factor described in the present invention are respectively compounded with the bone carrier to form a slow-release film, and the anti-infection bone graft material has multiple properties such as broad spectrum and no drug resistance. The polymer-stabilized broad-spectrum antibacterial nano-silver micropowder of the invention can be used for preparing antibacterial plastic products, home appliances, coatings and the like.

附图说明Description of drawings

附图是纳米银抗菌效果图。Accompanying drawing is nano-silver antibacterial effect picture.

具体实施方式Detailed ways

实施例1Example 1

以高聚物为稳定剂的纳米银溶液制备方法:取5g壳聚糖溶于95ml水中,加入1.69g硝酸银,在剧烈搅拌下,缓慢加入5ml含有3.5g抗坏血酸的水溶液。搅拌持续5~6个小时。即得稳定纳米银溶液。Preparation method of nano-silver solution using high polymer as stabilizer: Dissolve 5g of chitosan in 95ml of water, add 1.69g of silver nitrate, and slowly add 5ml of aqueous solution containing 3.5g of ascorbic acid under vigorous stirring. Stirring was continued for 5-6 hours. That is, a stable nano-silver solution is obtained.

透射电镜结果表明:纳米银颗粒平均100nm。The results of transmission electron microscopy show that the average size of nano-silver particles is 100nm.

实施例2Example 2

以高聚物为稳定剂的纳米银溶液制备方法:取0.1g甲基纤维素溶于95ml水中,加入34mg硝酸银,在剧烈搅拌下,缓慢加入5ml含有9mg甲醛的水溶液。搅拌持续5~6个小时。即得稳定纳米银溶液。Preparation method of nano-silver solution with high polymer as stabilizer: Dissolve 0.1g of methylcellulose in 95ml of water, add 34mg of silver nitrate, and slowly add 5ml of aqueous solution containing 9mg of formaldehyde under vigorous stirring. Stirring was continued for 5-6 hours. That is, a stable nano-silver solution is obtained.

透射电镜结果表明:纳米银颗粒粒度分布于80~100nm,平均90nm。The results of transmission electron microscopy show that the particle size distribution of nano-silver particles is 80-100nm, with an average of 90nm.

实施例3Example 3

以高聚物为稳定剂的纳米银溶液制备方法:取1g聚乙烯吡咯烷酮溶于95ml水中,加入16mg硝酸银,在剧烈搅拌下,缓慢加入5ml含有40mg硼氢化钠的水溶液。搅拌持续12~15个小时。即得稳定纳米银溶液。Preparation method of nano-silver solution with high polymer as stabilizer: Dissolve 1g of polyvinylpyrrolidone in 95ml of water, add 16mg of silver nitrate, and slowly add 5ml of aqueous solution containing 40mg of sodium borohydride under vigorous stirring. Stirring was continued for 12-15 hours. That is, a stable nano-silver solution is obtained.

透射电镜结果表明:纳米银颗粒粒度分布于20~30nm,平均27nm。The results of transmission electron microscopy showed that the particle size distribution of nano-silver particles was 20-30nm, with an average of 27nm.

实施例4Example 4

以高聚物为稳定剂的纳米银溶液制备方法:取0.05g聚羧乙胺溶于95ml水中,加入34mg硝酸银,在剧烈搅拌下,缓慢加入5ml含有17.6mg的抗坏血酸的水溶液。搅拌持续5~6个小时。即得稳定纳米银溶液。Preparation method of nano-silver solution with high polymer as stabilizer: Dissolve 0.05g of polycarboxyethylamine in 95ml of water, add 34mg of silver nitrate, and slowly add 5ml of an aqueous solution containing 17.6mg of ascorbic acid under vigorous stirring. Stirring was continued for 5-6 hours. That is, a stable nano-silver solution is obtained.

透射电镜结果表明:纳米银颗粒粒度分布于20~50nm,平均30nm。The results of transmission electron microscopy showed that the particle size distribution of nano-silver particles was 20-50nm, with an average of 30nm.

实施例5Example 5

以高聚物为稳定剂的纳米银溶液制备方法:取0.18g淀粉溶于95ml水中,加入34mg硝酸银,在剧烈搅拌下,缓慢加入5ml含有40mg的葡萄糖的水溶液。在37℃搅拌过夜。即得稳定纳米银溶液。Preparation method of nano-silver solution with high polymer as stabilizer: Dissolve 0.18g of starch in 95ml of water, add 34mg of silver nitrate, and slowly add 5ml of aqueous solution containing 40mg of glucose under vigorous stirring. Stir overnight at 37°C. That is, a stable nano-silver solution is obtained.

透射电镜结果表明:纳米银颗粒粒度分布于3~10hm,平均5nm。即得以淀粉为稳定剂的纳米银溶液。所得的纳米银溶液可以将96%的细菌杀死(见附图所示)The results of transmission electron microscopy showed that the particle size distribution of nano-silver particles was in the range of 3-10hm, with an average of 5nm. That is, the nano-silver solution with starch as a stabilizer. The resulting nano-silver solution can kill 96% of bacteria (see attached picture)

实施例6Example 6

以高聚物为稳定剂的纳米银粉体制备方法:取5g壳聚糖溶于95ml水中,加入1.69g硝酸银,在剧烈搅拌下,缓慢加入5ml含有3.5g抗坏血酸的水溶液。搅拌持续5~6个小时。往纳米银溶液中滴加氢氧化钠溶液,并过滤。将过滤所得固体用蒸馏水洗涤,并在约80℃条件下烘干。将干燥后的样品适当研磨分散。即得纳米银微粉。透射电镜结果表明:纳米银颗粒平均100nm。Preparation method of nano-silver powder with high polymer as stabilizer: Dissolve 5g of chitosan in 95ml of water, add 1.69g of silver nitrate, and slowly add 5ml of aqueous solution containing 3.5g of ascorbic acid under vigorous stirring. Stirring was continued for 5-6 hours. Add sodium hydroxide solution dropwise to the nano-silver solution, and filter. The filtered solid was washed with distilled water and dried at about 80°C. The dried samples were properly ground and dispersed. That is, nano-silver powder is obtained. The results of transmission electron microscopy show that the average size of nano-silver particles is 100nm.

实施例7Example 7

以高聚物为稳定剂的纳米银粉体制备方法:取0.4g壳聚糖溶于95ml水中,加入16mg硝酸银,在剧烈搅拌下,缓慢加入5ml含有40mg硼氢化钠的水溶液。搅拌持续5~6个小时。往纳米银溶液中滴加氢氧化钠溶液,并过滤。将过滤所得固体用蒸馏水洗涤,并在约80℃条件下烘干。将干燥后的样品适当研磨分散。即得纳米银微粉。透射电镜结果表明:纳米银颗粒平均20nm。Preparation method of nano-silver powder with polymer as stabilizer: Dissolve 0.4g of chitosan in 95ml of water, add 16mg of silver nitrate, and slowly add 5ml of aqueous solution containing 40mg of sodium borohydride under vigorous stirring. Stirring was continued for 5-6 hours. Add sodium hydroxide solution dropwise to the nano-silver solution, and filter. The filtered solid was washed with distilled water and dried at about 80°C. The dried samples were properly ground and dispersed. That is, nano-silver powder is obtained. The results of transmission electron microscopy show that the average size of nano-silver particles is 20nm.

实施例8Example 8

以高聚物为稳定剂的纳米银粉体制备方法:取0.1g壳聚糖溶于95ml水中,加入16mg硝酸银,在剧烈搅拌下,缓慢加入5ml含有3mg甲醛的水溶液。搅拌持续5~6个小时。往纳米银溶液中滴加氢氧化钠溶液,并过滤。将过滤所得固体用蒸馏水洗涤,并在约80℃条件下烘干。将干燥后的样品适当研磨分散。即得纳米银微粉。透射电镜结果表明:纳米银颗粒平均5nm。Preparation method of nano-silver powder with polymer as stabilizer: Dissolve 0.1g of chitosan in 95ml of water, add 16mg of silver nitrate, and slowly add 5ml of aqueous solution containing 3mg of formaldehyde under vigorous stirring. Stirring was continued for 5-6 hours. Add sodium hydroxide solution dropwise to the nano-silver solution, and filter. The filtered solid was washed with distilled water and dried at about 80°C. The dried samples were properly ground and dispersed. That is, nano-silver powder is obtained. The results of transmission electron microscopy show that the average size of nano-silver particles is 5nm.

实施例9Example 9

以高聚物为稳定剂的纳米银粉体制备方法:取2g壳聚糖溶于95ml水中,加入80mg硝酸银,在剧烈搅拌下,缓慢加入5ml含有200mg的葡萄糖的水溶液。在37℃搅拌过夜。往纳米银溶液中滴加氢氧化钠溶液,并过滤。将过滤所得固体用蒸馏水洗涤,并在约80℃条件下烘干。将干燥后的样品适当研磨分散。即得纳米银微粉。透射电镜结果表明:纳米银颗粒平均50nm。Preparation method of nano-silver powder with high polymer as stabilizer: Dissolve 2g of chitosan in 95ml of water, add 80mg of silver nitrate, and slowly add 5ml of aqueous solution containing 200mg of glucose under vigorous stirring. Stir overnight at 37°C. Add sodium hydroxide solution dropwise to the nano-silver solution, and filter. The filtered solid was washed with distilled water and dried at about 80°C. The dried samples were properly ground and dispersed. That is, nano-silver powder is obtained. The results of transmission electron microscopy show that the average size of silver nanoparticles is 50nm.

Claims (5)

1.一种以高聚物为稳定剂的纳米银溶液制备方法,其特征在于浓度为0.001~0.05g/ml水溶性高聚物稳定剂与浓度为0.001~0.1mol/L硝酸银复合,再使用浓度为0.001~0.2mol/L水溶性还原剂将硝酸银还原为纳米银,纳米银的粒径为5~100nm。1. a method for preparing nano-silver solution with high polymer as stabilizer, characterized in that concentration is 0.001~0.05g/ml water-soluble high polymer stabilizer and concentration is 0.001~0.1mol/L silver nitrate compound, then The silver nitrate is reduced to nano-silver by using a water-soluble reducing agent with a concentration of 0.001-0.2 mol/L, and the particle size of the nano-silver is 5-100 nm. 2.根据权利要求1所述的一种以高聚物为稳定剂的纳米银溶液制备方法,其特征在于,所述的水溶性高聚物为:淀粉类衍生物、壳聚糖、纤维素衍生物、聚乙烯吡咯烷酮或聚羧乙胺一种或多种。2. a kind of nano-silver solution preparation method taking high polymer as stabilizer according to claim 1, is characterized in that, described water-soluble high polymer is: starch derivative, chitosan, cellulose One or more of derivatives, polyvinylpyrrolidone or polycarboxyethylamine. 3.根据权利要求1所述的一种以高聚物为稳定剂的纳米银溶液制备方法,其特征在于,所述的水溶性还原剂为:葡萄糖、抗坏血酸、甲醛或硼氢化钠。3. a kind of nano-silver solution preparation method that takes high polymer as stabilizer according to claim 1, is characterized in that, described water-soluble reducing agent is: glucose, ascorbic acid, formaldehyde or sodium borohydride. 4.一种以高聚物为稳定剂的纳米银粉体制备方法,其特征在于,浓度为0.001~0.05g/ml壳聚糖稳定剂与浓度为0.001~0.1mol/L硝酸银复合,使用浓度为0.001~0.2mol/L水溶性还原剂将硝酸银还原为纳米银,再使用氢氧化钠溶液将纳米银沉积、洗涤、干燥、粉碎,获得粒径为5~100nm的纳米银。4. A method for preparing a nano-silver powder with a high polymer as a stabilizer, characterized in that the chitosan stabilizer with a concentration of 0.001 to 0.05g/ml is compounded with silver nitrate at a concentration of 0.001 to 0.1mol/L. Using 0.001-0.2mol/L water-soluble reducing agent to reduce silver nitrate to nano-silver, and then use sodium hydroxide solution to deposit, wash, dry and pulverize nano-silver to obtain nano-silver with a particle size of 5-100nm. 5.根据权利要求4所述的一种以高聚物为稳定剂的纳米银粉体制备方法,其特征在于,所述的水溶性还原剂为葡萄糖、抗坏血酸、甲醛或硼氢化钠。5. a kind of nano-silver powder preparation method using high polymer as stabilizer according to claim 4, is characterized in that, described water-soluble reducing agent is glucose, ascorbic acid, formaldehyde or sodium borohydride.
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