阅读说明：本技术 一种高分散性紫外屏蔽剂及其制备方法和应用 (High-dispersity ultraviolet shielding agent and preparation method and application thereof ) 是由 王斌 马祥梅 董哲昊 刘义星 于 2021-08-26 设计创作，主要内容包括：本发明公开了一种高分散性紫外屏蔽剂及其制备方法和应用,属于复合材料技术领域。该高分散性紫外屏蔽剂制备方法包括以下步骤：将纳米ZnO和H-(2)O-(2)溶液混合并反应,得到ZnO-OH,将ZnO-OH与无水乙醇混合并反应,之后加入3-氨丙基三乙氧基硅烷并反应,得到ZnO-NH-(2),将间苯二酚二缩水甘油醚溶于N,N-二甲基甲酰胺,之后加入所述ZnO-NH-(2)超声分散并反应制得高分散性紫外屏蔽剂。通过上述方法制备的紫外屏蔽剂具有在高分子基材中分散性好、紫外线屏蔽效率高、能够有效抑制纳米ZnO光催化作用的优点,制备方法简单,适合大规模生产。(The invention discloses a high-dispersity ultraviolet shielding agent and a preparation method and application thereof, and belongs to the technical field of composite materials. The preparation method of the high-dispersity ultraviolet shielding agent comprises the following steps: nano ZnO and H 2 O 2 Mixing the solutions and reacting to obtain ZnO-OH, mixing ZnO-OH with anhydrous ethanol and reacting, adding 3-aminopropyl triethoxysilane and reacting to obtain ZnO-NH 2 Dissolving resorcinol diglycidyl ether in N, N-bisMethyl formamide, followed by addition of the ZnO-NH 2 And (4) carrying out ultrasonic dispersion and reaction to obtain the high-dispersity ultraviolet shielding agent. The ultraviolet shielding agent prepared by the method has the advantages of good dispersibility in a high-molecular base material, high ultraviolet shielding efficiency and capability of effectively inhibiting the photocatalysis of nano ZnO, and the preparation method is simple and suitable for large-scale production.)

1. The preparation method of the high-dispersity ultraviolet shielding agent is characterized in that H is used₂O₂The solution is an oxidant and reacts with nano ZnO to obtain ZnO-OH; carrying out amination reaction on the ZnO-OH and 3-aminopropyltriethoxysilane to obtain ZnO-NH₂Introducing said ZnO-NH₂Reacting with resorcinol diglycidyl ether to obtain the high-dispersity ultraviolet shielding agent ZnO-Ph.

2. The preparation method according to claim 1, comprising the following steps:

nano ZnO and H₂O₂Mixing the solution, stirring, centrifuging, washing, drying to obtain ZnO-OH, mixing ZnO-OH with anhydrous ethanol, adding 3-aminopropyltriethoxysilane, stirring, centrifuging, washing, drying to obtain ZnO-NH₂Dissolving resorcinol diglycidyl ether in N, N-dimethylformamide, and adding the ZnO-NH₂Ultrasonic dispersion, stirring, cooling at normal temperature, centrifuging, washing and drying to obtain the high-dispersity ultraviolet shielding agent.

3. The method of claim 1, wherein the H is₂O₂The mass percentage of the solution is 30 wt%, the grain diameter of the nano ZnO is 30 +/-10 nm, and the nano ZnO and the H are₂O₂The feed-liquid ratio of the solution is 1 g: 50 mL.

4. The preparation method according to claim 1, wherein the mass-to-volume ratio of ZnO-OH to 3-aminopropyltriethoxysilane is 1 g: 5 mL.

5. The method according to claim 1, wherein the mass-to-volume ratio of the resorcinol diglycidyl ether to the N, N-dimethylformamide is 1 g: 30 mL.

6. The method according to claim 1, wherein the resorcinol diglycidyl ether is reacted with ZnO-NH₂The mass ratio of (1): (0.2-0.6).

7. The preparation method according to claim 1, wherein the mass-to-volume ratio of ZnO-OH to absolute ethyl alcohol is 1 g: 50 mL.

8. A highly dispersible ultraviolet screening agent prepared by the method of any one of claims 1 to 7.

9. An ultraviolet shielding composite film comprising the highly dispersible ultraviolet shielding agent of claim 8, which is prepared by the following steps: mixing the high-dispersity ultraviolet shielding agent with a polymer material solution at room temperature, uniformly dispersing by ultrasonic to obtain a film forming solution, defoaming the film forming solution, carrying out tape casting on a flat plate to form a film, standing in air for forming, carrying out vacuum drying, and stripping to obtain an ultraviolet shielding composite film; the flat plate is a glass flat plate.

10. The use of the highly dispersible uv screening agent of claim 8 in automotive windows, architectural windows and doors, packaging protective materials.

Technical Field

The invention relates to a high-dispersity ultraviolet shielding agent and a preparation method and application thereof, belonging to the technical field of composite materials.

Background

The main source of ultraviolet is the sun, and it can shine through the atmosphere on ground, and ultraviolet has the effect such as can make film sensitization, disinfection, and widely used in fields such as hospital, biological assay, but long-time exposure can cause compound material's ageing, sclerosis, fracture scheduling problem under the ultraviolet radiation, and then influences the life of material, so provide a compound material that resists ultraviolet and be a technical problem that needs to solve now urgently.

As a novel semiconductor material, nano ZnO is nontoxic and tasteless, good in stability and high in transparency, has extremely strong ultraviolet shielding capability in UVB (medium wave ultraviolet) and UVA (long wave ultraviolet) regions, and has the characteristics of large specific surface area, high chemical activity, low melting point, lower densification temperature and the like, so that the nano ZnO is used as an ultraviolet shielding agent, but because the nano ZnO has large specific surface area, the nano ZnO has poor compatibility with a high polymer base material in the process of preparing the ultraviolet shielding material, and has the defects of easy agglomeration, difficult dispersion and the like, and the photocatalytic activity of the nano ZnO is activated under the action of ultraviolet rays, so that a photocatalytic side reaction is initiated, the service life of the ultraviolet shielding material is further shortened, currently, many researches are carried out to obtain high-quality nano ZnO by strictly controlling various conditions in the preparation process of the nano ZnO, and the oxidative degradation of the nano ZnO is reduced by adding part of film forming substances, or the surface of the nano ZnO particles is modified by adding the surfactant, but the application range of the nano ZnO is limited to a certain extent due to the defects of harsh preparation conditions, high cost, complex process, high industrialization difficulty, complex subsequent modification operation and the like of the nano ZnO, so that the preparation method is simple, is suitable for industrial production, can realize nano-scale dispersion of the nano ZnO in an organic base material, can effectively inhibit the photocatalysis of the nano ZnO, and is the key for preparing the high-performance ultraviolet-resistant application material.

Disclosure of Invention

In order to solve the technical problems, the invention provides the high-dispersity ultraviolet screening agent and the preparation method and application thereof.

In order to achieve the purpose, the invention provides the following scheme:

the invention provides a preparation method of a high-dispersity ultraviolet shielding agent, which is prepared from H₂O₂The solution is an oxidant and reacts with nano ZnO to obtain ZnO-OH; carrying out amination reaction on the ZnO-OH and 3-Aminopropyltriethoxysilane (APTES) to obtain ZnO-NH₂Introducing said ZnO-NH₂And reacting with resorcinol diglycidyl ether (RDGE) to obtain the high-dispersity ultraviolet shielding agent ZnO-Ph.

Further, the method specifically comprises the following steps:

nano ZnO and H₂O₂Mixing the solutions, performing ultrasonic-assisted stirring reaction at room temperature for 4h, centrifuging, washing, drying to obtain ZnO-OH, mixing ZnO-OH with anhydrous ethanol, performing ultrasonic dispersion, adding 3-Aminopropyltriethoxysilane (APTES), stirring at 80 deg.C for 12h, centrifuging, washing, and drying to obtain ZnO-NH₂Dissolving resorcinol diglycidyl ether (RDGE) in N, N-Dimethylformamide (DMF), and adding the ZnO-NH₂Uniformly dispersing by ultrasonic, stirring, heating, reacting for 4h, cooling at normal temperature, centrifuging, washing, and drying to obtain the high-dispersibility ultraviolet shielding agent (ZnO-Ph).

Further, 20% of ethanol water solution is used for washing.

Further, said H₂O₂The mass percentage of the solution is 30 wt%, the grain diameter of the nano ZnO is 30 +/-10 nm, and the nano ZnO and the H are₂O₂The feed-liquid ratio of the solution is 1 g: 50 mL.

Further, the mass-to-volume ratio of the ZnO-OH to the 3-Aminopropyltriethoxysilane (APTES) is 1 g: 5 mL.

Further, the mass-to-volume ratio of resorcinol diglycidyl ether (RDGE) to N, N-Dimethylformamide (DMF) is 1 g: 30 mL.

Further, the resorcinol diglycidyl ether (RDGE) and ZnO-NH₂The mass ratio of (1): (0.2-0.6).

Further, the mass-volume ratio of the ZnO-OH to the absolute ethyl alcohol is 1 g: 50 mL.

The invention also provides the high-dispersity ultraviolet screening agent prepared by the preparation method.

The invention also provides an ultraviolet shielding composite film comprising the high-dispersity ultraviolet shielding agent, and the ultraviolet shielding composite film is prepared by the following steps:

and ultrasonically dispersing the high-dispersity ultraviolet shielding agent (ZnO-Ph) in a solvent for dissolving a base material, mixing the high-dispersity ultraviolet shielding agent (ZnO-Ph) with a solution in which a high-molecular base material is dissolved at room temperature, stirring and uniformly ultrasonically dispersing to obtain a film forming solution, forming a film on a flat plate after the film forming solution is defoamed, standing in air for forming, drying in vacuum to constant weight, and stripping to obtain the ultraviolet shielding composite film.

Further, the flat plate is a glass flat plate.

The invention also provides application of the high-dispersity ultraviolet screening agent in automobile windows, building doors and windows and packaging protective materials.

The invention discloses the following technical effects:

1) the invention adopts green environmental protection type oxidant H₂O₂Aqueous solution oxidation of nano ZnO particles by H₂O₂The water solution increases the number of hydroxyl groups participating in the modification reaction on the surface of the nano ZnO particles, and the nano ZnO particles are mutually connected through the hydroxyl groups to form a hydroxyl bridge network structure, thereby achieving the purpose of reducing the overall energyThe purpose of stable existence is to accelerate the reaction speed with 3-Aminopropyltriethoxysilane (APTES), the 3-Aminopropyltriethoxysilane (APTES) introduces Si-O bond with ultraviolet shielding performance and amino functional group required by modification of nano ZnO particles, the agglomeration performance of the ZnO nano particles is reduced, and the existence of a silane layer can inhibit the photocatalysis of ZnO to improve the weather resistance of the base material.

2) The amino group introduced by the 3-aminopropyl triethoxysilane (APTES) silane layer reacts with the epoxy part of resorcinol diglycidyl ether (RDGE) to introduce an organic group containing a benzene ring, and the organic group containing the benzene ring has strong oleophylic characteristics, so that the compatibility of the organic group and a polymer during blending is improved, and the problem of uneven dispersion of nano ZnO in a base material is effectively solved. Meanwhile, the pi bond structure of the benzene ring enhances the ultraviolet absorption capacity of the shielding agent, the epoxy ring open loop reaction generates N-H and O-H bonds, and the energy irradiated by ultraviolet light can be converted into lower vibration energy through the intramolecular hydrogen bond action between the epoxy ring open loop reaction and the N-H and O-H bonds, so that the energy is dissipated, and the synergistic effect of the organic-inorganic composite ultraviolet shielding agent is better exerted.

3) The nano ZnO used in the invention is nontoxic, has stable property after the action of 3-aminopropyl triethoxysilane (APTES) and resorcinol diglycidyl ether (RDGE), has cheap and easily obtained preparation raw materials, and is simple in preparation method and suitable for large-scale production.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.

FIG. 1 is a scanning electron micrograph of the prepared composite film S1 (2%)/PVC;

FIG. 2 is a scanning electron microscope image of ZnO-OH (2%)/PVC of the prepared composite film;

FIG. 3 shows the prepared composite film ZnO-NH₂(2%)/PVC scanning Electron microscopy;

FIG. 4 is a diagram of the UV shielding performance of the composite film when different nanoparticles account for 2% of the mass of PVC;

FIG. 5 is a diagram of the ultraviolet shielding performance of S1/PVC composite films with different S1 contents.

Detailed Description

Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.

As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.

The materials referred to in the examples of the present invention are well known and commonly used, and may be purchased conventionally, unless otherwise specified.

The technical solution of the present invention is further illustrated by the following examples.

Example 1

3g of nano ZnO (particle size of 30 +/-10 nm) and 150mL of H₂O₂Mixing the solutions (with the mass fraction of 30 wt.%), carrying out ultrasonic-assisted reaction for 4 hours, then continuing stirring and reacting at room temperature for 12 hours, centrifuging, washing with an ethanol water solution with the mass fraction of 20%, and drying to obtain ZnO-OH;

mixing 1g of ZnO-OH and 50mL of absolute ethanol, adding 5mL of 3-Aminopropyltriethoxysilane (APTES) after uniform ultrasonic dispersion, continuing to perform ultrasonic dispersion until uniform dispersion is achieved, stirring and reacting for 12 hours at 80 ℃, washing with 20 mass percent ethanol aqueous solution after centrifugation, and drying to obtain ZnO-NH₂；

Dissolving 1g resorcinol diglycidyl ether (RDGE) in 30mL N, N-Dimethylformamide (DMF), mixing well, adding 0.4g nano ZnO-NH₂And (3) uniformly dispersing the particles by ultrasonic, stirring and reacting for 4h at 50 ℃, cooling, centrifuging, washing and drying to obtain the high-dispersity ultraviolet screening agent (ZnO-Ph) which is marked as S1.

Example 2

The only difference from example 1 is that 1g of resorcinol diglycidyl ether (RDGE) was dissolved in 30mL of N, N-Dimethylformamide (DMF), mixed well, and 0.6g of nano ZnO-NH was added₂Particles. A highly dispersible UV screening agent (ZnO-Ph) was obtained and is designated S2.

Example 3

The only difference from example 1 is that 1g of resorcinol diglycidyl ether (RDGE) was dissolved in 30mL of N, N-Dimethylformamide (DMF), mixed well, and 0.2g of nano ZnO-NH was added₂Particles. A highly dispersible UV screening agent (ZnO-Ph) was obtained and is designated S3.

Preparation of ultraviolet shielding composite film (polyvinyl chloride PVC as high molecular base material)

Nano ZnO and ZnO-OH and ZnO-NH obtained in example 1₂And S1, S2 and S3 are respectively taken as nano particles, the addition amount of the nano particles is 2% of the PVC dosage, S1 is taken as nano particles, the addition amount of the nano particles is 0.3%, 0.5%, 0.8% and 1% of the PVC dosage, a certain amount of nano particles and PVC are weighed according to the conditions, PVC powder is slowly added into a DMF solution under the condition of stirring at room temperature, a certain amount of nano particles are dissolved in DMF, after ultrasonic dispersion treatment is carried out for 1h, the nano particles and the DMF solution dissolved with the PVC are stirred for 2h at room temperature and then are ultrasonically mixed and dispersed for 0.5h, a film forming solution is obtained after uniform dispersion, then a film is formed on a glass flat plate, standing forming is carried out in air, stripping is carried out after vacuum drying, and the ultraviolet shielding composite film with the thickness of 50 micrometers can be obtained.

Performing electron microscope scanning on the prepared composite film, wherein an electron microscope scanning picture of S1 (2%)/PVC (the addition amount of ZnO-Ph in example 1 is 2% of the PVC dosage) is shown in figure 1, an electron microscope scanning picture of ZnO-OH (2%)/PVC of the composite film is shown in figure 2, and the composite film ZnO-NH is shown in figure 2₂The (2%)/PVC scanning electron micrograph is shown in figure 3, and it can be seen that the nanoparticles in the composite film S1 (2%)/PVC hardly undergo agglomeration, and the dispersibility is obviously superior to that of ZnO-OH (2%)/PVC and ZnO-NH₂(2%)/nanoparticles in PVC.

Ultraviolet shielding performance test of each composite film group

50mL of RhB (rhodamine B) solution (10) is taken^-5M) and 50mg of UV-photocatalyst TiO₂Mix in a beaker and magnetically stir for 30min away from light to allow for equilibrium adsorption.

Covering the prepared PVC composite membrane as an ultraviolet shielding membrane on the mouths of the beakers respectively, vertically irradiating the RhB solution right above an ultraviolet lamp (20w, 365nm wavelength), stirring and radiating the RhB solution at room temperature, taking 6mL of solution from the beakers respectively when the ultraviolet lamp is radiated for 20min, 40 min, 60 min, 80 min, 100 min and 120min, centrifuging the solution, taking the supernatant for absorbance test, and recording ultraviolet spectrograms; and after the test is finished, the solution is recovered, centrifugally dispersed uniformly and poured back to the beaker for the next time period of irradiation, and the steps are repeated for each measurement.

The ultraviolet light shielding ability of the ultraviolet light shielding film passes (A)_t/A₀) Comparison of changes in% A₀To representAbsorbance at 554nm of RhB initially irradiated with UV light, A_tIndicates the absorbance at 554nm of RhB irradiated by ultraviolet rays under the protection of the film. The ultraviolet shielding performance of the composite film when different nano particles account for 2% of the mass of PVC is shown in figure 4, and the ultraviolet shielding performance of the S1/PVC composite film with different S1 contents is shown in figure 5.

From the test results of fig. 4 and 5, it can be seen that the ultraviolet absorber prepared by using nano zinc oxide has good dispersibility in the polymer base material, and the ultraviolet shielding effect is obviously enhanced, and the effective shielding of ultraviolet can be realized by adjusting the content of the ultraviolet shielding agent.

The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.