CN111053089B - Nano sterilizing and formaldehyde removing composition and preparation method thereof - Google Patents
Nano sterilizing and formaldehyde removing composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of nano zinc oxide materials, in particular to a nano sterilizing and formaldehyde removing composition and a preparation method thereof. According to the invention, by controlling the proportion and the content of the organosilane dispersing agent and the block polymer copolymer dispersing agent in the mixture, a large amount of foam and floating flowers are not generated when the mixture is subjected to dispersion treatment, so that the problem of reduction of production efficiency due to foam and floating flowers generated in the dispersion process is avoided, the dispersion treatment can be smoothly performed, and the production efficiency is greatly improved. According to the invention, through optimizing the compounding of the organosilane dispersing agent and the block polymer copolymer dispersing agent in the composition and optimizing the contents of the dispersing agent, ethanol and water, the stability of the composition is obviously improved, the composition is a transparent solution, the transparency of the composition does not change obviously after being placed for a long time, flocculation and precipitation are avoided, and the sterilization performance and the formaldehyde removal performance are good.
Description
Technical Field
The invention relates to the technical field of nano zinc oxide materials, in particular to a nano sterilizing and formaldehyde removing composition and a preparation method thereof.
Background
In life, people inevitably come into contact with various microorganisms such as bacteria, fungi, viruses and the like. Wherein the spread and spread of various harmful microorganisms seriously threatens human health. The inorganic antibacterial agent and the product thereof have safe, reliable, stable and durable antibacterial performance, and become a research and development hotspot in the field of current antibacterial materials. Nano zinc oxide is one of the excellent inorganic antibacterial agents. The nanometer zinc oxide can decompose free moving electron and cavity under the sunlight, especially under the ultraviolet irradiation, the cavity activates oxygen in the air to generate active oxygen, and the active oxygen can generate oxidation reaction with various organic matters, including organic matters in bacteria, thereby killing most of germs and viruses.
In recent years, the interior decoration materials still release formaldehyde during storage and use, so that the interior decoration materials are extremely harmful to human bodies and environment. At present, the ways of removing indoor formaldehyde mainly include methods such as physical adsorption, ventilation, plant absorption and purification, photocatalytic degradation and the like, and the photocatalytic degradation of formaldehyde has become a research hotspot at home and abroad. Among them, the nano titanium dioxide and the nano zinc oxide are widely paid attention to by their excellent photocatalytic performance so as to be applied to formaldehyde-removing products. The nano titanium dioxide and the nano zinc oxide are prepared into the spray, so that the limitation of the application of a nano powder product can be overcome to a certain extent, compared with nano slurry, the spray is simpler and easier to operate and use, and the utilization rate of nano materials is greatly improved. CN106881093A discloses a preparation method of a formaldehyde removing spray of zinc oxide, titanium oxide and ferric oxide ternary nano composite powder, which has high formaldehyde removing efficiency. CN107151462A discloses a long-acting aldehyde-removing, antibacterial and mildew-proof household spray, which mainly comprises nano zinc oxide or nano titanium oxide, a dispersing agent, a quick aldehyde-removing factor and a film-forming agent, can quickly remove formaldehyde and has excellent antibacterial and mildew-proof performances. CN108434986A discloses a preparation method of a formaldehyde removing spray agent of tin-doped titanium dioxide powder, which has high formaldehyde removing efficiency under ultraviolet irradiation and also has high formaldehyde removing efficiency under visible light irradiation. However, the price of the nano titanium dioxide is relatively high, and the defects of ultraviolet irradiation and easy discoloration exist, and the defects of easy recombination of photoproduction electrons and photoproduction holes, low light quantum yield of less than 10%, low photocatalysis efficiency and high energy consumption exist in the photocatalysis process, so that the practical application of the titanium dioxide is greatly restricted by the defects. In addition, the conventional surface active agent type dispersants generate foams, resulting in defects such as fish eyes, pits, etc., on the coating, and the foams, which occur during grinding, result in a decrease in productivity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the nano sterilizing formaldehyde-removing composition which takes nano zinc oxide as a substrate material and has good stability, high antibacterial formaldehyde-removing efficiency, simple and efficient production process and a preparation method of the nano sterilizing formaldehyde-removing composition.
In order to achieve the purpose, the invention adopts the following technical scheme.
The invention provides a nano sterilizing and formaldehyde-removing composition, which is prepared from a composite liquid and an ethanol solution; the composite liquid comprises the following components in percentage by mass: 5-30% of nano material using nano zinc oxide as base, 0.8-7% of organosilane dispersing agent, 0.8-1.6% of block high-molecular copolymer dispersing agent containing acid group, and the rest is solvent; the solvent is ethanol water solution, and the mass of ethanol in the solvent is 20-50% of that of water.
Preferably, the mass of ethanol in the composition is 5-25% of the mass of water.
Preferably, the mass percentage of the nano material in the composition is 1-8%.
Preferably, the mass of the block polymer copolymer dispersant in the composite liquid is 10 to 100% of that of the organosilane dispersant.
Preferably, the organosilane dispersant is methacryloxypropyl modified silane, gamma-methacryloxypropyl trimethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane, or gamma-aminopropyltriethoxysilane.
Preferably, the acidic group-containing block polymer copolymer dispersant is HH2003 or BYK 190.
Preferably, the nano material is nano zinc oxide, Y and Al doped nano zinc oxide, Co and Ce doped nano zinc oxide, nano zinc oxide composite graphene oxide, Y and Al doped nano zinc oxide composite graphene oxide, Co and Ce doped nano zinc oxide composite graphene oxide or nano zinc oxide coated nano silver.
Preferably, the particle size of the nano material is 50-300 nm.
In another aspect of the present invention, there is provided a method for preparing the nano bactericidal and formaldehyde-removing composition, comprising the following steps:
s1, dissolving an organosilane dispersing agent in water to form a solution A, and dissolving a block high-molecular copolymer dispersing agent in absolute ethyl alcohol to form a solution B;
s2, uniformly mixing the solution A and the solution B to form a solution C;
s3, adding the nano material into the solution C to form a dispersion liquid D, then adding water and ethanol into the dispersion liquid D, and uniformly dispersing the mixture to form a composite liquid;
s4, adding water and ethanol into the complex liquid to form the composition.
Preferably, in step S1, the organosilane dispersant is present in the solution A in an amount of 5 to 30% by mass, and the block polymer copolymer dispersant is present in the solution B in an amount of 1 to 10% by mass.
Preferably, in step S3, the mixture is first crushed by an ultrasonic cell crusher for 20-30min, and then ground by zirconia beads stabilized with 0.1-0.3mmYb in a rod-and-mortar type sand mill for 1-3h to form a composite liquid.
Compared with the prior art, the invention has the beneficial effects that:
the invention disperses the nanometer material taking nanometer zinc oxide as the substrate in the ethanol water solution composed of organosilane dispersant and block macromolecule copolymer dispersant, and the mixture is dispersed without a great deal of foam and floating flower by controlling the proportion and the content of the organosilane dispersant and the block macromolecule copolymer dispersant in the mixture, thereby avoiding the problem of reducing the production efficiency due to the foam and the floating flower generated in the dispersion process, being capable of smoothly dispersing and greatly improving the production efficiency. According to the invention, the stability of the composition is obviously improved by optimizing the compounding of the organosilane dispersing agent and the block polymer copolymer dispersing agent in the composition and optimizing the contents of the dispersing agent, ethanol and water, the composition is a transparent solution, and the color and the transparency of the composition are not obviously changed, flocculation is not caused, and precipitation is not caused after the composition is placed for a long time. The sterilization rate of the composition is more than 94 percent, and the formaldehyde removal rate is more than 97 percent.
Detailed Description
In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and illustrated with reference to the following specific embodiments.
The nano-materials with the functions of sterilization and formaldehyde removal are selected, the nano-materials used in the examples and comparative examples listed below are A-G, and other nano-materials with the functions of sterilization and formaldehyde removal can be used in other embodiments.
(A) Nano zinc oxide: the average particle size is 80 nm;
(B) y and Al doped nano zinc oxide (Y/Al-ZnO): the doping amount of Y is 3 wt%, the doping amount of Al is 7 wt%, and the average grain diameter is 100 nm;
(C) co and Ce doped nano zinc oxide (Co/Ce-ZnO): the doping amount of Co is 6 wt%, the doping amount of Ce is 4 wt%, and the average grain diameter is 100 nm;
(D) nano zinc oxide composite graphene oxide (ZnO/graphene oxide): the mass of the graphite oxide is 5 percent of that of the nano zinc oxide, and the average grain diameter is 100 nm;
(E) y and Al-doped nano-zinc oxide composite graphene oxide (Y/Al-ZnO/graphene oxide): the ZnO/graphene oxide uses the nano material D, the doping amount of Y is 3 wt%, the doping amount of Al is 7 wt%, and the average grain diameter is 100 nm;
(F) co-and Ce-doped nano-zinc oxide composite graphene oxide (Co/Ce-ZnO/graphene oxide): the ZnO/graphene oxide adopts the nano material D, the Co doping amount is 6 wt%, the Ce doping amount is 4 wt%, and the average grain diameter is 150 nm;
(G) coating nano silver with nano zinc oxide: (the silver content was 5% by weight, and the average particle diameter was 100 nm).
Among them, the B-F nano materials can be prepared according to the method disclosed in chinese patent document 201810898174.2.
The dispersants used in the examples and comparative examples set forth herein below are as follows:
AC-63T (Canoe): methacryloxypropyl-modified silanes;
KH-570 (Chinese academy of sciences)/A-174 (United states Union carbon)/Z-6030 (Dow Corning Corp.)/KBM-503 (Japanese shiner Corp.)/GF-31 (Germany Wake chemical): gamma-methacryloxypropyltrimethoxysilane;
KH-560 (Chinese academy)/A-187 (United states Union carbon)/Z-6040 (Dow Corning Corp.)/KBM-403 (Japanese shiner Corp.): gamma- (2, 3-glycidoxy) propyltrimethoxysilane;
KH-550 (Chinese academy)/A-1100 (United states Union carbon)/KBE-903 (Japanese Credit): gamma-aminopropyltriethoxysilane;
HH 2003: guangzhou thick scholar assistant company
The aqueous rare earth dispersant is a high-molecular block copolymer containing pigment affinity groups;
BYK 190: bib, germany, BYK dispersant;
BYK 180: bib, germany, BYK dispersant;
w597: creating in France, wetting dispersant synthro PON W597;
a987: french pioneer, dispersant synthro PONA 987, acrylic polymer dispersant;
HH 2054: guangzhou thick scholar assistant company
A dispersant for aqueous coating materials, a carboxylic acid-containing polymer block;
HH 2018: guangzhou thick scholar assistant company
An aqueous wetting dispersant, an acrylic block copolymer.
Example 1
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which specifically comprises the following steps:
dissolving 10g of dispersant A (AC-63T) in 90g of water to form solution A, dissolving 3g of dispersant B (HH2003) in 47g of absolute ethyl alcohol to form solution B, uniformly mixing the solution A and the solution B to form solution C, adding 50g of nano zinc oxide with the average particle size of 80nm to the solution C to form solution D, adding 40g of water and 10g of absolute ethyl alcohol to the solution D to form a mixture with the nano zinc oxide as a substrate, crushing the mixture for 20min by using an ultrasonic cell crusher, and sanding zirconium beads (0.2mm Yb-stabilized zirconium oxide) in a rod-and-nitrate sand mill for 3h to obtain the composite liquid. And adding 2kg of water and 250g of absolute ethyl alcohol into the composite liquid to obtain the nano bactericidal noraldehyde composition.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The compositions prepared in this example were tested for stability, including high temperature stability and low temperature stability tests, and the compositions in the bottles were observed for turbidity, precipitation, and color changes. The test method comprises the following steps: the high-temperature stability test is to place the composition in a bottle after sealing at 45 +/-2 ℃ for one month, and to return to the room temperature of 25 +/-5 ℃ for observation of the appearance; the low temperature stability test is to place the composition in a bottle after sealing, and then to keep the temperature at 0 + -2 deg.C for one month, and to return to room temperature at 25 + -5 deg.C for observation of the appearance.
The composition prepared in the embodiment is qualified in the high-temperature stability test and the low-temperature stability test, has no turbidity and precipitation, is unchanged in color and has good stability.
In the embodiment, the AC-63T dispersing agent and the HH2003 dispersing agent are jointly used, the composite liquid is diluted by water and ethanol until the content of the nano zinc oxide in the composition is 2%, the composite liquid still has good stability, no precipitate appears after long-time standing, the transparency of the solution is not obviously changed, the color is not obviously changed, and the composite liquid is suitable for preparing a spray formulation product.
Example 2
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which specifically comprises the following steps:
dissolving 20g of dispersant A (KH-570) in 80g of water to form solution A, dissolving 5g of dispersant B (HH2003) in 45g of absolute ethyl alcohol to form solution B, uniformly mixing the solution A with the solution B to form solution C, adding 90g of Y/Al-ZnO with the average particle size of 100nm into the solution C to form solution D, adding 50g of water and 10g of absolute ethyl alcohol into the solution D to form a mixture with nano zinc oxide as a substrate, crushing the mixture for 30min by using an ultrasonic cell crusher, grinding zirconium beads (0.2mm Yb-stable zirconium oxide) in a rod-and-nitrate sand mill for 2h to obtain a composite liquid, and adding 1.4Kg of water and 100g of absolute ethyl alcohol into the composite liquid to obtain the nano bactericidal formaldehyde-removing composition.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The stability of the composition prepared in this example was tested as described in example 1, and the composition prepared in this example was acceptable in the high temperature stability test and the low temperature stability test, and no turbidity or precipitation occurred in the composition, and the color remained unchanged, and had good stability.
In this example, the KH-570 dispersant and the HH2003 dispersant are used in combination, and the complex liquid is diluted with water and ethanol until the content of Y/Al-ZnO in the composition is 5%, so that the complex liquid has good stability, no precipitation appears after long-term standing, the transparency of the solution is not obviously changed, and the color is not obviously changed, so that the complex liquid is suitable for preparing a product of a spray formulation.
Example 3
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which specifically comprises the following steps:
dissolving 15g of dispersant A (KH-560) in 85g of water to form solution A, dissolving 2g of dispersant B (HH2003) in 48g of absolute ethyl alcohol to form solution B, uniformly mixing the solution A with the solution B to form solution C, adding 60g of Co/Ce-ZnO/graphene oxide with the average particle size of 150nm into the solution C to form dispersion D, adding 165g of water and 25g of absolute ethyl alcohol into the dispersion D to form a mixture with nano zinc oxide as a substrate, crushing the mixture for 25min by using an ultrasonic cell crusher, adding zirconium beads (0.2 mmYb-stabilized zirconium oxide) into a rod-nitrate type sand mill for 2h to obtain a composite liquid, and adding 750g of water and 50g of absolute ethyl alcohol into the composite liquid to obtain the nano bactericidal formaldehyde-removing composition.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The stability of the composition prepared in this example was tested as described in example 1, and the composition prepared in this example was acceptable in the high temperature stability test and the low temperature stability test, and no turbidity or precipitation occurred in the composition, and the color remained unchanged, and had good stability.
In this example, the KH-560 dispersant and the HH2003 dispersant are used in combination, and the composite solution is diluted with water and ethanol until the content of Co/Ce-ZnO/graphene oxide in the composition is 5%, so that the composite solution still has good stability, no precipitate appears after long-term standing, the transparency of the solution does not change significantly, the color does not change significantly, and the composite solution is suitable for preparing a spray-type product.
Example 4
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which specifically comprises the following steps:
dissolving 5g of dispersant A (KH-550) in 95g of water to form solution A, dissolving 5g of dispersant B (HH2003) in 45g of absolute ethyl alcohol to form solution B, uniformly mixing the solution A with the solution B to form solution C, adding 60g of nano zinc oxide with the average particle size of 100nm to wrap nano silver into the solution C to form dispersion D, adding 300g of water and 90g of absolute ethyl alcohol into the dispersion D to form mixed solution with the nano zinc oxide as a substrate, crushing the mixed solution for 30min by using an ultrasonic cell crusher, adding zirconium beads (0.2mm Yb-stable zirconium oxide) into a rod-and-nitrate type sand mill for 3h to obtain composite solution, and adding 2.3kg of water and 100g of absolute ethyl alcohol into the composite solution to obtain the nano bactericidal formaldehyde-removing composition.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The stability of the composition prepared in this example was tested as described in example 1, and the composition prepared in this example was acceptable in the high temperature stability test and the low temperature stability test, and no turbidity or precipitation occurred in the composition, and the color remained unchanged, and had good stability.
In the embodiment, the KH-550 dispersant and the HH2003 dispersant are jointly used, and the composite liquid is diluted by water and ethanol until the content of nano silver coated by nano zinc oxide in the composite liquid is 2%, so that the composite liquid still has good stability, does not precipitate after being placed for a long time, has no obvious change in transparency of the solution, does not change color, and is suitable for preparing products of spray formulations.
Example 5
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which comprises the steps that the specific steps are basically the same as those of the embodiment 1, the difference is that the added nano material is different, the added nano material is 100nm Co/Ce-ZnO, namely the Co/Ce-ZnO is used for replacing the nano zinc oxide described in the embodiment 1, and the others are the same as those of the embodiment 1.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The stability of the composition prepared in this example was tested as described in example 1, and the composition prepared in this example was tested to be acceptable in the high temperature stability test and the low temperature stability test, and no turbidity or precipitation occurred in the composition, and the color remained unchanged, and the composition had good stability, and was suitable for use in the manufacture of spray dosage form products.
Example 6
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which has the same specific steps as those of embodiment 1, except that the added nano material is different, the added nano material is 100nm ZnO/graphene oxide, that is, ZnO/graphene oxide is used to replace the nano zinc oxide described in embodiment 1, and the others are the same as those of embodiment 1.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The stability of the composition prepared in this example was tested as described in example 1, and the composition prepared in this example was tested to be acceptable in the high temperature stability test and the low temperature stability test, and no turbidity or precipitation occurred in the composition, and the color remained unchanged, and the composition had good stability, and was suitable for use in the manufacture of spray dosage form products.
Example 7
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which has the same specific steps as those of embodiment 1, except that the added nano material is different, the added nano material is 100nm of Y/Al-ZnO/graphene oxide, that is, Y/Al-ZnO/graphene oxide is used to replace the nano zinc oxide described in embodiment 1, and the others are the same as those of embodiment 1.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The stability of the composition prepared in this example was tested as described in example 1, and the composition prepared in this example was tested to be acceptable in the high temperature stability test and the low temperature stability test, and no turbidity or precipitation occurred in the composition, and the color remained unchanged, and the composition had good stability, and was suitable for use in the manufacture of spray dosage form products.
Example 8
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which is different from the embodiment 1 mainly in that the amount of added nano materials is different, and 13g of nano zinc oxide is added in the embodiment, and the specific steps are as follows:
dissolving 10g of dispersant A (AC-63T) in 90g of water to form solution A, dissolving 3g of dispersant B (HH2003) in 47g of absolute ethyl alcohol to form solution B, uniformly mixing the solution A and the solution B to form solution C, adding 13g of nano zinc oxide with the average particle size of 80nm into the solution C to form solution D, adding 70g of water and 17g of absolute ethyl alcohol into the solution D to form mixed solution with the nano zinc oxide as a substrate, crushing the mixed solution for 20min by using an ultrasonic cell crusher, and sanding zirconium beads (0.2mm Yb-stabilized zirconium oxide) in a rod-and-nitrate sand mill for 3h to obtain the composite solution. And adding 2kg of water and 250g of absolute ethyl alcohol into the composite liquid to obtain the nano bactericidal noraldehyde composition.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The stability of the composition prepared in this example was tested as described in example 1, and the composition prepared in this example was tested to be acceptable in the high temperature stability test and the low temperature stability test, and no turbidity or precipitation occurred in the composition, and the color remained unchanged, and the composition had good stability, and was suitable for use in the manufacture of spray dosage form products.
Example 9
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which is mainly different from the embodiment 1 in that the amount of water and absolute ethyl alcohol added into a dispersion liquid D is different, and the preparation method comprises the following specific steps:
dissolving 10g of dispersant A (AC-63T) in 90g of water to form solution A, dissolving 3g of dispersant B (HH2003) in 47g of absolute ethyl alcohol to form solution B, uniformly mixing the solution A and the solution B to form solution C, adding 50g of nano zinc oxide with the average particle size of 80nm into the solution C to form solution D, adding 35g of water and 15g of absolute ethyl alcohol into the solution D to form mixed solution with the nano zinc oxide as a substrate, crushing the mixed solution for 20min by using an ultrasonic cell crusher, and sanding zirconium beads (0.2mm Yb-stabilized zirconium oxide) in a rod-and-nitrate sand mill for 3h to obtain the composite solution. And adding 2kg of water and 250g of absolute ethyl alcohol into the composite liquid to obtain the nano bactericidal noraldehyde composition.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The stability of the composition prepared in this example was tested as described in example 1, and the composition prepared in this example was tested to be acceptable in the high temperature stability test and the low temperature stability test, and no turbidity or precipitation occurred in the composition, and the color remained unchanged, and the composition had good stability, and was suitable for use in the manufacture of spray dosage form products.
Example 10
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which is mainly different from the embodiment 3 in that the amount of water and absolute ethyl alcohol added into a dispersion liquid D is different, and the preparation method comprises the following specific steps:
dissolving 15g of dispersant A (KH-560) in 85g of water to form solution A, dissolving 2g of dispersant B (HH2003) in 48g of absolute ethyl alcohol to form solution B, uniformly mixing the solution A and the solution B to form solution C, adding 60g of Co/Ce-ZnO/graphene oxide with the average particle size of 150nm into the solution C to form dispersion D, adding 173g of water and 17g of absolute ethyl alcohol into the dispersion D to form a mixture with nano zinc oxide as a substrate, crushing the mixture for 25min by using an ultrasonic cell crusher, adding zirconium beads (0.2 mmYb-stabilized zirconium oxide) into a rod-nitrate type sand mill for 2h to obtain a composite liquid, and adding 750g of water and 50g of absolute ethyl alcohol into the composite liquid to obtain the nano bactericidal noraldehyde composition.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The stability of the composition prepared in this example was tested as described in example 1, and the composition prepared in this example was tested to be acceptable in the high temperature stability test and the low temperature stability test, and no turbidity or precipitation occurred in the composition, and the color remained unchanged, and the composition had good stability, and was suitable for use in the manufacture of spray dosage form products.
Example 11
This example provides a method for preparing a nano-bactericidal and formaldehyde-removing composition, which is the same as that of example 1, and is different from example 1 mainly in that water and absolute ethyl alcohol are added into the composite liquid in different amounts, and 328g of water and 47g of absolute ethyl alcohol are added into the composite liquid.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The stability of the composition prepared in this example was tested as described in example 1, and the composition prepared in this example was tested to be acceptable in the high temperature stability test and the low temperature stability test, and no turbidity or precipitation occurred in the composition, and the color remained unchanged, and the composition had good stability, and was suitable for use in the manufacture of spray dosage form products.
Example 12
The embodiment provides a preparation method of a nano sterilizing and formaldehyde-removing composition, which is mainly different from the embodiment 1 in that a dispersant B is BYK190, and the preparation method comprises the following specific steps:
dissolving 10g of dispersant A (AC-63T) in 90g of water to form solution A, dissolving 3g of dispersant B (BYK190) in 47g of absolute ethyl alcohol to form solution B, uniformly mixing the solution A and the solution B to form solution C, adding 50g of nano zinc oxide with the average particle size of 80nm into the solution C to form dispersion D, finally adding 40g of water and 10g of absolute ethyl alcohol into the dispersion D to form mixed solution with the nano zinc oxide as a substrate, crushing the mixed solution for 20min by using an ultrasonic cell crusher, and sanding by using zirconium beads (0.2mm Yb-stabilized zirconium oxide) in a rod-and-nitrate sand mill for 3h to obtain the composite solution. And adding 2kg of water and 250g of absolute ethyl alcohol into the composite liquid to obtain the nano bactericidal noraldehyde composition.
In the process of dispersing the mixture by using the ultrasonic cell crusher and the rod-nitre type sand mill, a large amount of foam/floating flowers are not generated in the mixture, and the dispersing treatment can be smoothly carried out.
The stability of the composition prepared in this example was tested as described in example 1, and the composition prepared in this example was tested to be acceptable in the high temperature stability test and the low temperature stability test, and no turbidity or precipitation occurred in the composition, and the color remained unchanged, and the composition had good stability, and was suitable for use in the manufacture of spray dosage form products.
Comparative example 1
The embodiment provides a preparation method of a nano sterilizing and formaldehyde-removing composition, which is mainly different from the embodiment 1 in that a dispersant B is not added, and the preparation method comprises the following specific steps:
firstly, 13g of dispersing agent A (AC-63T) is dissolved in 137g of water to form solution A, then 50g of nano zinc oxide with the average particle size of 80nm is added into the solution A to form dispersion liquid, finally, 40g of water and 10g of absolute ethyl alcohol are added into the dispersion liquid to form mixed liquid with the nano zinc oxide as a substrate, the mixed liquid is crushed for 20min by an ultrasonic cell crusher, and then, zirconium beads (0.2mm Yb stable zirconium oxide) are subjected to sanding for 3h in a rod-nitre type sand mill to obtain the composite liquid. And adding 2kg of water and 250g of absolute ethyl alcohol into the composite liquid to obtain the nano bactericidal noraldehyde composition.
The composition formed right after preparation is colorless transparent liquid, but the transparency of the solution gradually decreases and becomes turbid in the process of standing at room temperature (26-30 ℃), and the composition in a bottle appears flocculent precipitate after standing for 10 days, so that the stability is poor.
Comparative example 2
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which is mainly different from the embodiment 1 in that no dispersant A is added, and the specific steps are as follows:
firstly, 13g of dispersant B (HH2003) is dissolved in 137g of absolute ethyl alcohol to form a B solution, then 50g of nano zinc oxide with the average particle size of 80nm is added into the B solution to form a dispersion, finally, 40g of water and 10g of absolute ethyl alcohol are added into the dispersion to form a mixed solution taking the nano zinc oxide as a substrate, the mixed solution is crushed for 20min by an ultrasonic cell crusher and then is subjected to sand milling for 3h in a rod-nitre type sand mill by zirconium beads (0.2mm Yb stabilized zirconium oxide) to obtain a composite solution. And adding 2kg of water and 250g of absolute ethyl alcohol into the composite liquid to obtain the nano bactericidal noraldehyde composition.
During the dispersion treatment of the mixture with an ultrasonic cell disruptor and a pin-nitre type sander, the mixture produced a large amount of foam/bloom.
The composition just formed is poorly dispersible, solution-stratified, and not suitable for making spray products.
Comparative example 3
This example provides a method for preparing a nano bactericidal and formaldehyde-removing composition, which is different from that of example 1 mainly in that the dispersant B used in this example is BYK dispersant-BYK 180 in Germany, that is, BYK180 is used to replace the dispersant B (HH2003) described in example 1, and the rest is the same as that of example 1.
During the dispersion treatment of the mixture with an ultrasonic cell disruptor and a pin-nitre type sander, the mixture produced a large amount of foam/bloom.
The composition just formed is poorly dispersible, solution-stratified, and not suitable for making spray products.
Comparative example 4
This example provides a method for preparing a nano bactericidal and formaldehyde-removing composition, which is different from that of example 1 mainly in that the dispersant B used in this example is W597, that is, W597 is used instead of the dispersant B (HH2003) described in example 1, and the rest is the same as that of example 1.
During the dispersion treatment of the mixture with an ultrasonic cell disruptor and a pin-nitre type sander, the mixture produced a large amount of foam/bloom.
The composition just formed is poorly dispersible, solution-stratified, and not suitable for making spray products.
Comparative example 5
This example provides a method for preparing a nano bactericidal and formaldehyde-removing composition, which is different from that of example 1 mainly in that the dispersant B used in this example is A987, i.e. A987 is used instead of the dispersant B (HH2003) described in example 1, and the rest is the same as that of example 1.
During the dispersion treatment of the mixture with an ultrasonic cell disruptor and a pin-nitre type sander, the mixture produced a large amount of foam/bloom.
The composition just formed is poorly dispersible, solution-stratified, and not suitable for making spray products.
Comparative example 6
This example provides a method for preparing a nano bactericidal and formaldehyde-removing composition, which is different from that of example 1 mainly in that the dispersant B used in this example is HH2054, i.e. HH2054 is used to replace the dispersant B (HH2003) described in example 1, and the rest is the same as that of example 1.
During the dispersion treatment of the mixture with an ultrasonic cell disruptor and a pin-nitre type sander, the mixture produced a large amount of foam/bloom.
The composition just formed is poorly dispersible, solution-stratified, and not suitable for making spray products.
Comparative example 7
This example provides a method for preparing a nano bactericidal and formaldehyde-removing composition, which is different from that of example 1 mainly in that the dispersant B used in the comparative example is HH2018, i.e. HH2018 is used to replace the dispersant B (HH2003) described in example 1, and the rest is the same as that of example 1.
During the dispersion treatment of the mixture with an ultrasonic cell disruptor and a pin-nitre type sander, the mixture produced a large amount of foam/bloom.
The composition just formed is poorly dispersible, solution-stratified, and not suitable for making spray products.
Comparative example 8
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which is mainly different from the embodiment 1 in the addition amount of a dispersant A and a dispersant B, and comprises the following specific steps:
dissolving 10g of dispersant A (AC-63T) in 90g of water to form solution A, dissolving 5g of dispersant B (HH2003) in 45g of absolute ethyl alcohol to form solution B, uniformly mixing the solution A and the solution B to form solution C, adding 50g of nano zinc oxide with the average particle size of 80nm into the solution C to form solution D, adding 40g of water and 10g of absolute ethyl alcohol into the solution D to form mixed solution with the nano zinc oxide as a substrate, crushing the mixed solution for 20min by using an ultrasonic cell crusher, and sanding zirconium beads (0.2mm Yb-stabilized zirconium oxide) in a rod-and-nitrate sand mill for 3h to obtain the composite solution. And adding 2kg of water and 250g of absolute ethyl alcohol into the composite liquid to obtain the nano bactericidal noraldehyde composition.
The composition formed just after preparation is colorless transparent liquid, but the transparency of the solution gradually decreases and becomes turbid in the standing process at room temperature (26-30 ℃), and the composition in a bottle appears flocculent precipitate after standing for 10 days, so that the stability is poor.
Comparative example 9
The embodiment provides a preparation method of a nano sterilizing and formaldehyde removing composition, which is mainly different from the embodiment 1 in the addition amount of a dispersant A and a dispersant B, and comprises the following specific steps:
firstly, 23g of dispersant A (AC-63T) is dissolved in 77g of water to form solution A, 7g of dispersant B (HH2003) is dissolved in 43g of absolute ethyl alcohol to form solution B, then the solution A and the solution B are uniformly mixed to form solution C, then 50g of nano zinc oxide with the average particle size of 80nm is added into the solution C to form dispersion D, finally, 40g of water and 10g of absolute ethyl alcohol are added into the dispersion D to form mixed solution with the nano zinc oxide as a substrate, the mixed solution is crushed for 20min by an ultrasonic cell crusher, and then, zirconium beads (0.2mm Yb stabilized zirconium oxide) are sanded for 3h in a rod-nitre type sand mill to obtain the composite solution. And adding 2kg of water and 250g of absolute ethyl alcohol into the composite liquid to obtain the nano bactericidal noraldehyde composition.
During the dispersion treatment of the mixture by using an ultrasonic cell crusher and a mirabilite type sand mill, more foams/floating flowers are generated in the mixture.
Comparative example 10
The present example provides a preparation method of a nano-bactericidal and formaldehyde-removing composition, the composite liquid prepared in this example is the same as that of example 1, and the difference from example 1 is mainly that only 2250g of water is added to the composite liquid, and absolute ethyl alcohol is not added.
The composition formed just after preparation is colorless transparent liquid, but the transparency of the solution gradually decreases and becomes turbid in the standing process at room temperature (26-30 ℃), and the composition in a bottle appears flocculent precipitate after standing for 10 days, so that the stability is poor.
And (3) testing: the compositions prepared in the above examples were tested for their bactericidal and formaldehyde-removing properties
Testing one: the compositions prepared in the above examples were tested for bactericidal properties
The detection method comprises the following steps: taking a certain volume of the prepared composition and an isometric staphylococcus aureus liquid, uniformly mixing the composition and the isometric staphylococcus aureus liquid, then oscillating the mixture on an oscillator for 30min, then uniformly coating 50ml of the solution on a plate for experiment, putting the plate for experiment and a control plate without the composition into a thermostatic chamber, standing for 24h, taking out, counting the colony number of the plate respectively, and then calculating the sterilization rate.
The bactericidal ratio (number of colonies in control experiment-number of colonies in sample experiment)/number of colonies in control experiment X100%
And (2) testing: the compositions prepared in the above examples were tested for their formaldehyde-removing properties
The detection method comprises the following steps: the composition is sprayed on a clean glass plate, and after air drying, detection is carried out according to JC/1074 plus 2008 'indoor air purification function coating material purification performance'.
The results of the tests one and two are shown in the following table.
The technical contents of the present invention are further illustrated by the examples, so as to facilitate the understanding of the reader, but the embodiments of the present invention are not limited thereto, and any technical extension or re-creation based on the present invention is protected by the present invention.
Claims (9)
1. A nanometer bactericidal formaldehyde-removing composition is characterized by being prepared from a composite liquid and an ethanol solution; the composite liquid comprises the following components in percentage by mass: 5-30% of nano material using nano zinc oxide as substrate, 0.8-7% of organosilane dispersing agent, 0.8-1.6% of block high-molecular copolymer dispersing agent containing acid group and the rest is solvent; the solvent is ethanol water solution, and the mass of ethanol in the solvent is 20-50% of that of water; the organosilane dispersing agent is one of AC-63T, KH570, KH560 and KH550, and the dispersing agent of the block polymer copolymer containing acidic groups is HH2003 or BYK 190.
2. The nano bactericidal noraldehyde composition as claimed in claim 1, wherein the mass of ethanol in the composition is 5-25% of the mass of water.
3. The nano bactericidal noraldehyde composition as claimed in claim 2, wherein the nano material in the composition accounts for 1-8% by mass.
4. The nano bactericidal noraldehyde composition as claimed in claim 1, wherein the mass of the block polymer copolymer dispersant in the composite liquid is 10-100% of that of the organosilane dispersant.
5. The nano bactericidal noral composition as set forth in claim 1, wherein the organosilane dispersing agent is methacryloxypropyl modified silane, gamma-methacryloxypropyl trimethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane, or gamma-aminopropyltriethoxysilane.
6. The nano bactericidal formaldehyde-removing composition as claimed in claim 1, wherein the nano material is nano zinc oxide, Y and Al doped nano zinc oxide, Co and Ce doped nano zinc oxide, nano zinc oxide composite graphene oxide, Y and Al doped nano zinc oxide composite graphene oxide, Co and Ce doped nano zinc oxide composite graphene oxide, or nano zinc oxide coated nano silver.
7. The nano bactericidal noraldehyde composition as defined in claim 6, wherein the particle size of the nano material is 50-300 nm.
8. A method for preparing the nano sterilizing and formaldehyde-removing composition as claimed in claim 1, which comprises the following steps:
s1, dissolving an organosilane dispersing agent in water to form a solution A, and dissolving a block high-molecular copolymer dispersing agent in absolute ethyl alcohol to form a solution B;
s2, uniformly mixing the solution A and the solution B to form a solution C;
s3, adding the nano material into the solution C to form a dispersion liquid D, then adding water and ethanol into the dispersion liquid D, and uniformly dispersing the mixture to form a composite liquid;
s4, adding water and ethanol into the complex liquid to form the composition.
9. The method for preparing a nano bactericidal formaldehyde-removing composition as claimed in claim 8, wherein in step S3, the mixture is first crushed by an ultrasonic cell crusher for 20-30min, and then ground by 0.1-0.3mm Yb-stabilized zirconia beads in a pin-and-mortar type sand mill for 1-3h to form a composite liquid.
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