CN101142919B - Sepiolite broad-spectrum inorganic antibiotic agent containing composite metal ion and its preparation method - Google Patents
Sepiolite broad-spectrum inorganic antibiotic agent containing composite metal ion and its preparation method Download PDFInfo
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- CN101142919B CN101142919B CN2007100498746A CN200710049874A CN101142919B CN 101142919 B CN101142919 B CN 101142919B CN 2007100498746 A CN2007100498746 A CN 2007100498746A CN 200710049874 A CN200710049874 A CN 200710049874A CN 101142919 B CN101142919 B CN 101142919B
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Abstract
The invention discloses a sepiolite-typed inorganic antimicrobial agent with compound metal antimicrobial ion and a preparation method, which belongs to the field of antimicrobial material. The invention is characterized in that the natural sepiolite with low cost is adopted as carrying material, and then after activation modification, the sepiolite carries compound silver ion and zinc ion or compound silver ion and copper ion with the method of ion exchange and absorption, therefore, the inorganic antimicrobial agent with strong antimicrobial capability is prepared well. The compound antimicrobial agent provided by the invention has simple preparation process, low cost, no discoloration, strong broad-spectrum antimicrobial capability and a wide range of use. The invention not only can be used as antimicrobial material separately, but also can be added into a plurality of materials, such as plastic, coating, fiber, ceramic, decorative and architectural material and daily cosmetic, therefore, product with antimicrobial property can be prepared for application. Meanwhile, as the sepiolite carrier has good rheological property, thermal stability, dispersion, mechanical strength and other good properties, overall performance of the product can be improved.
Description
One, technical field
The present invention relates to class broad-spectrum inorganic antibiotic agent and preparation method thereof.What be specifically related to is sepiolite type inorganic antiseptic that contains the composite antibiosis metal ion and preparation method thereof.Belong to the anti-biotic material field.
Two, technical background
Harmful microorganism (bacterium, fungi and mould etc.) and virus are extensive in distributed in nature, of a great variety, the serious threat human beings'health.Antibacterial agent is within a certain period of time, has the material of inhibition, kill harmful microorganism.The use of antibacterial agent keeps assanation to effectively preventing the growth and breeding of various bacteriums, fungi and mould, avoids epiphytotics generation and propagation that important effect is arranged.Along with the progress of society, the raising of living standards of the people, research and development novel, efficient, nontoxic (or low toxicity), lasting antibacterial agent and anti-biotic material has important practical significance and vast market prospect.
Antibacterial agent is divided into inorganic antiseptic and organic antibacterial agent.That the relative organic antibacterial agent of inorganic antiseptic has is safe, high temperature resistant, good stability, antibiotic a series of outstanding advantages such as lasting.The application feature of inorganic antiseptic shows at present, and metal ion type inorganic antibacterial material is used wider, and anti-microbial property is better.The main antibacterial metal ions of this class antibacterial agent is silver, zinc and copper.The antibacterial ability of silver is the strongest in three metal ion species, so carrying silver antimicrobials is occupied an leading position in this class antibacterial agent.But there are two big subject matters in the use of carrying silver antimicrobials, the one, and discoloration problem, because the chemism of silver ion is big, variable color takes place in easily oxidation and reduction, causes its antibacterial strength and antibiotic continuation to reduce, actual antibacterial effect and the scope of using of influence.The 2nd, on the high side, be difficult to the extensive use problem.Though using separately, zinc ion and copper ion kill the too late silver ion of the ability that presses down bacterium, but the effect that antimycotic by force and mould are arranged, and it is cheap, if itself and the compound use of silver ion not only can be reduced silver-colored consumption, reduce cost, avoid variable color to a certain extent, also can produce synergy, improve the ability of antimycotic and mould.The high reason of carrying silver antimicrobials price is except because silver ion on the high side, and is also higher relevant with the price of carrier material.The carrier material majority of current employing is zeolite, phosphate, adsorptivity silica gel of synthetic etc., though these materials have advantages such as purity height, fine size, whiteness height, ion-exchange capacity be strong, cost is higher.Sepiolite is the moisture magnesia silicate mineral of a kind of natural fibrous.Because of its unique pore passage structure and composition characteristics have big potential specific surface area and good adsorption performance, ion-exchange performance and catalysis.It is cheap, is the antibiotic carrier material that has fine exploitation to be worth.In addition sepiolite has excellent properties such as rheological characteristic, heat endurance, dispersiveness and mechanical strength preferably, can be used as additive and improves the use The comprehensive performance.
Based on above-mentioned analysis, the this patent invention is considered from carrier material and antibiotic ion, selecting excellent performance, cheap natural sepiolite for use is carrier, adopts the thinking research of silver-colored zinc, the compound use of the antibiotic ion of silver-bearing copper to prepare the novel sepiolite type broad-spectrum inorganic antibiotic agent that contains composite metal ion.By retrieval, do not find identical with it patent application or bibliographical information.
Three, summary of the invention
The objective of the invention is to fully utilize the excellence absorption and the switching performance of the antibacterial characteristics and the sepiolite of silver, copper, three kinds of ions of zinc, adopt the method for ion exchange absorption, with silver-colored zinc with silver-bearing copper is compound is stated from the sepiolite, prepare have strong antibacterium, antimycotic and antifungi ability, easy to change and not cheap broad-spectrum inorganic antibiotic agent.Concrete processing step of the present invention (method) is:
(1) sepiolite that will be through separate purifying and concentration are that the hydrochloric acid of 0.2～2.4mol/L is that 1: 20～40 ratio is mixed with solid-to-liquid ratio, stir 2～10h under 60～100 ℃ of temperature;
(2) centrifugal or filtering means dehydration, washing back are for several times dried under 80～120 ℃ temperature;
(4) at roasting temperature 1～4h of 100～300 ℃;
(5) be that the tertiary sodium phosphate of 0.1～5mol/L is 20～100 ℃ at bath temperature and filters washing and dry after handling down (4) set by step prepared sepiolite 3-10h with concentration;
(6) soluble silver salt is become soluble zinc salt or soluble copper salt are hybridly prepared into the salting liquid of argentiferous zinc or silver-bearing copper ion, wherein the mol ratio of silver ion and zinc ion or silver ion and copper ion is 1: 1～1: 6;
(7) will be set by step the solution prepared of sepiolite and (6) set by step of (5) preparation be that 1: 10～60 ratio is mixed with solid-to-liquid ratio, be to stir 2～8h under 5～8 the condition in 20～100 ℃ of temperature, pH value;
(8) will be set by step (7) preparation the product suction filtration, the washing after, under 105 ℃ of temperature the oven dry levigate, make compound silver-colored zinc or silver-bearing copper sepiolite antibacterial agent.
In the method for the invention, used silver salt, zinc salt and mantoquita refers to their nitrate or sulphate respectively.
In the method for the invention, used carrier sepiolite can replace with mineral palygorskite of the same clan.
The invention has the advantages that preparation technology is simple, cost is low, a little less than the discolouration, the effect of strong antibacterium, mould and fungi is arranged, and purposes is in extensive range.Both can use as anti-biotic material separately, also can add in the multiple materials such as plastics, coating, fiber, pottery, building decoration and daily cosmetics, and make goods and be applied with broad spectrum antibacterial performance.Moreover,, excellent properties such as rheological characteristic, heat endurance, dispersiveness and mechanical strength are preferably arranged, also can improve the use The comprehensive performance because the used carrier material is a sepiolite.
Four, embodiment
Following examples further specify the present invention, but do not limit the present invention.
Embodiment 1: the compound sepiolite inorganic antiseptic of a kind of silver-colored zinc ion (silver ion: preparation method zinc ion=1: 1)
The carrier sepiolite sample that present embodiment adopted comes from Nan Yang, Henan city precious sepiolite of heap of stone Co., Ltd, and the author adopts X-ray diffraction analysis (XRD), infrared absorption spectroscopy (IR) and SEM technical methods such as (SEM) that the used sepiolite former state of example has been carried out test analysis with sepiolite sample after separating purification and activation processing.The result shows that the sepiolite former state contains more quartz, talcum and carbonate mineral.By the sample after the purification activation processing, its impurity component is removed clean, and ion exchange and absorption property improve, but the structure of sepiolite remains unchanged.
A kind of compound silver-colored zinc ion sepiolite inorganic antiseptic in the present embodiment (zinc ion=1: 1) and preparation method thereof silver ion: carry out according to the following steps:
(1) sepiolite that will be through separate purifying and concentration are that the hydrochloric acid of 1.2mol/L is that 1: 40 ratio is mixed with solid-to-liquid ratio, stir 8h under 80 ℃ of temperature;
(2) centrifugal or filtering means dehydration, washing back are for several times dried under 105 ℃ temperature;
(4) at 230 ℃ roasting temperature 3.5h;
(5) be that the tertiary sodium phosphate of 0.5mol/L is 70 ℃ at bath temperature and filters washing and dry after handling down (4) set by step prepared sepiolite 6h with concentration;
(6) soluble silver salt and soluble zinc salt are hybridly prepared into the salting liquid of argentiferous zinc ion, wherein the mol ratio of silver ion and zinc ion is 1: 1;
(7) will be set by step the solution prepared of sepiolite and (6) set by step of (5) preparation be that 1: 15 ratio is mixed with solid-to-liquid ratio, be to stir 3.5h under 7 the condition in 60 ℃ of temperature, pH value;
(8) will be set by step (7) preparation the product suction filtration, the washing after, under 105 ℃ of temperature the oven dry levigate, make compound silver-colored zinc sepiolite antibacterial agent.
The anti-microbial property that the sepiolite inorganic antiseptic of the argentiferous zinc ion that above-mentioned processing step is made carries out Escherichia coli and staphylococcus aureus detects.In antibacterial agent concentration is 5mg/mL, and the contact action time is that the testing result under the condition of 2h shows that its antibiotic rate has all reached more than 90 percent.See for details appended: " antibacterial antiplaque agent performance test results table in the examples of implementation ".
Embodiment 2: a kind of compound silver-colored zinc ion sepiolite inorganic antiseptic (silver ion: preparation method zinc ion=1: 4)
Zinc ion=1: 4) and preparation method thereof a kind of compound silver-colored zinc ion sepiolite inorganic antiseptic in the present embodiment (silver ion: with (the silver ion: zinc ion=1: 1) and preparation method thereof identical on preparation raw material, process, but silver ion and zinc ion is compound than different of a kind of compound silver-colored zinc sepiolite inorganic antiseptic described in the embodiment 1.Analyze and the anti-microbial property detection by inductively coupled plasma atomic emission (ICP), compare with the similar antibacterial agent among the embodiment 1, the contained silver ion amount of this example antibacterial agent reduces, and the zinc ion amount increases, and anti-microbial property is still fine.The result sees for details appended " antibacterial antiplaque agent performance test results table in the examples of implementation ".This is to reducing cost, and the defective of avoiding the silver ion variable color is favourable.
Embodiment 3: the compound sepiolite inorganic antiseptic of a kind of silver-bearing copper ion (silver ion: preparation method copper ion=1: 1)
A kind of composite silver copper ion sepiolite inorganic antiseptic described in the present embodiment (silver ion: preparation method copper ion=1: 1) carries out according to the following steps:
(1) sepiolite that will be through separate purifying and concentration are that the hydrochloric acid of 1.2mol/L is that 1: 40 ratio is mixed with solid-to-liquid ratio, stir 8h under 80 ℃ of temperature;
(2) centrifugal or filtering means dehydration, washing back are for several times dried under 105 ℃ temperature;
(4) at 230 ℃ roasting temperature 3.5h;
(5) be that the tertiary sodium phosphate of 0.5mol/L is 60 ℃ at bath temperature and filters washing and dry after handling down (4) set by step prepared sepiolite 6h with concentration;
(6) soluble silver salt and soluble copper salt are hybridly prepared into the salting liquid of silver-bearing copper ion, wherein the mol ratio of silver ion and copper ion is 1: 1;
(7) will be set by step the solution prepared of sepiolite and (6) set by step of (5) preparation be that 1: 15 ratio is mixed with solid-to-liquid ratio, be to stir 4h under 7 the condition in 60 ℃ of temperature, pH value;
(8) will be set by step (7) preparation the product suction filtration, the washing after, under 105 ℃ of temperature the oven dry levigate, make composite silver copper sepiolite antibacterial agent.
The anti-microbial property that the sepiolite inorganic antiseptic of the silver-bearing copper ion that above-mentioned processing step is made advances back Escherichia coli and staphylococcus aureus detects, in antibacterial agent concentration is 5mg/mL, be that the testing result under the 2h condition shows action time, its antibiotic rate has all reached more than 90 percent, sees for details appended: " antibacterial antiplaque agent performance test results table in the examples of implementation ".
Embodiment 4: a kind of composite silver copper ion sepiolite inorganic antiseptic (silver ion: preparation method copper ion=1: 3)
Copper ion=1: 3) and preparation method thereof a kind of composite silver copper ion sepiolite inorganic antiseptic in the present embodiment (silver ion: with (the silver ion: copper ion=1: 1) and preparation method thereof identical on preparation raw material, process, but silver ion and copper ion is compound than different of a kind of composite silver copper sepiolite inorganic antiseptic described in the embodiment 3.Analyze and the anti-microbial property detection by inductively coupled plasma atomic emission (ICP), compare with the similar antibacterial agent among the embodiment 3, though the contained silver ion amount of this example antibacterial agent reduces, anti-microbial property is not subjected to tangible influence.The result sees for details appended " antibacterial antiplaque agent performance test results table in the examples of implementation ".This is to reducing cost, and the influence that reduces to produce because of the silver ion variable color is favourable.
The antibacterial antiplaque agent performance is examined table as a result in the examples of implementation
Claims (3)
1. the preparation method who contains the sepiolite broad-spectrum inorganic antibiotic agent of composite metal ion, it is characterized in that fully utilizing the anti-microbial property of silver, copper, zinc ion and the characteristics of the excellent absorption of sepiolite switching performance, adopt the method for ion exchange absorption, with silver-colored zinc ion with the silver-bearing copper ion is compound is stated from the sepiolite, preparation has strong antibacterium, antimycotic and antifungi ability, easy to change and not cheap broad-spectrum inorganic antibiotic agent, described preparation method, its feature has following processing step:
(1) sepiolite that will be through separate purifying and concentration are that the hydrochloric acid of 0.2～2.4mol/L is that 1: 20～100 ratio is mixed with solid-to-liquid ratio, stir 2～10h under 60～100 ℃ of temperature;
(2) centrifugal or filtering means dehydration, washing back are for several times dried under 80～120 ℃ temperature;
(4) at roasting temperature 1～4h of 100～300 ℃;
(5) be that the tertiary sodium phosphate of 0.1～5mol/L is 20～100 ℃ at bath temperature and filters washing and dry after handling down (4) set by step prepared sepiolite 3-10h with concentration;
(6) soluble silver salt and soluble zinc salt or soluble copper salt are hybridly prepared into the salting liquid of argentiferous zinc or silver-bearing copper ion, wherein the mol ratio of silver ion and zinc ion or silver ion and copper ion is 1: 1～1: 6;
(7) will be set by step the solution prepared of sepiolite and (6) set by step of (5) preparation be that 1: 10～60 ratio is mixed with solid-to-liquid ratio, be to stir 2～8h under 5～8 the condition in 20～100 ℃ of temperature, pH value;
(8) will be set by step behind the product suction filtration, washing of (7) preparation, under 105 ℃ of temperature oven dry levigate, make the sepiolite antibacterial agent of argentiferous zinc or silver-bearing copper composite metal ion.
2. the preparation method who contains the sepiolite broad-spectrum inorganic antibiotic agent of composite metal ion according to claim 1 is characterized in that: described soluble silver salt, zinc salt and mantoquita refer to their sulphate and nitrate respectively.
3. the preparation method who contains the sepiolite inorganic antiseptic of composite metal ion according to claim 1 is characterized in that: described carrier sepiolite can replace with mineral palygorskite of the same clan.
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| CN2007100498746A CN101142919B (en) | 2007-08-29 | 2007-08-29 | Sepiolite broad-spectrum inorganic antibiotic agent containing composite metal ion and its preparation method |
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| CN101142919B true CN101142919B (en) | 2010-06-16 |
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Families Citing this family (14)
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| CN102210302B (en) * | 2011-04-13 | 2013-04-10 | 华南理工大学 | Porous inorganic material with insecticidal and mothproof function and preparation method thereof |
| CN102274717B (en) * | 2011-08-10 | 2012-09-26 | 农业部环境保护科研监测所 | Method for preparing thio-modified sepiolite heavy metal absorbent |
| CN104161044A (en) * | 2014-08-07 | 2014-11-26 | 蔡惠萍 | Preparation method and application of organic/inorganic compound antibacterial agent |
| CN104206418A (en) * | 2014-08-07 | 2014-12-17 | 蔡惠萍 | Preparation method and application of discoloration-preventing powdery silver-containing anti-bacterial agent |
| CN105638731B (en) * | 2016-01-30 | 2016-10-12 | 湘潭大学 | A kind of preparation method of meerschaum antibacterial powder |
| CN106135275A (en) * | 2016-06-24 | 2016-11-23 | 湘潭大学 | A kind of preparation method of the sepiolite antimicrobial powder of organically-modified and load silver ion |
| CN107082929A (en) * | 2017-05-04 | 2017-08-22 | 宜宾天亿新材料科技有限公司 | A kind of feature PE feed pipes formula and preparation method thereof |
| CN107713007B (en) * | 2017-09-07 | 2020-08-18 | 滁州市光威化工有限公司 | Sepiolite antibacterial cigarette filter tip paper and preparation method thereof |
| CN109778373A (en) * | 2018-12-13 | 2019-05-21 | 北京方诣生物医药有限公司 | A kind of bacteriostasis, and deodorization blend fibre and preparation method thereof and textile |
| CN109527077A (en) * | 2018-12-27 | 2019-03-29 | 湘潭大学 | A kind of method that sepiolite/essential oil composite material prevents and treats rod method after grape harvest |
| CN111357764B (en) * | 2020-03-03 | 2021-06-11 | 北京大学 | Composite metal ion broad-spectrum sterilization antiviral material and preparation method thereof |
| CN112480725A (en) * | 2020-12-04 | 2021-03-12 | 广东海畅新材料有限公司 | Inorganic antibacterial building coating and preparation method thereof |
| CN114158571A (en) * | 2021-12-17 | 2022-03-11 | 武汉苏泊尔炊具有限公司 | Antibacterial material and preparation method and application thereof |
| CN115710818A (en) * | 2022-11-16 | 2023-02-24 | 湖南工程学院 | Silver ion-loaded sepiolite fiber carbon nanotube composite antibacterial material-finished polypropylene non-woven fabric |
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