阅读说明：本技术 一种高分散度的纳米TiO2接枝丙烯酸树脂涂层及制备方法 (Nano TiO with high dispersity2Grafted acrylic resin coating and preparation method thereof ) 是由 何伯韬 于 2020-11-23 设计创作，主要内容包括：本发明涉及丙烯酸树脂技术领域,且公开了一种高分散度的纳米TiO_2接枝丙烯酸树脂涂层,在硫酸铜和抗坏血酸钠的协同催化作用下,使纳米TiO_2的叠氮官能团与丙烯酸树脂的侧链炔基官能团发生简单高效的点击反应,从而将纳米TiO_2共价接枝的丙烯酸树脂的分子链上,显著改善了纳米TiO_2与丙烯酸树脂的界面作用力和相容性,大幅提高了纳米TiO_2的分散性,克服了其团聚和聚集的现象,避免了团聚问题对丙烯酸树脂的机械性能和使用性能造成影响,高度分散的纳米TiO_2对丙烯酸树脂的抗紫外性具有很大的同时,从而提高了耐老化性能。(The invention relates to the technical field of acrylic resin, and discloses nano TiO with high dispersity 2 Grafting acrylic resin coating, under the synergistic catalytic action of copper sulfate and sodium ascorbate, making nano TiO 2 The azido functional group and the side chain alkynyl functional group of the acrylic resin are subjected to simple and efficient click reaction, so that the nano TiO is prepared 2 The molecular chain of the acrylic resin grafted covalently obviously improves the nano TiO 2 Interface acting force and compatibility with acrylic resin are greatly improved, and nano TiO is greatly improved 2 The dispersibility of the acrylic resin, the agglomeration and aggregation phenomena of the acrylic resin are overcome, the influence of the agglomeration problem on the mechanical property and the service performance of the acrylic resin is avoided, and the highly dispersed nano TiO 2 Has great ultraviolet resistance to acrylic resin, thereby improving the aging resistance.)

1. Nano TiO with high dispersity₂The grafted acrylic resin coating is characterized in that: the nano TiO with high dispersity₂The preparation method of the grafted acrylic resin coating comprises the following steps:

(1) adding toluene solvent and nano TiO into a conical flask₂Uniformly dispersing in an ultrasonic dispersion instrument, adding 3-bromopropyltrichlorosilane, stirring and reacting for 18-36h at 70-90 ℃ in a nitrogen atmosphere to obtain the bromo-nano TiO₂；

(2) Adding N, N-dimethylformamide solvent and bromine-based nano TiO into a conical flask₂Adding sodium azide after ultrasonic dispersion is uniform, stirring and reacting for 24-48h at 80-120 ℃ in nitrogen atmosphere to obtain the stackNitrided nano TiO₂；

(3) Adding a distilled water solvent, methyl methacrylate, n-butyl acrylate, acrylic acid, propinyl acrylate and an emulsifier sodium dodecyl sulfate into a conical flask, heating to 70-80 ℃, slowly dropwise adding a potassium persulfate solution, and stirring for reacting for 3-6h to obtain an acrylic resin emulsion with a side chain containing alkynyl;

(4) adding nitrified nano TiO into acrylic resin emulsion with side chain containing alkynyl₂Adding copper sulfate and sodium ascorbate after ultrasonic dispersion, reacting at 40-70 deg.C for 48-96 hr, and dispersing the product in distilled water solvent to obtain high-dispersity nanometer TiO₂Grafting acrylic resin coating solution, pouring the emulsion into a mould, defoaming in vacuum, and curing to form a film to obtain the nano TiO with high dispersity₂And (4) grafting an acrylic resin coating.

2. The high-dispersity nano TiO of claim 1₂The grafted acrylic resin coating is characterized in that: ultrasonic dispersion appearance includes ultrasonic transducer and ultrasonic probe, the inside ultrasonic chamber that is provided with of ultrasonic dispersion appearance, ultrasonic chamber below fixedly connected with bracing piece, bracing piece top and cardboard swing joint, the inside spiro that is provided with of cardboard, spiro swing joint have the screw rod, cardboard upper surface and spring fixed connection, spring top fixedly connected with objective table, the objective table top is provided with the erlenmeyer flask.

3. The high-dispersity nano TiO of claim 1₂The grafted acrylic resin coating is characterized in that: the nano TiO in the step (1)₂And 3-bromopropyltrichlorosilane in a mass ratio of 100: 5-15.

4. The high-dispersity nano TiO of claim 1₂The grafted acrylic resin coating is characterized in that: bromine-based nano TiO in the step (2)₂The mass ratio of the sodium azide to the sodium azide is 100: 20-60.

5. Root of herbaceous plantThe method of claim 1, wherein the nano TiO has a high degree of dispersion₂The grafted acrylic resin coating is characterized in that: the mass ratio of the methyl methacrylate, the n-butyl acrylate, the acrylic acid, the propinyl acrylate, the sodium dodecyl sulfate and the potassium persulfate in the step (3) is 100:30-40:3-6:0.2-0.8:5-10: 0.8-1.5.

6. The high-dispersity nano TiO of claim 1₂The grafted acrylic resin coating is characterized in that: the solid content in the acrylic resin emulsion with the side chain containing alkynyl in the step (4) and the nitridized nano TiO₂The mass ratio of the copper sulfate to the sodium ascorbate is 100:0.5-2:0.01-0.02: 0.03-0.06.

Technical Field

The invention relates to the technical field of acrylic resin, in particular to nano TiO with high dispersity₂A grafted acrylic resin coating and a preparation method thereof.

Background

The acrylic resin mainly comprises thermoplastic and thermosetting acrylic resin, has good fullness, hardness and solvent resistance, is simple in production process, low in production cost, good in environmental protection performance and high in transparency, can be used as materials such as coatings and adhesives, and has wide application in the aspects of fabric finishing, automobile manufacturing, leather industry and the like, but the traditional acrylic resin has low ultraviolet resistance, and the materials are easy to age due to long-term exposure to light, so that the use performance of the materials is influenced, and in order to further improve the comprehensive performances such as ultraviolet resistance, ageing resistance and the like of the acrylic resin and meet the requirements of industrial development, the acrylic resin needs to be modified and enhanced.

Titanium dioxide is a common semiconductor material, has a narrow forbidden band width, has an excellent absorption effect on ultraviolet light, and has extensive research and application in the aspects of ultraviolet absorption, photocatalytic degradation, antibiosis and the like.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides nano TiO with high dispersity₂The grafted acrylic resin coating and the preparation method solve the problem that the ultraviolet resistance and the aging resistance of the acrylic resin are poor.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: nano TiO with high dispersity₂Grafting acrylic resin coating: the nano TiO with high dispersity₂The preparation method of the grafted acrylic resin coating comprises the following steps:

(1) adding toluene solvent and nano TiO into a conical flask₂Dispersing in ultrasonic disperser, adding 3-brominePropyl trichlorosilane, stirring and reacting for 18-36h at 70-90 ℃ in nitrogen atmosphere, distilling under reduced pressure, washing and drying to obtain the bromine-based nano TiO₂。

(2) Adding N, N-dimethylformamide solvent and bromine-based nano TiO into a conical flask₂Adding sodium azide after ultrasonic dispersion is uniform, stirring and reacting for 24-48h at 80-120 ℃ in nitrogen atmosphere, centrifugally separating, washing and drying to prepare the nitrified nano TiO₂。

(3) Adding a distilled water solvent, methyl methacrylate, n-butyl acrylate, acrylic acid, propinyl acrylate and an emulsifier sodium dodecyl sulfate into a conical flask, heating to 70-80 ℃, slowly dropwise adding a potassium persulfate solution, and stirring for reacting for 3-6h to obtain the acrylic resin emulsion with the side chain containing alkynyl.

(4) Adding nitrified nano TiO into acrylic resin emulsion with side chain containing alkynyl₂Adding copper sulfate and sodium ascorbate after ultrasonic dispersion, reacting at 40-70 deg.C for 48-96 hr, centrifuging, purifying, and dispersing the product in distilled water solvent to obtain high-dispersity nanometer TiO₂Grafting acrylic resin coating solution, pouring the emulsion into a mould, defoaming in vacuum, and curing to form a film to obtain the nano TiO with high dispersity₂And (4) grafting an acrylic resin coating.

Preferably, the ultrasonic dispersion appearance includes ultrasonic transducer and ultrasonic probe, the inside ultrasonic chamber that is provided with of ultrasonic dispersion appearance, ultrasonic chamber below fixedly connected with bracing piece, bracing piece top and cardboard swing joint, the inside spiro that is provided with of cardboard, spiro swing joint have the screw rod, cardboard upper surface and spring fixed connection, spring top fixedly connected with objective table, the objective table top is provided with the erlenmeyer flask.

Preferably, the nano TiO in the step (1)₂And 3-bromopropyltrichlorosilane in a mass ratio of 100: 5-15.

Preferably, the bromine-based nano TiO in the step (2)₂The mass ratio of the sodium azide to the sodium azide is 100: 20-60.

Preferably, the mass ratio of the methyl methacrylate, the n-butyl acrylate, the acrylic acid, the propinyl acrylate, the sodium dodecyl sulfate and the potassium persulfate in the step (3) is 100:30-40:3-6:0.2-0.8:5-10: 0.8-1.5.

Preferably, the solid content in the acrylic resin emulsion with alkynyl contained in the side chain in the step (4) is mixed with the nano TiO azide₂The mass ratio of the copper sulfate to the sodium ascorbate is 100:0.5-2:0.01-0.02: 0.03-0.06.

Drawings

FIG. 1 is a schematic diagram of the structure of an ultrasonic apparatus;

FIG. 2 is an enlarged view of the card board structure;

fig. 3 is a schematic view of screw adjustment.

1-an ultrasonic instrument; 2-an ultrasonic transducer; 3-an ultrasonic probe; 4-an ultrasound chamber; 5-a support rod; 6-clamping plate; 7-spiro ring; 8-screw rod; 9-a spring; 10-an object stage; 11-conical flask.

(III) advantageous technical effects

Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:

the high-dispersity nano TiO₂Grafting an acrylic resin coating on the nano-TiO by 3-bromopropyltrichlorosilane₂Surface modification is carried out to obtain bromine-based nano TiO₂Bromine atom further reacts with sodium azide to obtain nitridized nano TiO₂Carrying out emulsion polymerization on monomers such as propargyl acrylate containing alkynyl and methyl methacrylate to obtain acrylic resin with alkynyl-containing side chains, and then enabling the nano TiO to be under the synergistic catalysis action of copper sulfate and sodium ascorbate₂The azido functional group and the side chain alkynyl functional group of the acrylic resin are subjected to simple and efficient click reaction, so that the nano TiO is prepared₂The molecular chain of the acrylic resin grafted covalently obviously improves the nano TiO₂Interface acting force and compatibility with acrylic resin are greatly improved, and nano TiO is greatly improved₂The dispersibility of the acrylic resin, the agglomeration and aggregation phenomena of the acrylic resin are overcome, the influence of the agglomeration problem on the mechanical property and the service performance of the acrylic resin is avoided, and the highly dispersed nano TiO₂Has great ultraviolet resistance to acrylic resin, thereby improving the aging resistance.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: nano TiO with high dispersity₂The preparation method of the grafted acrylic resin coating comprises the following steps:

(1) adding toluene solvent and nano TiO into a conical flask₂The ultrasonic dispersion instrument comprises an ultrasonic transducer and an ultrasonic probe, an ultrasonic chamber is arranged inside the ultrasonic dispersion instrument, a supporting rod is fixedly connected below the ultrasonic chamber, the upper part of the supporting rod is movably connected with a clamping plate, a spiral ring is arranged inside the clamping plate, a screw rod is movably connected with the spiral ring, the upper surface of the clamping plate is fixedly connected with a spring, an objective table is fixedly connected above the spring, a conical bottle is arranged above the objective table, 3-bromopropyltrichlorosilane is added, and the nanometer TiO trichlorosilane are uniformly dispersed₂The mass ratio of the bromine-based nano TiO is 5-15:100, the mixture is stirred and reacted for 18-36h at the temperature of 70-90 ℃ in the nitrogen atmosphere, and the bromine-based nano TiO is prepared by reduced pressure distillation, washing and drying₂。

(2) Adding N, N-dimethylformamide solvent and bromine-based nano TiO into a conical flask₂Adding sodium azide in a mass ratio of 100:20-60 after ultrasonic dispersion is uniform, stirring and reacting for 24-48h at 80-120 ℃ in a nitrogen atmosphere, centrifugally separating, washing and drying to obtain the nitrified nano TiO₂。

(3) Adding a distilled water solvent, methyl methacrylate, n-butyl acrylate, acrylic acid, propinyl acrylate and an emulsifier sodium dodecyl sulfate into a conical flask, heating to 70-80 ℃, slowly dropwise adding a potassium persulfate solution, wherein the mass ratio of the methyl methacrylate, the n-butyl acrylate, the acrylic acid, the propinyl acrylate, the sodium dodecyl sulfate and the potassium persulfate is 100:30-40:3-6:0.2-0.8:5-10:0.8-1.5, and stirring for reaction for 3-6h to obtain the acrylic resin emulsion with the side chain containing alkynyl.

(4) Adding nitrified nano TiO into acrylic resin emulsion with side chain containing alkynyl₂Adding copper sulfate and sodium ascorbate after ultrasonic dispersion, wherein the side chain contains solid content in alkynyl acrylic resin emulsion and azide nano TiO₂The mass ratio of the copper sulfate to the sodium ascorbate is 100:0.5-2:0.01-0.02:0.03-0.06, the mixture reacts for 48-96h at the temperature of 40-70 ℃, the centrifugal separation is carried out for purification, the product is dispersed in a distilled water solvent to obtain the nano TiO with high dispersion degree₂Grafting acrylic resin coating solution, pouring the emulsion into a mould, defoaming in vacuum, and curing to form a film to obtain the nano TiO with high dispersity₂And (4) grafting an acrylic resin coating.

Example 1

(1) Adding toluene solvent and nano TiO into a conical flask₂The ultrasonic dispersion instrument comprises an ultrasonic transducer and an ultrasonic probe, an ultrasonic chamber is arranged inside the ultrasonic dispersion instrument, a supporting rod is fixedly connected below the ultrasonic chamber, the upper part of the supporting rod is movably connected with a clamping plate, a spiral ring is arranged inside the clamping plate, a screw rod is movably connected with the spiral ring, the upper surface of the clamping plate is fixedly connected with a spring, an objective table is fixedly connected above the spring, a conical bottle is arranged above the objective table, 3-bromopropyltrichlorosilane is added, and the nanometer TiO trichlorosilane are uniformly dispersed₂The mass ratio of the bromine-based nano TiO is 5:100, the mixture is stirred and reacted for 18 hours at 70 ℃ in the nitrogen atmosphere, and the bromine-based nano TiO is prepared by reduced pressure distillation, washing and drying₂。

(2) Adding N, N-dimethylformamide solvent and bromine-based nano TiO into a conical flask₂Adding sodium azide in a mass ratio of 100:20 after ultrasonic dispersion is uniform, stirring and reacting for 24 hours at 80 ℃ in a nitrogen atmosphere, centrifugally separating, washing and drying to obtain the nitrified nano TiO₂。

(3) Adding a distilled water solvent, methyl methacrylate, n-butyl acrylate, acrylic acid, propinyl acrylate and an emulsifier sodium dodecyl sulfate into a conical flask, heating to 70 ℃, slowly dropwise adding a potassium persulfate solution, wherein the mass ratio of the methyl methacrylate to the n-butyl acrylate to the acrylic acid to the propinyl acrylate to the sodium dodecyl sulfate to the potassium persulfate is 100:30:3:0.2:5:0.8, and stirring for reacting for 3 hours to obtain the acrylic resin emulsion with the side chain containing alkynyl.

(4) Adding nitrified nano TiO into acrylic resin emulsion with side chain containing alkynyl₂Adding copper sulfate after ultrasonic dispersionAnd sodium ascorbate, wherein the side chain contains solid content in alkynyl acrylic resin emulsion and azide nano TiO₂The mass ratio of the copper sulfate to the sodium ascorbate is 100:0.5:0.01:0.03, the mixture reacts for 48 hours at the temperature of 40 ℃, the centrifugal separation is carried out for purification, and the product is dispersed in a distilled water solvent to obtain the nano TiO with high dispersion degree₂Grafting acrylic resin coating solution, pouring the emulsion into a mould, defoaming in vacuum, and curing to form a film to obtain the nano TiO with high dispersity₂And (4) grafting an acrylic resin coating.

Example 2

(1) Adding toluene solvent and nano TiO into a conical flask₂The ultrasonic dispersion instrument comprises an ultrasonic transducer and an ultrasonic probe, an ultrasonic chamber is arranged inside the ultrasonic dispersion instrument, a supporting rod is fixedly connected below the ultrasonic chamber, the upper part of the supporting rod is movably connected with a clamping plate, a spiral ring is arranged inside the clamping plate, a screw rod is movably connected with the spiral ring, the upper surface of the clamping plate is fixedly connected with a spring, an objective table is fixedly connected above the spring, a conical bottle is arranged above the objective table, 3-bromopropyltrichlorosilane is added, and the nanometer TiO trichlorosilane are uniformly dispersed₂The mass ratio of (1) to (2) is 8:100, the mixture is stirred and reacted for 36 hours at the temperature of 90 ℃ in the nitrogen atmosphere, and the bromine-based nano TiO is prepared by reduced pressure distillation, washing and drying₂。

(2) Adding N, N-dimethylformamide solvent and bromine-based nano TiO into a conical flask₂Adding sodium azide at the mass ratio of 100:30 after ultrasonic dispersion is uniform, stirring and reacting for 24 hours at 100 ℃ in nitrogen atmosphere, centrifugally separating, washing and drying to obtain the nitrified nano TiO₂。

(3) Adding a distilled water solvent, methyl methacrylate, n-butyl acrylate, acrylic acid, propinyl acrylate and an emulsifier sodium dodecyl sulfate into a conical flask, heating to 70 ℃, slowly dropwise adding a potassium persulfate solution, wherein the mass ratio of the methyl methacrylate to the n-butyl acrylate to the acrylic acid to the propinyl acrylate to the sodium dodecyl sulfate to the potassium persulfate is 100:33:4:0.4:6:1, and stirring for reacting for 6 hours to obtain the acrylic resin emulsion with the side chain containing alkynyl.

(4) Containing alkynyl radicals in side chainsAdding nitridized nano TiO into the acrylic resin emulsion₂Adding copper sulfate and sodium ascorbate after ultrasonic dispersion, wherein the side chain contains solid content in alkynyl acrylic resin emulsion and azide nano TiO₂The mass ratio of copper sulfate to sodium ascorbate is 100:1:0.012:0.04, the mixture reacts for 48 hours at 70 ℃, the centrifugal separation is carried out for purification, and the product is dispersed in a distilled water solvent to obtain the nano TiO with high dispersion degree₂Grafting acrylic resin coating solution, pouring the emulsion into a mould, defoaming in vacuum, and curing to form a film to obtain the nano TiO with high dispersity₂And (4) grafting an acrylic resin coating.

Example 3

(1) Adding toluene solvent and nano TiO into a conical flask₂The ultrasonic dispersion instrument comprises an ultrasonic transducer and an ultrasonic probe, an ultrasonic chamber is arranged inside the ultrasonic dispersion instrument, a supporting rod is fixedly connected below the ultrasonic chamber, the upper part of the supporting rod is movably connected with a clamping plate, a spiral ring is arranged inside the clamping plate, a screw rod is movably connected with the spiral ring, the upper surface of the clamping plate is fixedly connected with a spring, an objective table is fixedly connected above the spring, a conical bottle is arranged above the objective table, 3-bromopropyltrichlorosilane is added, and the nanometer TiO trichlorosilane are uniformly dispersed₂The mass ratio of the bromine-based nano TiO is 12:100, the mixture is stirred and reacted for 24 hours at the temperature of 80 ℃ in the nitrogen atmosphere, and the bromine-based nano TiO is prepared by reduced pressure distillation, washing and drying₂。

(2) Adding N, N-dimethylformamide solvent and bromine-based nano TiO into a conical flask₂Adding sodium azide in a mass ratio of 100:45 after ultrasonic dispersion is uniform, stirring and reacting for 36 hours at 100 ℃ in a nitrogen atmosphere, centrifugally separating, washing and drying to obtain the nitrified nano TiO₂。

(3) Adding a distilled water solvent, methyl methacrylate, n-butyl acrylate, acrylic acid, propinyl acrylate and an emulsifier sodium dodecyl sulfate into a conical flask, heating to 75 ℃, slowly dropwise adding a potassium persulfate solution, wherein the mass ratio of the methyl methacrylate to the n-butyl acrylate to the acrylic acid to the propinyl acrylate to the sodium dodecyl sulfate to the potassium persulfate is 100:38:5:0.6:8:1.2, and stirring for reacting for 4 hours to obtain the acrylic resin emulsion with the side chain containing alkynyl.

(4) Adding nitrified nano TiO into acrylic resin emulsion with side chain containing alkynyl₂Adding copper sulfate and sodium ascorbate after ultrasonic dispersion, wherein the side chain contains solid content in alkynyl acrylic resin emulsion and azide nano TiO₂The mass ratio of the copper sulfate to the sodium ascorbate is 100:1.5:0.016:0.05, the mixture reacts for 72 hours at the temperature of 60 ℃, the centrifugal separation is carried out for purification, and the product is dispersed in a distilled water solvent to obtain the nano TiO with high dispersion degree₂Grafting acrylic resin coating solution, pouring the emulsion into a mould, defoaming in vacuum, and curing to form a film to obtain the nano TiO with high dispersity₂And (4) grafting an acrylic resin coating.

Example 4

(1) Adding toluene solvent and nano TiO into a conical flask₂The ultrasonic dispersion instrument comprises an ultrasonic transducer and an ultrasonic probe, an ultrasonic chamber is arranged inside the ultrasonic dispersion instrument, a supporting rod is fixedly connected below the ultrasonic chamber, the upper part of the supporting rod is movably connected with a clamping plate, a spiral ring is arranged inside the clamping plate, a screw rod is movably connected with the spiral ring, the upper surface of the clamping plate is fixedly connected with a spring, an objective table is fixedly connected above the spring, a conical bottle is arranged above the objective table, 3-bromopropyltrichlorosilane is added, and the nanometer TiO trichlorosilane are uniformly dispersed₂The mass ratio of (1) to (2) is 15:100, stirring and reacting for 36h at 90 ℃ in nitrogen atmosphere, carrying out reduced pressure distillation, washing and drying to obtain the bromine-based nano TiO₂。

(2) Adding N, N-dimethylformamide solvent and bromine-based nano TiO into a conical flask₂Adding sodium azide in a mass ratio of 100:60 after ultrasonic dispersion is uniform, stirring and reacting for 48 hours at 120 ℃ in a nitrogen atmosphere, centrifugally separating, washing and drying to obtain the nitrified nano TiO₂。

(3) Adding a distilled water solvent, methyl methacrylate, n-butyl acrylate, acrylic acid, propinyl acrylate and an emulsifier sodium dodecyl sulfate into a conical flask, heating to 80 ℃, slowly dropwise adding a potassium persulfate solution, wherein the mass ratio of the methyl methacrylate to the n-butyl acrylate to the acrylic acid to the propinyl acrylate to the sodium dodecyl sulfate to the potassium persulfate is 100:40:6:0.8:10:1.5, and stirring for reacting for 6 hours to obtain the acrylic resin emulsion with the side chain containing alkynyl.

(4) Adding nitrified nano TiO into acrylic resin emulsion with side chain containing alkynyl₂Adding copper sulfate and sodium ascorbate after ultrasonic dispersion, wherein the side chain contains solid content in alkynyl acrylic resin emulsion and azide nano TiO₂The mass ratio of copper sulfate to sodium ascorbate is 100:2:0.02:0.06, the mixture reacts for 96 hours at the temperature of 70 ℃, the centrifugal separation is carried out for purification, and the product is dispersed in a distilled water solvent to obtain the nano TiO with high dispersity₂Grafting acrylic resin coating solution, pouring the emulsion into a mould, defoaming in vacuum, and curing to form a film to obtain the nano TiO with high dispersity₂And (4) grafting an acrylic resin coating.

Comparative example 1

(1) Adding toluene solvent and nano TiO into a conical flask₂The ultrasonic dispersion instrument comprises an ultrasonic transducer and an ultrasonic probe, an ultrasonic chamber is arranged inside the ultrasonic dispersion instrument, a supporting rod is fixedly connected below the ultrasonic chamber, the upper part of the supporting rod is movably connected with a clamping plate, a spiral ring is arranged inside the clamping plate, a screw rod is movably connected with the spiral ring, the upper surface of the clamping plate is fixedly connected with a spring, an objective table is fixedly connected above the spring, a conical bottle is arranged above the objective table, 3-bromopropyltrichlorosilane is added, and the nanometer TiO trichlorosilane are uniformly dispersed₂The mass ratio of the bromine-based nano TiO is 2:100, the mixture is stirred and reacted for 18 hours at the temperature of 90 ℃ in the nitrogen atmosphere, and the bromine-based nano TiO is prepared by reduced pressure distillation, washing and drying₂。

(2) Adding N, N-dimethylformamide solvent and bromine-based nano TiO into a conical flask₂Adding sodium azide with the mass ratio of 100:10 after ultrasonic dispersion is uniform, stirring and reacting for 36 hours at 100 ℃ in nitrogen atmosphere, centrifugally separating, washing and drying to prepare the nano TiO azide₂。

(3) Adding a distilled water solvent, methyl methacrylate, n-butyl acrylate, acrylic acid, propinyl acrylate and an emulsifier sodium dodecyl sulfate into a conical flask, heating to 80 ℃, slowly dropwise adding a potassium persulfate solution, wherein the mass ratio of the methyl methacrylate to the n-butyl acrylate to the acrylic acid to the propinyl acrylate to the sodium dodecyl sulfate to the potassium persulfate is 100:25:2:0.1:3.5:0.6, and stirring for reacting for 6 hours to obtain the acrylic resin emulsion with the side chain containing alkynyl.

(4) Adding nitrified nano TiO into acrylic resin emulsion with side chain containing alkynyl₂Adding copper sulfate and sodium ascorbate after ultrasonic dispersion, wherein the side chain contains solid content in alkynyl acrylic resin emulsion and azide nano TiO₂The mass ratio of the copper sulfate to the sodium ascorbate is 100:0.2:0.008:0.02, the reaction is carried out for 72 hours at the temperature of 60 ℃, the centrifugal separation is carried out for purification, the product is dispersed in a distilled water solvent, and the nano TiO with high dispersity is obtained₂Grafting acrylic resin coating solution, pouring the emulsion into a mould, defoaming in vacuum, and curing to form a film to obtain the nano TiO with high dispersity₂And (4) grafting an acrylic resin coating.

High dispersion of nano TiO was tested using 5W UV as the light source₂The ultraviolet transmittance of the grafted acrylic resin coating is measured by GB/T18950-2003.