阅读说明：本技术 纳米微粒子的制备及其杀菌除味除醛组合物应用 (Preparation of nano-micro-particle and application of sterilization, odor removal and aldehyde removal composition thereof ) 是由 童飞 刘倩 蔡川旭 于 2020-12-15 设计创作，主要内容包括：本发明涉及纳米微粒子的制备与应用技术领域,尤其涉及纳米微粒子的制备及其杀菌除味除醛组合物应用。所述纳米微离子的制备步骤包括：(1)将异丙醇钛和聚合物螯合剂溶液混合并经过超声处理,得到混合液A；(2)将混合液A、乙醇水混合溶液、添加剂置于间歇式超临界流体处理装置中反应得到纳米微离子。本发明中的纳米微粒子在水中尤其是在纳米SOD水中具有良好的分散性,并且本发明的纳米微离子是一种液状的纳米微离子,具有较高的浓度和稳定性；本发明提供的纳米微离子的杀菌除味除醛组合物具有空气净化、水质净化、抗菌消毒、自清洁的功能。(The invention relates to the technical field of preparation and application of nano-particles, in particular to preparation of nano-particles and application of a composition for sterilizing, deodorizing and removing aldehyde. The preparation method of the nanometer micro-ions comprises the following steps: (1) mixing titanium isopropoxide and a polymer chelating agent solution, and performing ultrasonic treatment to obtain a mixed solution A; (2) and placing the mixed solution A, the ethanol-water mixed solution and the additive into an intermittent supercritical fluid treatment device for reaction to obtain the nano micro-ions. The nano microparticles have good dispersibility in water, particularly in nano SOD water, and the nano micro ions are liquid nano micro ions and have higher concentration and stability; the nano-micro-ion composition for sterilizing, deodorizing and removing aldehyde provided by the invention has the functions of air purification, water purification, antibiosis, disinfection and self-cleaning.)

1. The preparation method of the nanometer micro-ions is characterized by comprising the following steps:

(1) mixing titanium isopropoxide and a polymer chelating agent solution, and performing ultrasonic treatment to obtain a mixed solution A;

(2) and placing the mixed solution A, the ethanol-water mixed solution and the additive into an intermittent supercritical fluid treatment device for reaction to obtain the nano micro-ions.

2. The preparation of nano micro ions according to claim 1, wherein the volume ratio of titanium isopropoxide to the solution of the polymer chelating agent in step (1) is 1: (3-4).

3. The preparation of nano micro ions according to claim 1, wherein the volume ratio of the mixed material A to the ethanol-water mixed solution in the step (2) is 1: 1; the weight of the additive is 25-30% of that of the titanium isopropoxide.

4. The preparation of nanomicrons according to claim 1, wherein the polymer chelator solution consists of ethanol and a polymer chelator.

5. The preparation of nanoparticles of claim 1, wherein the polymer chelating agent is one of water-based alkyd resin, water-based acrylic resin, water-based epoxy resin, and water-based polyurethane.

6. The method for preparing nano micro ions according to claim 1, wherein the volume ratio of ethanol to water in the ethanol-water mixed solution is (3-5): 1.

7. the method of claim 1, wherein the additive is an acidic additive.

8. The method of claim 7, wherein the acidic additive is at least one of acetic acid, formic acid, phthalic acid, benzoic acid, terephthalic acid, and benzoic acid.

9. A nano-micro ionic bactericidal odor-removing aldehyde-removing composition, which comprises the nano-micro ions prepared according to any one of claims 1 to 8.

10. The application of the nano-micro ionic bactericidal odor-removing aldehyde-removing composition as claimed in claim 9, wherein the application of the nano-micro ionic bactericidal odor-removing aldehyde-removing composition comprises the treatment of beriberi, odor removal and formaldehyde removal.

Technical Field

The invention relates to the technical field of preparation and application of nano-particles, in particular to preparation of nano-particles and application of a composition for sterilizing, deodorizing and removing aldehyde.

Background

Since the nano-particles are relatively fine, especially the nano-titanium dioxide particles, the nano-particles are in the technical fields of catalysts, ultraviolet resistance, adsorbents and the like. The traditional preparation method of nano titanium dioxide particles comprises a gel-sol method, a titanium tetrachloride gas phase oxidation method, a titanium alkoxide gas phase hydrolysis method and a solid phase method. However, the nano titanium dioxide particles prepared by the methods have few remarkable functionalities, and on the one hand, the nano titanium dioxide particles are easy to agglomerate and have poor dispersibility in water.

Disclosure of Invention

In order to solve the above technical problems, a first aspect of the present invention provides a method for preparing nano micro-ions, the method comprising the steps of:

(1) mixing titanium isopropoxide and a polymer chelating agent solution, and performing ultrasonic treatment to obtain a mixed solution A;

(2) and placing the mixed solution A, the ethanol-water mixed solution and the additive into an intermittent supercritical fluid treatment device for reaction to obtain the nano micro-ions.

As a preferred technical solution of the present invention, the volume ratio of the titanium isopropoxide to the polymer chelating agent solution in the step (1) is 1: (3-4).

As a preferable technical scheme of the invention, the volume ratio of the mixed material a and the ethanol-water mixed solution in the step (2) is 1: 1; the weight of the additive is 25-30% of that of the titanium isopropoxide.

As a preferred technical scheme of the invention, the polymer chelating agent solution consists of ethanol and a polymer chelating agent.

As a preferable technical scheme of the invention, the polymer chelating agent is one of water-based alkyd resin, water-based acrylic resin, water-based epoxy resin and water-based polyurethane.

As a preferable technical scheme of the invention, the volume ratio of ethanol to water in the ethanol-water mixed solution is (3-5): 1.

in a preferred embodiment of the present invention, the additive is an acidic additive.

In a preferred embodiment of the present invention, the acidic additive is at least one of acetic acid, formic acid, phthalic acid, benzoic acid, terephthalic acid, and benzoic acid.

In a second aspect of the invention, a nano-micro ionic bactericidal odor-removing aldehyde-removing composition is provided, which comprises the nano-micro ions prepared by any one of the methods.

The third aspect of the invention provides application of a nano-micro-ion sterilization, odor removal and aldehyde removal composition, wherein the application of the nano-micro-ion sterilization, odor removal and aldehyde removal composition comprises beriberi treatment, odor removal and formaldehyde removal.

The invention has the following beneficial effects:

1. the nano-particles have good dispersibility and stability in water;

2. the nano-micro-ion composition for sterilizing, deodorizing and removing aldehyde has the functions of air purification, water purification, antibiosis, disinfection and self-cleaning;

3. the nanometer micro-ion is a liquid nanometer micro-ion and has higher concentration and stability;

4. the invention increases the dispersibility of the nanometer micro-ions in water through the additive;

5. the invention increases the dispersibility of the nanometer micro-ions in water by adding the polymer chelating agent.

Detailed Description

The first aspect of the present invention provides a method for preparing nano micro ions, wherein the method comprises the following steps:

(1) mixing titanium isopropoxide and a polymer chelating agent solution, and performing ultrasonic treatment to obtain a mixed solution A;

(2) and placing the mixed solution A, the ethanol-water mixed solution and the additive into an intermittent supercritical fluid treatment device for reaction to obtain the nano micro-ions.

In one embodiment, the volume ratio of titanium isopropoxide to the solution of the polymeric chelant in step (1) is 1: (3-4).

In one embodiment, the volume ratio of the mixture A to the ethanol-water mixed solution in the step (2) is 1: 1; the weight of the additive is 25-30% of that of the titanium isopropoxide.

In one embodiment, the ultrasonic treatment temperature in the step (1) is less than 60 ℃ and the ultrasonic treatment time is 40-50 min.

And (2) the ultrasonic treatment in the step (1) enables titanium isopropoxide to be dispersed in the polymer chelating agent solution, so that the subsequent reaction is facilitated, and the stability of the nano micro-ions in the step (2) is facilitated.

In one embodiment, the reaction temperature in step (2) is greater than 245 ℃ and the reaction pressure is greater than 6.3 MPa.

The critical temperature of the ethanol is 243 ℃, the critical pressure is 6.3MPa, and in the invention, the ethanol is reacted in a supercritical state, so that the time for preparing the nano-particles is reduced, and the stability and the dispersibility of the prepared nano-particles are improved.

In one embodiment, the nano micro-ions in step (2) are subjected to heat treatment at 200-220 ℃ after removing water, distilling under reduced pressure and removing organic solvent to obtain nano micro-ion powder.

In the present invention, nano micro ions and nano micro ion powder may be used as necessary.

The procurement was from Shanghai Tongyun Industrial Co., Ltd.

In one embodiment, the polymeric chelant solution is comprised of ethanol and polymeric chelant, wherein the polymeric chelant comprises 0.1 to 0.2 grams per milliliter of ethanol.

In one embodiment, the polymeric chelant is one of a waterborne alkyd resin, a waterborne acrylic resin, a waterborne epoxy resin, and a waterborne polyurethane.

In a preferred embodiment, the polymeric chelant is a waterborne alkyd resin.

Applicants have found that in the present invention, the stability and dispersibility of the use of waterborne alkyd resin nanoparticles is better. This may be related to the presence of certain hydroxyl groups on the waterborne alkyd.

The waterborne alkyd resin is purchased from Nantong Runfeng petrochemical Co.

In one embodiment, the volume ratio of ethanol to water in the ethanol-water mixture is (3-5): 1.

applicants have found that in the system of the present invention, the volume ratio of ethanol to water is (3-5): the nano-microparticles prepared in the step 1 have better dispersion performance, and the dispersion performance of the nano-microparticles is influenced by too much or too little water, probably because the water content influences the speed of the hydrolysis reaction of the titanium isopropoxide, so that the structure of the nano-microparticles is influenced, and the dispersion performance of the nano-microparticles is influenced.

In one embodiment, the additive is an acidic additive.

In a preferred embodiment, the acidic additive is at least one of acetic acid, formic acid, phthalic acid, benzoic acid, terephthalic acid, benzoic acid.

In a more preferred embodiment, the acidic additive is a mixture of formic acid and oxalic acid, wherein the weight ratio of formic acid to oxalic acid is (3-5): 1.

the applicant has found that when a mixture of formic acid and oxalic acid is used in a certain proportion, the dispersion of the nanoparticles formed is better, which may be related to the strength of the acid of the acidic additive, which varies in acidity, which provides H⁺In contrast, H adsorbed on the surface of the particles in the system⁺The force between them affects the dispersibility of the force aggregation particles.

In one embodiment, the nanoparticle dispersion system is water and/or SOD nanopowder.

In a second aspect of the invention, a nano-micro ionic bactericidal odor-removing aldehyde-removing composition is provided, which comprises the nano-micro ions prepared by any one of the methods.

The third aspect of the invention provides application of a nano-micro-ion sterilization, odor removal and aldehyde removal composition, wherein the application of the nano-micro-ion sterilization, odor removal and aldehyde removal composition comprises beriberi treatment, odor removal and formaldehyde removal. In one embodiment, the nano-micro ionic bactericidal odor-removing aldehyde-removing composition comprises any one of the nano-micro ions or nano-micro ionic powder described above.

In one embodiment, the nano-micro ionic bactericidal odor-removing and aldehyde-removing composition is applied, and the application of the nano-micro ionic bactericidal odor-removing and aldehyde-removing composition comprises beriberi treatment, odor removal and formaldehyde removal.

In one embodiment, the nano-micro ionic bactericidal odor-removing aldehyde-removing composition further comprises nano SOD water and polyhexamethylene guanidine.

In one embodiment, the weight of the nano micro-ionic powder is 4-6% of the weight of nano SOD water; the weight of the polyhexamethylene guanidine is 0.8-1.2% of the weight of the nanometer SOD water.

In the invention, the nano SOD water is obtained by mixing nano SOD and water, and the weight of the nano SOD in the water is 0.006-0.008%.

The nanometer SOD is purchased from Shanghai Gu' an company, Inc.

In the invention, the nano-micro-ion sterilizing and odor-removing aldehyde-removing composition can be diluted by water and used as aquaculture water, because the nano-micro-ions have good dispersibility in water and nano-SOD water, the nano-micro-ion sterilizing and odor-removing aldehyde-removing composition has excellent sterilizing performance as the aquaculture water and does not need to be replaced frequently.

The application of the nano-micro-ionic bactericidal odor-removing aldehyde-removing composition is not limited to the above application, and all the nano-micro-ionic bactericidal odor-removing aldehyde-removing compositions with the characteristics of nano-micro-particles in the invention belong to the protection scope of the invention.

In one embodiment, the composition for sterilizing, deodorizing and removing aldehyde can be used as an additive to prepare beriberi powder and a sterilizing insole, so that the purpose of preventing and treating beriberi is achieved.

In one embodiment, the bactericidal odor-removing and aldehyde-removing composition can be used as an additive to prepare adsorbent for purifying air, decomposing formaldehyde, etc.

In one embodiment, the water purifying agent can be prepared by using the sterilizing, deodorizing and aldehyde-removing composition as an additive, so as to remove metal ions, microorganisms, bacteria and the like.

In one embodiment, the composition for sterilizing, deodorizing and removing aldehyde can be used as an additive to be added into a skin care product to prepare a sun-screening and whitening skin care product.

In one embodiment, some cleaning materials can be prepared using germicidal odor-reducing aldehyde-removing compositions as additives.

Several specific examples of the present invention are given below, but the present invention is not limited by the examples.

In addition, the starting materials used are all commercially available, unless otherwise specified.

Examples

Example 1

Embodiment 1 of the present invention specifically provides a method for preparing nano micro ions, which comprises the following steps: (1) mixing titanium isopropoxide and a polymer chelating agent solution, and performing ultrasonic treatment to obtain a mixed solution A; (2) placing the mixed solution A, the ethanol-water mixed solution and the additive in an intermittent supercritical fluid treatment device for reaction to obtain nano micro-ions;

the volume ratio of the titanium isopropoxide to the polymer chelating agent solution in the step (1) is 1: 3;

the volume ratio of the mixed material A to the ethanol-water mixed solution in the step (2) is 1: 1; the weight of the additive is 25% of that of the titanium isopropoxide;

the ultrasonic treatment temperature in the step (1) is 50 ℃, and the ultrasonic treatment time is 50 min;

the reaction temperature in the step (2) is 250 ℃, and the reaction pressure is 6.5 MPa;

the polymer chelating agent solution consists of ethanol and a polymer chelating agent, wherein 0.1g of the polymer chelating agent is contained in each milliliter of the ethanol;

the polymer chelant is a waterborne alkyd resin;

the volume ratio of ethanol to water in the ethanol-water mixed solution is 3: 1;

the additive is an acidic additive;

the acidic additive is a mixture of formic acid and oxalic acid, wherein the weight ratio of the formic acid to the oxalic acid is 3: 1.

the purchase was made in Shanghai Tongyun Industrial Co., Ltd; the waterborne alkyd resin is purchased from Nantong Runfeng petrochemical Co.

Example 2

Embodiment 2 of the present invention specifically provides a method for preparing nano micro ions, which comprises the following steps: (1) mixing titanium isopropoxide and a polymer chelating agent solution, and performing ultrasonic treatment to obtain a mixed solution A; (2) placing the mixed solution A, the ethanol-water mixed solution and the additive in an intermittent supercritical fluid treatment device for reaction to obtain nano micro-ions;

the volume ratio of the titanium isopropoxide to the polymer chelating agent solution in the step (1) is 1: 4;

the volume ratio of the mixed material A to the ethanol-water mixed solution in the step (2) is 1: 1; the weight of the additive is 30% of that of the titanium isopropoxide;

the ultrasonic treatment temperature in the step (1) is 50 ℃, and the ultrasonic treatment time is 45 min;

the reaction temperature in the step (2) is 260 ℃, and the reaction pressure is 6.5 MPa;

the polymer chelating agent solution consists of ethanol and a polymer chelating agent, wherein 0.2g of the polymer chelating agent is contained in each milliliter of the ethanol;

the polymer chelant is a waterborne alkyd resin;

the volume ratio of ethanol to water in the ethanol-water mixed solution is 5: 1;

the additive is an acidic additive;

the acidic additive is a mixture of formic acid and oxalic acid, wherein the weight ratio of the formic acid to the oxalic acid is (5: 1).

The purchase was made in Shanghai Tongyun Industrial Co., Ltd; the waterborne alkyd resin is purchased from Nantong Runfeng petrochemical Co.

Example 3

Embodiment 3 of the present invention specifically provides a preparation method of nano micro ions, where the preparation method of nano micro ions includes: (1) mixing titanium isopropoxide and a polymer chelating agent solution, and performing ultrasonic treatment to obtain a mixed solution A; (2) placing the mixed solution A, the ethanol-water mixed solution and the additive in an intermittent supercritical fluid treatment device for reaction to obtain nano micro-ions;

the volume ratio of the titanium isopropoxide to the polymer chelating agent solution in the step (1) is 1: 3.6;

the volume ratio of the mixed material A to the ethanol-water mixed solution in the step (2) is 1: 1; the weight of the additive is 28% of that of the titanium isopropoxide;

the ultrasonic treatment temperature in the step (1) is 55 ℃, and the ultrasonic treatment time is 45 min;

the reaction temperature in the step (2) is 270 ℃, and the reaction pressure is 6.8 MPa;

the polymer chelating agent solution consists of ethanol and a polymer chelating agent, wherein 0.15g of the polymer chelating agent is contained in each milliliter of the ethanol;

the polymer chelant is a waterborne alkyd resin;

the volume ratio of ethanol to water in the ethanol-water mixed solution is 4: 1;

the additive is an acidic additive;

the acidic additive is a mixture of formic acid and oxalic acid, wherein the weight ratio of the formic acid to the oxalic acid is 4: 1.

the purchase was made in Shanghai Tongyun Industrial Co., Ltd; the waterborne alkyd resin is purchased from Nantong Runfeng petrochemical Co.

Comparative example 1

Comparative example 1 of the present invention specifically provides a preparation of nano-micro ions, which is the same as example 3, except that the volume ratio of ethanol to water is 1: 1.

comparative example 2

Comparative example 1 of the present invention specifically provides a preparation of nano-micro ions, which is the same as example 3, except that the volume ratio of ethanol to water is 6: 1.

comparative example 3

Comparative example 3 of the present invention specifically provides a preparation of nano-micro ions, which is the same as example 3, except that the volume ratio of ethanol to water is 2: 1.

comparative example 4

Comparative example 4 of the present invention specifically provides a preparation of nano-sized micro-ions, which is the same as example 3 except that no oxalic acid is used.

Performance testing

Adding the nano-particles prepared in the examples and the comparative examples into water, nano-SOD water, ethanol and methanol respectively, mixing and stirring uniformly, and then stabilizing for 30min to test the dispersion performance; the addition amount of the nano-micro particles is 25 percent of the weight of the system; evaluation criteria: the dispersing performance was scored by 5 experimenters experienced in the art with a full score of 100 and higher scores indicating better dispersing performance.

Wherein, the nanometer SOD water is obtained by mixing nanometer SOD and water, and the weight of the nanometer SOD in the water is 0.006-0.008%. The nanometer SOD is purchased from Shanghai Gu' an company, Inc.

The test results are shown in table 1:

TABLE 1

As can be seen from the test results in Table 1, the nano micro-ions provided by the invention have good dispersibility in water, especially in nano SOD water.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.