CN115028374A - Antibacterial glass and preparation method thereof - Google Patents
Antibacterial glass and preparation method thereof Download PDFInfo
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- CN115028374A CN115028374A CN202210463398.7A CN202210463398A CN115028374A CN 115028374 A CN115028374 A CN 115028374A CN 202210463398 A CN202210463398 A CN 202210463398A CN 115028374 A CN115028374 A CN 115028374A
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous glass
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Abstract
The invention relates to the technical field of materials, in particular to antibacterial glass and a preparation method thereof. The antibacterial glass is prepared from the following raw materials in parts by weight: 100-120 parts of glass, 100-150 parts of a modifier and 700-750 parts of a disinfectant, wherein the modifier is a silane coupling agent solution, and the disinfectant is a modified polyhexamethylene guanidine solution. According to the invention, by using the silane coupling agent, a 'molecular bridge' can be erected between the interfaces of the glass and the modified polyhexamethylene guanidine, two materials with different properties are compounded together, the interface bonding strength of the composite material is enhanced, and the antibacterial stability of the antibacterial glass is improved; by grafting the modified polyhexamethylene guanidine with better antibacterial effect with the glass, the antibacterial effect of the antibacterial glass can be enhanced, the antibacterial aging can be prolonged, and the antibacterial performance of the antibacterial glass can be improved. The preparation method of the antibacterial glass is simple to operate, low in production cost, non-toxic, harmless, high in safety and high in social value.
Description
Technical Field
The invention relates to the technical field of materials, in particular to antibacterial glass and a preparation method thereof.
Background
Glass products have high strength, hardness, wear resistance and corrosion resistance, and are widely used in the fields of daily necessities, electronic products and medical supplies. Along with the technological progress and the improvement of the living standard of people, people pay more and more attention to the environmental sanitation, and the antibacterial glass products are gradually known and contained by the public. The antibacterial glass is functional glass with built-in antibacterial performance, can inhibit the growth of bacteria and has long service life. The antibacterial glass not only keeps the characteristics of transparency, cleanness, high mechanical strength, good chemical stability and the like of the glass material, but also adds a new function of killing and inhibiting germs, and has important significance for improving ecological environment, keeping human health and guiding the research and development of related functional glass materials.
The existing preparation method of the antibacterial glass is to add an antibacterial agent on a glass carrier in a film coating mode so that the antibacterial glass has contact type antibacterial and bactericidal functions. However, the existing preparation method of the antibacterial glass has the following problems: (1) most of the existing antibacterial glass is formed by adding an inorganic antibacterial agent on a glass carrier in a film coating mode, the adsorption firmness of the inorganic antibacterial agent and the glass is poor, and the inorganic antibacterial agent is easy to separate and lose efficacy; (2) the prepared antibacterial glass has the advantages of unsatisfactory antibacterial effect, short antibacterial aging and unstable antibacterial performance. Therefore, the development of a new antibacterial glass has very important significance.
Disclosure of Invention
Based on the problems in the prior art, the invention provides the antibacterial glass and the preparation method thereof, the organic antibacterial agent is added to the glass carrier in a film coating manner, and the prepared antibacterial glass has good antibacterial effect, long antibacterial aging and stable antibacterial performance, and overcomes the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, an embodiment of the present invention provides an antibacterial glass, which is prepared from the following raw materials in parts by weight: 100-120 parts of glass, 100-150 parts of a modifier and 700-750 parts of a disinfectant, wherein the modifier is a silane coupling agent solution, and the disinfectant is a modified polyhexamethylene guanidine solution.
The antibacterial glass provided by the invention is prepared from glass, a silane coupling agent and modified polyhexamethylene guanidine, wherein the silane coupling agent is between an inorganic interface and an organic interface, and can form a bonding layer of an inorganic matrix, the silane coupling agent and an organic matrix; the modified polyhexamethylene guanidine has higher activity and better antibacterial effect, the modified polyhexamethylene guanidine is connected to the glass through the silane coupling agent and is connected through a covalent bond, and compared with the existing inorganic antibacterial agent, the modified polyhexamethylene guanidine is connected with the glass more firmly through adsorption, so that the antibacterial stability of the antibacterial glass can be enhanced, meanwhile, the antibacterial glass has better antibacterial effect, the antibacterial aging is longer, and the defects of the prior art are overcome.
Preferably, the silane coupling agent solution is a 3-chloropropyltrimethoxysilane solution or an aminopropyltrimethoxysilane solution.
The 3-chloropropyltrimethoxysilane solution or aminopropyltrimethoxysilane solution can be grafted with glass and modified polyhexamethylene guanidine at normal temperature, and has the advantages of low cost, simple reaction condition and high safety.
Preferably, the 3-chloropropyltrimethoxysilane solution is an ethanol solution of 2-4% by volume of 3-chloropropyltrimethoxysilane, and the pH value of the 3-chloropropyltrimethoxysilane solution is 3.5-4.5.
3-chloropropyltrimethoxysilane can be hydrolyzed in a mixed solvent of absolute ethyl alcohol and deionized water, the 3-chloropropyltrimethoxysilane has a high hydrolysis speed under the condition that the pH value is 3.5-4.5, and Si-OH generated after hydrolysis can be subjected to a grafting reaction with glass.
Preferably, the mass ratio of aminopropyltrimethoxysilane to distilled water to absolute ethyl alcohol in the aminopropyltrimethoxysilane solution is 1: 2-4: 5-7.
The aminopropyl trimethoxysilane can be hydrolyzed in a mixed solvent of absolute ethyl alcohol and distilled water, the aminopropyl trimethoxysilane is alkaline, the aminopropyl trimethoxysilane has a high hydrolysis speed under the alkaline condition, and Si-OH generated after hydrolysis can be subjected to a grafting reaction with glass.
Preferably, the preparation method of the modified polyhexamethylene guanidine comprises the following steps: adding a solvent into the polyhexamethylene monoguanidine to dissolve the polyhexamethylene monoguanidine, adding a grafting agent to react, removing the solvent after the reaction is finished, purifying and drying to obtain the modified polyhexamethylene monoguanidine.
Polyhexamethylene guanidine is an environment-friendly high-molecular polymer disinfectant, is easily soluble in water, can be used at normal temperature, and has no side effect. The polyhexamethylene monoguanidine polymer can generate ionization in aqueous solution, and the hydrophilic group part of the polyhexamethylene monoguanidine polymer has strong electropositivity, adsorbs various bacteria and viruses which are usually electronegative, inhibits the synthesis of liposome in cell membranes, causes the apoptosis of thalli and achieves the optimal sterilization effect. The antibacterial effect of the polyhexamethylene guanidine can be obviously improved by modifying the polyhexamethylene guanidine, so that the antibacterial effect of the antibacterial glass is enhanced, and the antibacterial stability of the antibacterial glass is improved.
Preferably, the relative score amount of the polyhexamethylene guanidine is 4000 to 5000.
Preferably, the solvent is a mixed solution of water and ethanol, wherein the mass ratio of the water to the ethanol is 1: 1.5-2.5, and the mass ratio of the polyhexamethylene guanidine to the solvent is 1: 1.5-2.0.
The mixed solution of water and ethanol is used as a solvent, so that polar substances and nonpolar substances can be dissolved, and the modification time of the polyhexamethylene guanidine can be shortened.
Preferably, the grafting agent is maleic anhydride, the molar ratio of the polyhexamethylene guanidine to the maleic anhydride is 1: 1-1.5, the reaction temperature is 40-50 ℃, and the reaction time is 10-20 h.
Preferably, the solvent is removed by adopting a rotary evaporation instrument, the rotary evaporation temperature is 30-50 ℃, and the rotary evaporation time is 10-30 min.
Preferably, the drying time is 11-13 h.
The modified polyhexamethylene guanidine with polymerization activity is generated by grafting polyhexamethylene guanidine with an antibacterial effect to micromolecule maleic anhydride containing unsaturated double bonds for bonding, has better thermal stability, contains active groups such as vinyl, tertiary amino and the like, and can be synthesized into a polymer material with the specific functions of active amino or quaternary ammonium group through polymerization reaction. According to the invention, the polyhexamethylene monoguanidine is grafted to the maleic anhydride substrate through a chemical reaction, so that the loss of the antibacterial agent can be reduced, the antibacterial performance of the polyhexamethylene monoguanidine is enhanced, and the problem of compatibility of the polyhexamethylene monoguanidine and resin can be solved.
Preferably, the grafting agent is thiourea, the mass ratio of the polyhexamethylene guanidine to the thiourea is 1: 0.07-0.09, the reaction temperature is 90-110 ℃, and the reaction time is 1-2 h.
Preferably, the solvent is removed by adopting a rotary evaporation instrument, the rotary evaporation temperature is 80-90 ℃, and the rotary evaporation time is 10-30 min.
Preferably, the drying time is 11-13 h.
Thiourea is grafted on the polyhexamethylene guanidine disinfectant, and the thiourea can increase electrophilic active groups in molecules, so that the antibacterial performance of the polyhexamethylene guanidine is enhanced.
In a second aspect, an embodiment of the present invention provides a method for preparing antibacterial glass, including the following steps: cleaning glass, heating at 500-600 ℃ for 1-2 h, and naturally cooling to room temperature to obtain pretreated glass;
immersing the pretreated glass into a modifier for modification to obtain modified glass;
and (3) immersing the modified glass into a disinfectant for grafting reaction, taking out after 4-5 hours, immersing into distilled water, ultrasonically cleaning for 2-3 times, and drying to obtain the antibacterial glass.
According to the preparation method of the antibacterial glass, firstly, silicon-oxygen bonds on the surface of the glass can be opened through high-temperature heating, then the glass subjected to high-temperature pretreatment is immersed into a solution of a silane coupling agent, Si-OH generated by hydrolysis of the silane coupling agent in the solution of the silane coupling agent reacts with O-Si-O of the glass to form Si-O-Si-O bonds, and the silane coupling agent is further firmly grafted to the glass; immersing the glass grafted with silane coupling agent in the solution of modified polyhexamethylene guanidine, wherein the chloropropyl or aminopropyl on the silane coupling agent and-NH on the modified polyhexamethylene guanidine 2 The reaction is carried out, and the modified polyhexamethylene guanidine is connected to the glass through the coupling agent, so that the antibacterial glass with better antibacterial effect, long antibacterial aging and stable antibacterial performance is obtained.
Preferably, when the modifier is a 3-chloropropyltrimethoxysilane solution, the modification time is 110-130 min, and drying is carried out at 100-120 ℃ for 1.5-2.5 h after the modification is finished; the disinfectant is an aqueous solution of modified polyhexamethylene guanidine with the mass concentration of 1-2%, and the temperature of the grafting reaction is room temperature.
When the modifier is 3-chloropropyltrimethoxysilane solution, the C-C on the 3-chloropropyltrimethoxysilanel and-NH on modified polyhexamethylene monoguanidine 2 Grafting reaction is carried out to form a C-N bond, and the modified polyhexamethylene guanidine is connected to the glass through a coupling agent.
Preferably, when the modifier is aminopropyltrimethoxysilane solution, the modification time is 18-24 h; the disinfectant is an isopropanol solution of modified polyhexamethylene guanidine with the mass concentration of 1-2%, and the temperature of the grafting reaction is 75-80 ℃.
When the modifier is aminopropyltrimethoxysilane solution, the C-NH on the aminopropyltrimethoxysilane 2 with-NH on modified polyhexamethylene monoguanidine 2 Grafting reaction is carried out to form a new C-N bond, and the modified polyhexamethylene guanidine is connected to the glass through a coupling agent.
According to the invention, by using the silane coupling agent, a 'molecular bridge' can be erected between the interfaces of the glass and the modified polyhexamethylene guanidine, two materials with different properties are compounded together, the interface bonding strength of the composite material is enhanced, and the antibacterial stability of the antibacterial glass is improved; by grafting the modified polyhexamethylene guanidine with better antibacterial effect with the glass, the antibacterial effect of the antibacterial glass can be enhanced, the antibacterial aging can be prolonged, and the antibacterial performance of the antibacterial glass can be improved. The preparation method of the antibacterial glass disclosed by the invention is simple to operate, low in production cost, non-toxic, harmless and high in safety, and the prepared antibacterial glass is good in antibacterial effect, long in antibacterial aging, stable in antibacterial performance and high in social value.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment provides a preparation method of modified polyhexamethylene guanidine, wherein polyhexamethylene guanidine and a solvent are added into a three-neck flask, the mass ratio of the polyhexamethylene guanidine to the solvent is 1:1.5, (the solvent is a mixed solution of water and ethanol, and the mass ratio of the water to the ethanol is 1:2.5), the mixture is stirred to dissolve the polyhexamethylene guanidine, maleic anhydride is added for reaction, the molar ratio of the polyhexamethylene guanidine to the maleic anhydride is 1:1.5, the reaction temperature is 50 ℃, and the reaction time is 10 hours; after the reaction is finished, removing the solvent by using a rotary evaporation instrument, wherein the rotary evaporation temperature is 50 ℃, and the rotary evaporation time is 10 min; removing solvent, adding acetone for settling, filtering to obtain supernatant, repeating the filtering for 3 times, and drying for 13h to obtain modified polyhexamethylene guanidine.
Example 2
The embodiment provides a preparation method of modified polyhexamethylene monoguanidine, wherein polyhexamethylene monoguanidine and a solvent are added into a three-neck flask, the mass ratio of the polyhexamethylene monoguanidine to the solvent is 1:2.0, (the solvent is a mixed solution of water and ethanol, and the mass ratio of the water to the ethanol is 1:1.5), the mixture is stirred to dissolve the polyhexamethylene monoguanidine, maleic anhydride is added for reaction, the molar ratio of the polyhexamethylene monoguanidine to the maleic anhydride is 1:1, the reaction temperature is 40 ℃, and the reaction time is 20 hours; after the reaction is finished, removing the solvent by using a rotary evaporation instrument, wherein the rotary evaporation temperature is 30 ℃, and the rotary evaporation time is 30 min; removing solvent, adding acetone, settling, filtering to obtain supernatant, repeating filtering for 3 times, and drying for 11 hr to obtain modified polyhexamethylene guanidine.
Example 3
The embodiment provides a preparation method of modified polyhexamethylene monoguanidine, wherein polyhexamethylene monoguanidine and a solvent are added into a three-neck flask, the mass ratio of the polyhexamethylene monoguanidine to the solvent is 1:1.8, (the solvent is a mixed solution of water and ethanol, and the mass ratio of the water to the ethanol is 1:2), the mixture is stirred to dissolve the polyhexamethylene monoguanidine, maleic anhydride is added for reaction, the molar ratio of the polyhexamethylene monoguanidine to the maleic anhydride is 1:1.2, the reaction temperature is 45 ℃, and the reaction time is 15 hours; after the reaction is finished, removing the solvent by using a rotary evaporation instrument, wherein the rotary evaporation temperature is 40 ℃, and the rotary evaporation time is 20 min; removing solvent, adding acetone, settling, filtering to obtain supernatant, repeating filtering for 3 times, and drying for 12 hr to obtain modified polyhexamethylene guanidine.
Example 4
The embodiment provides a preparation method of modified polyhexamethylene monoguanidine, wherein polyhexamethylene monoguanidine and a solvent are added into a three-neck flask, the mass ratio of the polyhexamethylene monoguanidine to the solvent is 1:2.0, (the solvent is a mixed solution of water and ethanol, and the mass ratio of the water to the ethanol is 1:1.5), the mixture is stirred to dissolve the polyhexamethylene monoguanidine, thiourea is added for reaction, the mass ratio of the polyhexamethylene monoguanidine to the thiourea is 1:0.09, the reaction temperature is 90 ℃, and the reaction time is 2 hours; after the reaction is finished, removing the solvent by using a rotary evaporation instrument, wherein the rotary evaporation temperature is 80 ℃, and the rotary evaporation time is 30 min; and removing the solvent, and drying for 11h to obtain the modified polyhexamethylene guanidine.
Example 5
The embodiment provides a preparation method of modified polyhexamethylene monoguanidine, wherein polyhexamethylene monoguanidine and a solvent are added into a three-neck flask, the mass ratio of the polyhexamethylene monoguanidine to the solvent is 1:1.5, (the solvent is a mixed solution of water and ethanol, and the mass ratio of the water to the ethanol is 1:2.5), the mixture is stirred to dissolve the polyhexamethylene monoguanidine, thiourea is added for reaction, the mass ratio of the polyhexamethylene monoguanidine to the thiourea is 1:0.07, the reaction temperature is 110 ℃, and the reaction time is 1 h; after the reaction is finished, removing the solvent by using a rotary evaporation instrument, wherein the rotary evaporation temperature is 90 ℃, and the rotary evaporation time is 10 min; and removing the solvent, and drying for 13h to obtain the modified polyhexamethylene guanidine.
Example 6
The embodiment provides a preparation method of modified polyhexamethylene monoguanidine, wherein polyhexamethylene monoguanidine and a solvent are added into a three-neck flask, the mass ratio of the polyhexamethylene monoguanidine to the solvent is 1:1.7, (the solvent is a mixed solution of water and ethanol, and the mass ratio of the water to the ethanol is 1:2.1), the polyhexamethylene monoguanidine is dissolved by stirring, thiourea is added for reaction, the mass ratio of the polyhexamethylene monoguanidine to the thiourea is 1:0.08, the reaction temperature is 100 ℃, and the reaction time is 1.6 h; after the reaction is finished, removing the solvent by using a rotary evaporation instrument, wherein the rotary evaporation temperature is 70 ℃, and the rotary evaporation time is 20 min; and removing the solvent, and drying for 12h to obtain the modified polyhexamethylene guanidine.
Example 7
The embodiment provides antibacterial glass which is prepared from the following raw materials in parts by weight: 100 parts of glass, 150 parts of an ethanol solution (volume percentage concentration of 2% and pH value of 4.5) of 3-chloropropyltrimethoxysilane and 700 parts of an aqueous solution (mass concentration of 1%) of modified polyhexamethylene monoguanidine prepared in example 1.
The preparation method comprises the following steps:
cleaning the glass with acetone for 2 times, putting the glass into a muffle furnace, heating at 600 ℃ for 1h, and naturally cooling to room temperature;
immersing the glass pretreated at high temperature into an ethanol solution of 3-chloropropyltrimethoxysilane, standing for 130min for modification, taking out the glass, and drying at 100 ℃ for 2.5 h;
and (2) immersing the modified glass into the aqueous solution of the modified polyhexamethylene guanidine prepared in the example 1, adding magnetons into the solution to perform grafting reaction, stirring for 4 hours, taking out the glass, immersing the glass into distilled water, performing ultrasonic cleaning for 3 times, and drying to obtain the antibacterial glass.
Example 8
The embodiment provides antibacterial glass which is prepared from the following raw materials in parts by weight: 120 parts of glass, 100 parts of aminopropyltrimethoxysilane solution (the mass ratio of aminopropyltrimethoxysilane to distilled water to absolute ethyl alcohol is 1:2:7) and 750 parts of isopropanol solution (the mass concentration is 2%) of modified polyhexamethylene monoguanidine prepared in example 2.
The preparation method comprises the following steps:
cleaning the glass with acetone for 3 times, putting the glass into a muffle furnace, heating the glass at 500 ℃ for 2 hours, and naturally cooling the glass to room temperature;
immersing the glass pretreated at high temperature into aminopropyltrimethoxysilane solution, standing for 18h for modification, taking out the glass, and drying at 120 ℃ for 1.5 h;
and (2) immersing the modified glass into the isopropanol solution of the modified polyhexamethylene guanidine prepared in the example 2, adding magnetons into the solution, connecting a water bath heating device and a condensation reflux device, heating to carry out grafting reaction at the temperature of 75 ℃, taking out the glass after 5h, immersing the glass into distilled water, carrying out ultrasonic cleaning for 2 times, and drying to obtain the antibacterial glass.
Example 9
The embodiment provides antibacterial glass which is prepared from the following raw materials in parts by weight: 110 parts of glass, 140 parts of an ethanol solution (3 volume percent concentration and pH value of 3.5) of 3-chloropropyltrimethoxysilane and 710 parts of an aqueous solution (2 mass percent concentration) of the modified polyhexamethylene guanidine prepared in example 3.
The preparation method comprises the following steps:
cleaning the glass with acetone for 3 times, putting the glass into a muffle furnace, heating the glass for 2 hours at 510 ℃, and naturally cooling the glass to room temperature;
immersing the glass pretreated at high temperature into an ethanol solution of 3-chloropropyltrimethoxysilane, standing for 115min for modification, taking out the glass, and drying at 120 ℃ for 1.5 h;
and (3) immersing the modified glass into the aqueous solution of the modified polyhexamethylene guanidine prepared in the example 3, adding magnetons into the solution to perform grafting reaction, stirring for 5 hours, taking out the glass, immersing the glass into distilled water, performing ultrasonic cleaning for 2 times, and drying to obtain the antibacterial glass.
Example 10
The embodiment provides antibacterial glass which is prepared from the following raw materials in parts by weight: 100 parts of glass, 150 parts of aminopropyltrimethoxysilane solution (the mass ratio of aminopropyltrimethoxysilane to distilled water to absolute ethyl alcohol is 1:4:5) and 700 parts of isopropanol solution (mass concentration is 1%) of modified polyhexamethylene monoguanidine prepared in example 4.
The preparation method comprises the following steps:
cleaning the glass with acetone for 2 times, putting the glass into a muffle furnace, heating at 600 ℃ for 1h, and naturally cooling to room temperature;
immersing the glass pretreated at high temperature into aminopropyl trimethoxy silane solution, standing for 24h for modification, taking out the glass, and drying at 100 ℃ for 2.5 h;
and (2) immersing the modified glass into the isopropanol solution of the modified polyhexamethylene guanidine prepared in the example 4, adding magnetons into the solution, connecting a water bath heating device and a condensation reflux device, heating to carry out grafting reaction at the temperature of 80 ℃, taking out the glass after 4h, immersing the glass into distilled water, carrying out ultrasonic cleaning for 3 times, and drying to obtain the antibacterial glass.
Example 11
The embodiment provides antibacterial glass which is prepared from the following raw materials in parts by weight: 120 parts of glass, 130 parts of an ethanol solution (the volume percentage concentration is 3 percent and the pH value is 4) of 3-chloropropyltrimethoxysilane and 720 parts of an aqueous solution (the mass concentration is 1.5 percent) of the modified polyhexamethylene guanidine prepared in example 5.
The preparation method comprises the following steps:
cleaning the glass with acetone for 3 times, putting the glass into a muffle furnace, heating at 550 ℃ for 1.5h, and naturally cooling to room temperature;
immersing the glass pretreated at high temperature into an ethanol solution of 3-chloropropyltrimethoxysilane, standing for 120min for modification, taking out the glass, and drying at 110 ℃ for 2 h;
and (3) immersing the modified glass into the aqueous solution of the modified polyhexamethylene guanidine prepared in the example 5, adding magnetons into the solution to perform grafting reaction, stirring for 4.5h, taking out the glass, immersing the glass into distilled water, ultrasonically cleaning for 2 times, and drying to obtain the antibacterial glass.
Example 12
The embodiment provides antibacterial glass which is prepared from the following raw materials in parts by weight: 115 parts of glass, 140 parts of aminopropyltrimethoxysilane solution (the mass ratio of aminopropyltrimethoxysilane to distilled water to absolute ethyl alcohol is 1:3:6) and 730 parts of isopropanol solution (mass concentration is 1.5%) of modified polyhexamethylene monoguanidine prepared in example 6.
The preparation method comprises the following steps:
cleaning the glass with acetone for 3 times, putting the glass into a muffle furnace, heating at 550 ℃ for 1h, and naturally cooling to room temperature;
immersing the glass pretreated at high temperature into aminopropyltrimethoxysilane solution, standing for 20 hours for modification, taking out the glass, and drying at 110 ℃ for 2 hours;
and (2) immersing the modified glass into the isopropanol solution of the modified polyhexamethylene guanidine prepared in the embodiment 6, adding magnetons into the solution, connecting a water bath heating device and a condensation reflux device, heating to carry out grafting reaction at the temperature of 78 ℃, taking out the glass after 4.5 hours, immersing the glass into distilled water, carrying out ultrasonic cleaning for 2 times, and drying to obtain the antibacterial glass.
Comparative example 1
The comparative example provides antibacterial glass tested in the research process, which is prepared from the following raw materials in parts by weight: 120 parts of glass, 130 parts of an ethanol solution (the volume percentage concentration is 3%) of 3-chloropropyltrimethoxysilane and 720 parts of an aqueous solution (the mass concentration is 1.5%) of the modified polyhexamethylene guanidine prepared in example 5.
The preparation method comprises the following steps:
cleaning the glass with acetone for 3 times, putting the glass into a muffle furnace, heating at 550 ℃ for 1.5h, and naturally cooling to room temperature;
immersing the glass pretreated at high temperature into an ethanol solution of 3-chloropropyltrimethoxysilane, standing for 120min for modification, taking out the glass, and drying at 110 ℃ for 2 h;
and (3) immersing the modified glass into the aqueous solution of the modified polyhexamethylene guanidine prepared in the embodiment 5, adding magnetons into the solution to perform grafting reaction, stirring for 4.5 hours, taking out the glass, immersing the glass into distilled water, performing ultrasonic cleaning for 2 times, and drying to obtain the antibacterial glass.
Comparative example 2
The comparative example provides antibacterial glass tested in the research process, which is prepared from the following raw materials in parts by weight: 120 parts of glass, 130 parts of an ethanol solution (the volume percentage concentration is 3 percent, the pH value is 4) of 3-chloropropyltrimethoxysilane and 720 parts of an aqueous solution (the mass concentration is 1.5 percent) of polyhexamethylene guanidine.
The preparation method comprises the following steps:
cleaning the glass with acetone for 3 times, putting the glass into a muffle furnace, heating at 550 ℃ for 1.5h, and naturally cooling to room temperature;
immersing the glass pretreated at high temperature into an ethanol solution of 3-chloropropyltrimethoxysilane, standing for 120min for modification, taking out the glass, and drying at 110 ℃ for 2 h;
and (3) immersing the modified glass into a polyhexamethylene guanidine aqueous solution, adding magnetons into the solution to perform grafting reaction, stirring for 4.5h, taking out the glass, immersing the glass into distilled water, performing ultrasonic cleaning for 2 times, and drying to obtain the antibacterial glass.
Comparative example 3
The comparative example provides antibacterial glass tested in the research process, which is prepared from the following raw materials in parts by weight: 120 parts of glass, 130 parts of an ethanol solution (3 volume percent concentration and pH value of 4) of 3-chloropropyltrimethoxysilane and 720 parts of an aqueous solution (1.5 mass percent concentration) of the modified polyhexamethylene guanidine prepared in example 5.
The preparation method comprises the following steps:
cleaning the glass with acetone for 3 times;
soaking the cleaned glass into an ethanol solution of 3-chloropropyltrimethoxysilane, standing for 120min for modification, taking out the glass, and drying at 110 ℃ for 2 h;
the modified glass is immersed in the aqueous solution of the modified polyhexamethylene guanidine prepared in the example 5, stirred for 4.5 hours, taken out, immersed in distilled water, ultrasonically cleaned for 2 times, and dried to obtain the antibacterial glass.
Comparative example 4
The comparative example provides antibacterial glass tested in the research process, which is prepared from the following raw materials in parts by weight: 115 parts of glass, 140 parts of titanate coupling agent solution (the mass ratio of the titanate coupling agent to the distilled water to the absolute ethyl alcohol is 1:3:6) and 730 parts of modified polyhexamethylene monoguanidine aqueous solution (the mass concentration is 1.5%) prepared in example 6.
The preparation method comprises the following steps:
cleaning the glass with acetone for 3 times, putting the glass into a muffle furnace, heating at 550 ℃ for 1h, and naturally cooling to room temperature;
immersing the glass pretreated at high temperature into a titanate coupling agent solution, standing for 20h for modification, taking out the glass, and drying at 110 ℃ for 2 h;
the modified glass is immersed in the aqueous solution of the modified polyhexamethylene guanidine prepared in the embodiment 6, magnetons are added into the solution, a water bath heating device and a condensation reflux device are connected, heating is carried out for grafting reaction, the temperature of the grafting reaction is 78 ℃, the glass is taken out after 4.5 hours, immersed in distilled water, ultrasonic cleaning is carried out for 2 times, and drying is carried out, so that the antibacterial glass is obtained.
Comparative example 5
The comparative example provides antibacterial glass tested in the research process, which is prepared from the following raw materials in parts by weight: 115 parts of glass, 140 parts of aminopropyltrimethoxysilane solution (the mass ratio of aminopropyltrimethoxysilane to distilled water to absolute ethyl alcohol is 1:3:6) and 730 parts of isopropanol solution of polyhexamethylene monoguanidine (the mass concentration is 1.5%).
The preparation method comprises the following steps:
cleaning the glass with acetone for 3 times, putting the glass into a muffle furnace, heating the glass for 1h at 550 ℃, and naturally cooling the glass to room temperature;
immersing the glass pretreated at high temperature into aminopropyltrimethoxysilane solution, standing for 20 hours for modification, taking out the glass, and drying at 110 ℃ for 2 hours;
and (2) immersing the modified glass into an isopropanol solution of polyhexamethylene guanidine, adding magnetons into the solution, connecting a water bath heating device and a condensation reflux device, heating for grafting reaction at the temperature of 78 ℃, taking out the glass after 4.5 hours, immersing the glass into distilled water, ultrasonically cleaning for 2 times, and drying to obtain the antibacterial glass.
Comparative example 6
The comparative example provides antibacterial glass tested in the research process, which is prepared from the following raw materials in parts by weight: 115 parts of glass, 140 parts of aminopropyltrimethoxysilane solution (the mass ratio of aminopropyltrimethoxysilane to distilled water to absolute ethyl alcohol is 1:3:6) and 730 parts of the aqueous solution of modified polyhexamethylene monoguanidine (the mass concentration is 1.5%) prepared in example 6.
The preparation method comprises the following steps:
cleaning the glass with acetone for 3 times, putting the glass into a muffle furnace, heating at 550 ℃ for 1h, and naturally cooling to room temperature;
immersing the glass pretreated at high temperature into aminopropyltrimethoxysilane solution, standing for 20 hours for modification, taking out the glass, and drying at 110 ℃ for 2 hours;
the modified glass is immersed in the aqueous solution of the modified polyhexamethylene guanidine prepared in the example 6, the glass is taken out after 4.5 hours, immersed in distilled water, ultrasonically cleaned for 2 times, and dried to obtain the antibacterial glass.
Examples of effects
The antibacterial glass provided in examples 7 to 12 of the present invention and comparative examples 1 to 6 was subjected to bacteriostatic and transmittance tests, wherein a number of bacteria existing in the nature were classified according to a certain rule, and classified into gram-negative bacteria and gram-positive bacteria according to the gram staining method. The bacteria representative of gram-negative bacteria are Escherichia coli, and the bacteria representative of gram-positive bacteria are Staphylococcus aureus. Staphylococcus aureus is measured according to the national standard of coated antibacterial glass JC/T1054-2007, and Escherichia coli is measured according to the HG3950-2007 antibacterial coating.
The light transmittance was measured according to the method specified in GB/T2680. The specific test results are shown in table 1:
TABLE 1
| Anti-staphylococcus aureus | Anti-colibacillus | |
| Example 7 | 98％ | 99％ |
| Example 8 | 97％ | 98％ |
| Example 9 | 98％ | 97％ |
| Example 10 | 96％ | 97％ |
| Example 11 | 96％ | 99％ |
| Example 12 | 97％ | 99％ |
| Comparative example 1 | 25％ | 28％ |
| Comparative example 2 | 93％ | 94％ |
| Comparative example 3 | 89％ | 89％ |
| Comparative example 4 | 94％ | 95％ |
| Comparative example 5 | 93％ | 94％ |
| Comparative example 6 | 57％ | 60％ |
As can be seen from the data in the table, the antibacterial performance of the antibacterial glass to escherichia coli and staphylococcus aureus can reach more than 95% generally, and meanwhile, the visible light transmittance of the antibacterial glass still meets the national standard requirements of flat glass.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. An antibacterial glass characterized in that: the feed is prepared from the following raw materials in parts by weight: 100-120 parts of glass, 100-150 parts of a modifier and 700-750 parts of a disinfectant, wherein the modifier is a silane coupling agent solution, and the disinfectant is a modified polyhexamethylene guanidine solution.
2. The antimicrobial glass according to claim 1, wherein: the silane coupling agent solution is 3-chloropropyltrimethoxysilane solution or aminopropyltrimethoxysilane solution.
3. The antimicrobial glass according to claim 2, wherein: the 3-chloropropyl trimethoxyl silane solution is an ethanol solution of 2-4% by volume of 3-chloropropyl trimethoxyl silane, and the pH value of the 3-chloropropyl trimethoxyl silane solution is 3.5-4.5.
4. The antimicrobial glass according to claim 2, wherein: the mass ratio of aminopropyltrimethoxysilane to distilled water to absolute ethyl alcohol in the aminopropyltrimethoxysilane solution is 1: 2-4: 5-7.
5. The antimicrobial glass according to claim 1, wherein: the preparation method of the modified polyhexamethylene guanidine comprises the following steps: adding a solvent into the polyhexamethylene monoguanidine to dissolve the polyhexamethylene monoguanidine, adding a grafting agent to react, removing the solvent after the reaction is finished, purifying and drying to obtain the modified polyhexamethylene monoguanidine.
6. The antimicrobial glass according to claim 5, wherein: the relative score amount of the polyhexamethylene monoguanidine is 4000-5000; and/or
The solvent is a mixed solution of water and ethanol, wherein the mass ratio of the water to the ethanol is 1: 1.5-2.5, and the mass ratio of the polyhexamethylene guanidine to the solvent is 1: 1.5-2.0.
7. The antimicrobial glass according to claim 5, wherein: the grafting agent is maleic anhydride, the molar ratio of the polyhexamethylene guanidine to the maleic anhydride is 1: 1-1.5, the reaction temperature is 40-50 ℃, and the reaction time is 10-20 h; and/or
Removing the solvent by using a rotary evaporation instrument, wherein the rotary evaporation temperature is 30-50 ℃, and the rotary evaporation time is 10-30 min; and/or
The drying time is 11-13 h.
8. The antimicrobial glass according to claim 5, wherein: the grafting agent is thiourea, the mass ratio of the polyhexamethylene guanidine to the thiourea is 1: 0.07-0.09, the reaction temperature is 90-110 ℃, and the reaction time is 1-2 h; and/or
Removing the solvent by using a rotary evaporation instrument, wherein the rotary evaporation temperature is 80-90 ℃, and the rotary evaporation time is 10-30 min; and/or
The drying time is 11-13 h.
9. The method for producing an antibacterial glass according to any one of claims 1 to 8, characterized in that: the method comprises the following steps: cleaning the glass, heating at 500-600 ℃ for 1-2 h, and naturally cooling to room temperature to obtain pretreated glass;
immersing the pretreated glass into the modifier for modification to obtain modified glass;
and immersing the modified glass into the disinfectant for grafting reaction, taking out after 4-5 hours, immersing into distilled water, ultrasonically cleaning for 2-3 times, and drying to obtain the antibacterial glass.
10. The method for producing an antibacterial glass according to claim 9, characterized in that: when the modifier is a 3-chloropropyltrimethoxysilane solution, the modification time is 110-130 min, and drying is carried out at 100-120 ℃ for 1.5-2.5 h after the modification is finished; the disinfectant is an aqueous solution of modified polyhexamethylene guanidine with the mass concentration of 1-2%, and the temperature of the grafting reaction is room temperature; and/or
When the modifier is an aminopropyltrimethoxysilane solution, the modification time is 18-24 h; the disinfectant is an isopropanol solution of modified polyhexamethylene guanidine with the mass concentration of 1-2%, and the temperature of the grafting reaction is 75-80 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06183785A (en) * | 1992-12-17 | 1994-07-05 | Mitsubishi Materials Corp | Antibacterial and antimold glass |
| CN104086088A (en) * | 2014-06-07 | 2014-10-08 | 北京化工大学 | Method of preparing glass with surface antibacterial property by photopolymerization |
| CN110772508A (en) * | 2019-11-19 | 2020-02-11 | 石家庄学院 | Broad-spectrum antibacterial agent and preparation method thereof |
| CN112970773A (en) * | 2021-02-26 | 2021-06-18 | 河北佩清科技有限公司 | Preparation method and device of efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant |
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2022
- 2022-04-28 CN CN202210463398.7A patent/CN115028374A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06183785A (en) * | 1992-12-17 | 1994-07-05 | Mitsubishi Materials Corp | Antibacterial and antimold glass |
| CN104086088A (en) * | 2014-06-07 | 2014-10-08 | 北京化工大学 | Method of preparing glass with surface antibacterial property by photopolymerization |
| CN110772508A (en) * | 2019-11-19 | 2020-02-11 | 石家庄学院 | Broad-spectrum antibacterial agent and preparation method thereof |
| CN112970773A (en) * | 2021-02-26 | 2021-06-18 | 河北佩清科技有限公司 | Preparation method and device of efficient and environment-friendly maleic anhydride grafted polyguanidine disinfectant |
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| 张孜文;张康民;杨建军;吴庆云;吴明元;张建安;刘久逸;: "聚六亚甲基胍盐酸盐功能化中空纳米二氧化硅制备新型抗菌剂的研究", 材料工程, no. 03, pages 40 - 46 * |
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