CN103980665A - Waterborne antibacterial composite material and preparation method thereof - Google Patents
Waterborne antibacterial composite material and preparation method thereof Download PDFInfo
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- CN103980665A CN103980665A CN201410211413.4A CN201410211413A CN103980665A CN 103980665 A CN103980665 A CN 103980665A CN 201410211413 A CN201410211413 A CN 201410211413A CN 103980665 A CN103980665 A CN 103980665A
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Abstract
The invention discloses a waterborne antibacterial composite material and a preparation method thereof. The preparation method comprises the steps of firstly modifying epoxy resin (EP) by polyethylene glycol (PEG) to obtain a water-soluble epoxy resin (EP-PEG); and then preparing Ag/(EP-PEG) (water-soluble modified epoxy resin) sol by a method for reducing silver nitrate to obtain a polymer silver nanoparticle coated antibacterial composite material emulsion with stable dispersion, wherein the water-soluble modified epoxy resin (EP-PEG) is taken as a reducing agent as well as a stabilizer and water is taken as a reaction medium. Latex obtained by the method has the advantages of uniform particle size, good water solubility and no obvious agglomeration and can effectively inhibit and kill various bacteria.
Description
Technical field
The present invention relates to a kind of water-soluble Antibacterial Composite Material and Preparation Method, belong to macromolecule material preparation area.
Background technology
Along with growth in the living standard, quality and the health level of people to living environment had higher requirement, particularly to healthy consciousness also in continuous enhancing.On the other hand, various pathogenic microorganisms are very extensive in distributed in nature, and grow under certain condition, breed, and even variation not only can cause the decomposition, rotten and corrupt of various materials, the health that is also threatening the mankind.Thereby expedited the emergence of a large amount of generations of antiseptic-germicide, also promote the fast development of antimicrobial technology and anti-biotic material simultaneously.
Anti-biotic material or antimicrobial prod are to make by adding antiseptic-germicide, and antiseptic-germicide, according to the difference of its material, can be divided into the Four types such as inorganic antiseptic, organic antibacterial agent, natural antibacterial agent and polymer antibacterial agent.
Inorganic antiseptic be utilize silver, copper, zinc, metal and the sterilization of ion or the class antiseptic-germicide that bacteriostasis makes such as admire.Inorganic antiseptic is normally by having the metal ion of anti-microbial activity and the body that carrier forms at present, mainly, taking silver-series antibacterial agent as main, have antibacterial ability strong, the antibacterial phase is long, low toxin, but easily variable color, manufacture the reasons such as difficulty, use cost are high and limited its use.
Organic antibacterial agent is mainly the materials such as organic acid, vinegar, alcohol, phenol, compared with dissolution type inorganic antiseptic, organic antibacterial agent Application and Development is wanted early manyly, there is easy to process, miscellaneous feature, be widely used in the industrial circles such as plastics, fiber, paper, rubber, resin, coating and water treatment.
In modern chemical industry is produced, pollution problem not only derives from raw material, and is derived from the material using in production process, is mainly the solvent using in reaction, sepn process.The solvent the most generally using is volatile organic compound, in use can cause the pollution of water resources.Therefore the synthetic method of developing and use nontoxic solvent to substitute volatile solvent becomes one of important research direction of Green Chemistry.
Summary of the invention
The invention provides a kind of water-soluble Antibacterial Composite Material and Preparation Method, to solve the above-mentioned problems in the prior art.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of water-soluble antimicrobial composite material is the colloidal sol of the water-soluble epoxy resin of bag Ag-bearing nanoparticle.
A kind of preparation method of water-soluble antimicrobial composite material as described in the present invention, it comprises the steps: soluble in water water-soluble epoxy resin emulsion, stir the solution to form homogeneous at 20～60 DEG C after, dropwise add silver nitrate solution, continue to be stirred to the micro-yellow of appearance or yellow-green colour colloidal sol, stop heating, temperature adjustment continues to stir 10～20 minutes to room temperature, discharging, wherein, the preparation of described water-soluble epoxy resin emulsion is that polyoxyethylene glycol and epoxy resin are added to the water, add again concentrated hydrochloric acid, be warming up to 45～70 DEG C, stirring reaction, obtain water-soluble epoxy resin emulsion.
As preferred version, in reaction solution, Silver Nitrate is 1:(15～50 with the ratio of the dry weight of water-soluble epoxy resin).
As preferred version, the polyoxyethylene glycol that described polyoxyethylene glycol is commercially available various molecular weight, preferably PEG-2000; Described epoxy resin is the epoxy resin of commercially available various molecular weight, preferably E-20.
As further preferred version, the mol ratio of described polyoxyethylene glycol and epoxy resin is 1:(2～5).
The invention has the advantages that: Ag/ (EP-PEG) (water miscible epoxy resin) sol particle making is little, good dispersion, does not significantly reunite between particle, and Average Particle Diameters is 70nm left and right; Ag/ (EP-PEG) (water miscible epoxy resin) colloidal sol can reach 0.06 μ g.mL to streptococcus aureus minimal inhibitory concentration (MIC)
-1below, minimal bactericidal concentration reaches 0.15 μ g.mL
-1below; Colibacillary minimal inhibitory concentration and minimal bactericidal concentration are reached and all reach 0.03 μ g.mL
-1left and right.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of the water-soluble epoxy resin colloidal sol of the Bao Zaiyin for preparing of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.
In the present invention, concentrated hydrochloric acid used is commercially available concentrated hydrochloric acid.
Embodiment 1
One, in reactor, add epoxy resin E-20 and the 5L deionized water of PEG2000, the 2mol of 1mol, then add the concentrated hydrochloric acid of 2mL, be warming up to 50 DEG C, stirring reaction 2.5 hours, obtains water-soluble epoxy resin emulsion, for subsequent use;
Two, in the Erlenmeyer flask of 1L, add 200mL deionized water, get a certain amount of water-soluble epoxy resin and be dissolved in wherein, at 60 DEG C, vigorous stirring makes it form the solution of homogeneous, dropwise adds 50mL0.01molL
-1silver nitrate solution, in the hierarchy of control, the dry weight ratio of Silver Nitrate and water-soluble epoxy resin is 1:40, be stirred well to and occur micro-yellow or yellow-green colour colloidal sol, illustrate that silver ions is reduced to simple substance silver, stop heating, after being cooled to room temperature, continue to stir after 15 minutes, obtain silver-colored/water-soluble epoxy resin mixture colloidal sol.
As shown in Figure 1, sol particle is little for the transmission electron microscope photo of silver/water-soluble epoxy resin mixture colloidal sol that the present embodiment obtains, and good dispersion is not significantly reunited between particle, and Average Particle Diameters is 70nm left and right.
The anti-microbial property of silver/water-soluble epoxy resin mixture colloidal sol that the present embodiment obtains is as shown in table 1,
Minimal inhibitory concentration (MIC) and the minimal bactericidal concentration (MBC) of table 1 silver/EP-PEG colloidal sol to different bacterium
| ? | Streptococcus aureus | Intestinal bacteria |
| MIC(μg.mL -1) | 0.06213 | 0.03187 |
| MBC(μg.mL -1) | 0.11852 | 0.03062 |
Embodiment 2
One, in reactor, add epoxy resin E-20 and the 5L deionized water of PEG4000, the 3mol of 1mol, then add the concentrated hydrochloric acid of 2mL, be warming up to 60 DEG C, stirring reaction 3 hours, obtains water-soluble epoxy resin emulsion, for subsequent use;
Two, in the Erlenmeyer flask of 1L, add 250mL deionized water, get a certain amount of water-soluble epoxy resin and be dissolved in wherein, at 60 DEG C, vigorous stirring makes it form the solution of homogeneous, dropwise adds 50mL0.1molL
-1silver nitrate solution, in the hierarchy of control, the dry weight ratio of Silver Nitrate and water-soluble epoxy resin is 1:50, be stirred well to and occur micro-yellow or yellow-green colour colloidal sol, illustrate that silver ions is reduced to simple substance silver, stop heating, after being cooled to room temperature, continue to stir after 30 minutes, obtain silver-colored/water-soluble epoxy resin mixture colloidal sol.
Embodiment 3
One, in reactor, add epoxy resin E-51 and the 5L deionized water of PEG2000, the 4mol of 1.5mol, then add the concentrated hydrochloric acid of 2mL, be warming up to 60 DEG C, stirring reaction 2.5 hours, obtains water-soluble epoxy resin emulsion, for subsequent use;
Two, in the Erlenmeyer flask of 1L, add 300mL deionized water, get a certain amount of water-soluble epoxy resin and be dissolved in wherein, at 65 DEG C, vigorous stirring makes it form the solution of homogeneous, dropwise adds 50mL0.01molL
-1silver nitrate solution, in the hierarchy of control, the dry weight ratio of Silver Nitrate and water-soluble epoxy resin is 1:30, be stirred well to and occur micro-yellow or yellow-green colour colloidal sol, illustrate that silver ions is reduced to simple substance silver, stop heating, after being cooled to room temperature, continue to stir after 20 minutes, obtain silver-colored/water-soluble epoxy resin mixture colloidal sol.
Embodiment 4
One, in reactor, add epoxy resin E-44 and the 5L deionized water of PEG2000, the 1mol of 1mol, then add the concentrated hydrochloric acid of 2mL, be warming up to 60 DEG C, stirring reaction 2 hours, obtains water-soluble epoxy resin emulsion, for subsequent use;
Two, in the Erlenmeyer flask of 1L, add 200mL deionized water, get a certain amount of water-soluble epoxy resin and be dissolved in wherein, at 60 DEG C, vigorous stirring makes it form the solution of homogeneous, dropwise adds 50mL0.01molL
-1silver nitrate solution, in the hierarchy of control, the dry weight ratio of Silver Nitrate and water-soluble epoxy resin is 1:20, be stirred well to and occur micro-yellow or yellow-green colour colloidal sol, illustrate that silver ions is reduced to simple substance silver, stop heating, after being cooled to room temperature, continue to stir after 20 minutes, obtain silver-colored/water-soluble epoxy resin mixture colloidal sol.
Embodiment 5
One, in reactor, add epoxy resin E-20 and the 5L deionized water of PEG600, the 3mol of 1mol, then add the concentrated hydrochloric acid of 2mL, be warming up to 60 DEG C, stirring reaction 3 hours, obtains water-soluble epoxy resin emulsion, for subsequent use;
Two, in the Erlenmeyer flask of 1L, add 250mL deionized water, get a certain amount of water-soluble epoxy resin and be dissolved in wherein, at 60 DEG C, vigorous stirring makes it form the solution of homogeneous, dropwise adds 50mL0.01molL
-1silver nitrate solution, in the hierarchy of control, the dry weight ratio of Silver Nitrate and water-soluble epoxy resin is 1:40, be stirred well to and occur micro-yellow or yellow-green colour colloidal sol, illustrate that silver ions is reduced to simple substance silver, stop heating, after being cooled to room temperature, continue to stir after 15 minutes, obtain silver-colored/water-soluble epoxy resin mixture colloidal sol.
Embodiment 6
One, in reactor, add epoxy resin E-51 and the 5L deionized water of PEG6000, the 3mol of 1mol, then add the concentrated hydrochloric acid of 2mL, be warming up to 60 DEG C, stirring reaction 3 hours, obtains water-soluble epoxy resin emulsion, for subsequent use;
Two, in the Erlenmeyer flask of 1L, add 250mL deionized water, get a certain amount of water-soluble epoxy resin and be dissolved in wherein, at 60 DEG C, vigorous stirring makes it form the solution of homogeneous, dropwise adds 50mL0.01molL
-1silver nitrate solution, in the hierarchy of control, the dry weight ratio of Silver Nitrate and water-soluble epoxy resin is 1:25, be stirred well to and occur micro-yellow or yellow-green colour colloidal sol, illustrate that silver ions is reduced to simple substance silver, stop heating, after being cooled to room temperature, continue to stir after 15 minutes, obtain silver-colored/water-soluble epoxy resin mixture colloidal sol.
Embodiment 7
One, in reactor, add in the epoxy resin E-31 and 5L deionized water of PEG400,4mol of 1mol, then add the concentrated hydrochloric acid of 2mL, be warming up to 60 DEG C, stirring reaction 2.5 hours, obtains water-soluble epoxy resin emulsion, for subsequent use;
Two, in the Erlenmeyer flask of 1L, add 200mL deionized water, get a certain amount of water-soluble epoxy resin and be dissolved in wherein, at 60 DEG C, vigorous stirring makes it form the solution of homogeneous, dropwise adds 50mL0.1molL
-1silver nitrate solution, in the hierarchy of control, the dry weight ratio of Silver Nitrate and water-soluble epoxy resin is 1:20, be stirred well to and occur micro-yellow or yellow-green colour colloidal sol, illustrate that silver ions is reduced to simple substance silver, stop heating, after being cooled to room temperature, continue to stir after 15 minutes, obtain silver-colored/water-soluble epoxy resin mixture colloidal sol.
Finally be necessary explanation: above embodiment is only for being described in further detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (7)
1. a water-soluble antimicrobial composite material, is characterized in that: for wrapping the colloidal sol of the water-soluble epoxy resin that is loaded with simple-substance nano silvery.
2. the preparation method of a water-soluble antimicrobial composite material as claimed in claim 1, it is characterized in that, comprise the steps: soluble in water water-soluble epoxy resin emulsion, stir the solution to form homogeneous at 20～60 DEG C after, dropwise add silver nitrate solution, continue to be stirred to the micro-yellow of appearance or yellow-green colour colloidal sol, stop heating, temperature adjustment continues to stir 10～20 minutes to room temperature, discharging, wherein, the preparation of described water-soluble epoxy resin emulsion is that polyoxyethylene glycol and epoxy resin are added to the water, add again concentrated hydrochloric acid, be warming up to 45～70 DEG C, stirring reaction, obtain water-soluble epoxy resin emulsion.
3. the preparation method of water-soluble antimicrobial composite material according to claim 1, is characterized in that: the volumetric molar concentration of described silver nitrate solution is 0.01～0.1mol.L
-1.
4. the preparation method of water-soluble antimicrobial composite material according to claim 1, is characterized in that: in reaction solution, Silver Nitrate is 1:(15～50 with the ratio of the dry weight of water-soluble epoxy resin).
5. the preparation method of water-soluble antimicrobial composite material according to claim 1, is characterized in that: the polyoxyethylene glycol that described polyoxyethylene glycol is commercially available various molecular weight, the epoxy resin that described epoxy resin is commercially available various molecular weight.
6. the preparation method of water-soluble antimicrobial composite material according to claim 4, is characterized in that: the mol ratio of described polyoxyethylene glycol and epoxy resin is 1:(2～5).
7. the preparation method of water-soluble antimicrobial composite material according to claim 5, is characterized in that: described polyoxyethylene glycol is PEG-2000, and described epoxy resin is E-20.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106065039A (en) * | 2015-04-21 | 2016-11-02 | 王式禹 | Preparation method of water-soluble antibacterial acrylic polymer silver salt |
| CN106633595A (en) * | 2016-11-25 | 2017-05-10 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | Antibacterial 3D printing line and preparation method thereof |
| CN106674864A (en) * | 2016-11-25 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | Bacteriostatic 3d printing wire material and preparation method thereof |
| CN109692971A (en) * | 2018-12-10 | 2019-04-30 | 太原氦舶新材料有限责任公司 | A kind of nano-silver powder and its preparation and the application in low-temperature cured conductive silver paste |
| CN110621747A (en) * | 2017-05-12 | 2019-12-27 | 因希比特涂层有限公司 | Composite resin containing silver nanoparticles |
| CN111567556A (en) * | 2020-07-03 | 2020-08-25 | 吴飞 | Modified nano Ag-doped epoxy resin antibacterial material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106065039A (en) * | 2015-04-21 | 2016-11-02 | 王式禹 | Preparation method of water-soluble antibacterial acrylic polymer silver salt |
| CN106065039B (en) * | 2015-04-21 | 2018-11-13 | 王式禹 | Preparation method of water-soluble antibacterial acrylic polymer silver salt |
| CN106633595A (en) * | 2016-11-25 | 2017-05-10 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | Antibacterial 3D printing line and preparation method thereof |
| CN106674864A (en) * | 2016-11-25 | 2017-05-17 | 安徽省春谷3D打印智能装备产业技术研究院有限公司 | Bacteriostatic 3d printing wire material and preparation method thereof |
| CN110621747A (en) * | 2017-05-12 | 2019-12-27 | 因希比特涂层有限公司 | Composite resin containing silver nanoparticles |
| CN109692971A (en) * | 2018-12-10 | 2019-04-30 | 太原氦舶新材料有限责任公司 | A kind of nano-silver powder and its preparation and the application in low-temperature cured conductive silver paste |
| CN111567556A (en) * | 2020-07-03 | 2020-08-25 | 吴飞 | Modified nano Ag-doped epoxy resin antibacterial material and preparation method thereof |
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Application publication date: 20140813 |