阅读说明：本技术 一种高耐候钢结构水性丙烯酸树脂的制备方法 (Preparation method of high-weather-resistance steel structure water-based acrylic resin ) 是由 李维格 于 2021-01-13 设计创作，主要内容包括：本发明适用材料技术领域,提供了一种高耐候钢结构水性丙烯酸树脂的制备方法,高耐候钢结构水性丙烯酸树脂包括以下原料：复配溶剂、丙烯酸、丙烯酸酯、改性卤氧化铋微球、叔碳酸乙烯酯、含羟基甲基丙烯酸酯、甲基丙烯酸月桂酸酯、甲基丙烯酸甲酯、偶联剂、链转移剂、引发剂、中和剂；本发明实施例提供的高耐候钢结构水性丙烯酸树脂膜面透明光亮、平整,有着良好的耐水性、耐候性以及耐腐蚀性,提高了表面硬度,并保持高抗冲击性以及高韧性,卤氧化铋是由纳米级别的纳米片自组装形成的具有花簇结构的微球,改性后与其他组分相互协同,可增强表面自清洁能力,提高了耐水性、耐腐蚀性和耐候性,值得推广。(The invention is applicable to the technical field of materials, and provides a preparation method of high weather-resistant steel structure water-based acrylic resin, which comprises the following raw materials: the preparation method comprises the following steps of compounding a solvent, acrylic acid, acrylic ester, modified bismuth oxyhalide microspheres, vinyl versatate, hydroxyl-containing methacrylate, lauryl methacrylate, methyl methacrylate, a coupling agent, a chain transfer agent, an initiator and a neutralizer; the high weather-resistant steel structure water-based acrylic resin provided by the embodiment of the invention has a transparent, bright and flat film surface, good water resistance, weather resistance and corrosion resistance, improves the surface hardness, keeps high impact resistance and high toughness, is a microsphere with a flower cluster structure formed by self-assembling nano-scale nano-sheets, is modified and mutually cooperated with other components, can enhance the surface self-cleaning capability, improves the water resistance, the corrosion resistance and the weather resistance, and is worthy of popularization.)

1. The high weather-resistant steel structure water-based acrylic resin is characterized by comprising the following raw materials in parts by weight: 10-16 parts of a compound solvent, 6-12 parts of acrylic acid, 15-25 parts of acrylate, 15-23 parts of modified bismuth oxyhalide microspheres, 2-10 parts of vinyl versatate, 30-38 parts of hydroxyl-containing methacrylate, 6-12 parts of methacrylic laurate, 8-14 parts of methyl methacrylate, 2-7 parts of a coupling agent, 1-3 parts of a chain transfer agent, 2-5 parts of an initiator and 2-6 parts of a neutralizer;

the preparation method of the modified bismuth oxyhalide microspheres comprises the following steps: pouring 25ml of glacial acetic acid and 0.1mol of bismuth nitrate into 35ml of distilled water, stirring and mixing, slowly pouring a solution of 25wt% of hexadecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium chloride while stirring, adding 3 x 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at 25 ℃ for 10min, filtering, vacuum-drying at 60 ℃ for 24h, grinding to obtain bismuth oxyhalide microspheres, mixing each gram of bismuth oxyhalide microspheres with 10ml of n-hexane, stirring for 30min to obtain uniformly dispersed suspension, adding one fourth of hydrophobic modifier with low surface energy and micro weight of bismuth oxyhalide, continuously stirring for 2h, vacuum-drying at 60 ℃ for 24h, and grinding to obtain the modified bismuth oxyhalide microspheres.

2. The high weather-resistant steel structure water-based acrylic resin as claimed in claim 1, wherein the compound solvent is a composition of ethanol, n-butanol, isopropanol and ethylene glycol monobutyl ether.

3. The highly weatherable, steel structured, water-based acrylic resin according to claim 1, wherein the initiator is azobisisobutyronitrile or dicumyl peroxide.

4. The highly weatherable steel structural waterborne acrylic resin according to claim 1, wherein the coupling agent is methacryloxy trimethoxysilane.

5. The water-based acrylic resin with high weather-resistant steel structure as claimed in claim 1, wherein the neutralizer is any one of N, N-dimethylethanolamine, N-methyldiethanolamine and triethanolamine.

6. The highly weatherable steel structural waterborne acrylic resin according to claim 1, wherein the chain transfer agent is thioglycolic acid.

7. The high weather-resistant steel structure water-based acrylic resin as claimed in claim 1, which comprises the following raw materials in parts by weight: 12-15 parts of compound solvent, 6-10 parts of acrylic acid, 17-23 parts of acrylate, 16-20 parts of modified bismuth oxyhalide microspheres, 4-9 parts of ethylene versatate, 31-36 parts of hydroxyl-containing methacrylate, 7-11 parts of methacrylic laurate, 8-12 parts of methyl methacrylate, 2-5 parts of coupling agent, 1-3 parts of chain transfer agent, 2-4 parts of initiator and 2-4 parts of neutralizer.

8. The high weather-resistant steel structure water-based acrylic resin as claimed in claim 1, which comprises the following raw materials in parts by weight: 13 parts of compound solvent, 9 parts of acrylic acid, 21 parts of acrylate, 17 parts of modified bismuth oxyhalide microspheres, 5 parts of vinyl versatate, 34 parts of hydroxyl-containing methacrylate, 9 parts of methacrylic laurate, 11 parts of methyl methacrylate, 4 parts of coupling agent, 2 parts of chain transfer agent, 4 parts of initiator and 3 parts of neutralizer.

9. The method for preparing the high weather-resistant steel structure water-based acrylic resin as claimed in any one of claims 1 to 8, comprising the steps of:

1) preparing modified bismuth oxyhalide microspheres for later use; preparing a compound solvent for later use;

2) taking the following raw materials in parts by weight: 10-16 parts of a compound solvent, 6-12 parts of acrylic acid, 15-25 parts of acrylate, 15-23 parts of modified bismuth oxyhalide microspheres, 2-10 parts of vinyl versatate, 30-38 parts of hydroxyl-containing methacrylate, 6-12 parts of methacrylic laurate, 8-14 parts of methyl methacrylate, 2-7 parts of a coupling agent, 1-3 parts of a chain transfer agent, 2-5 parts of an initiator and 2-6 parts of a neutralizer;

3) adding 90% of compound solvent and 90% of initiator into a reaction kettle, and heating to 85 ℃ to obtain a solution A;

4) uniformly stirring acrylic acid, acrylic ester, ethylene versatate, hydroxyl-containing methacrylate, methacrylic laurate, methyl methacrylate, a coupling agent and a chain transfer agent to obtain a mixed solution B;

5) adding 25% of mixed solution B into the solution A for priming, keeping the temperature at 82 ℃ for 30min, then beginning to dropwise add the rest mixed solution B, after finishing dropwise adding for 2-3h, keeping the temperature at 82 ℃ for 1-2h, adding the rest compound solvent and initiator, heating to 87 ℃, and keeping the temperature at 87 ℃ for 2-3 h;

6) cooling to 45 ℃, adding a neutralizing agent and the modified bismuth oxyhalide microspheres, stirring for 30min, adding 180 parts of deionized water, cooling to room temperature, discharging, and filtering to obtain the acrylic resin.

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a preparation method of high weather-resistant steel structure water-based acrylic resin.

Background

With the increasing global environmental pollution, the environment on which human beings live is seriously damaged, and more strict laws and regulations are issued from various countries in the world to treat the pollution so as to reduce the carbon emission and the environmental pollution. In the field of coating, the adoption of water-based coating instead of solvent-based coating is a necessary trend in the current era of development, namely, the substitution of water-based resin for solvent-based resin. Compared with solvent type resin, the water-based resin has the advantages of no odor or low odor, low cost, easy cleaning of equipment and the like.

The water-based acrylic resin has good light resistance, weather resistance, light color, good heat resistance, chemical reagent resistance and good construction performance, and is widely applied to the aspects of building emulsion paint and water-based industrial coating. But the defects of hard and brittle coating film, poor adhesion, insufficient corrosion resistance and water resistance and the like of the water-based acrylic coating are also exposed.

The acrylic resin prepared by the general method has high solid content viscosity, high hardness, brittleness, good flexibility, and poor water resistance and solvent resistance. The acrylic resin in the prior art can only solve part of problems and can not meet the requirement of coating a high-weather-resistance steel structure.

Therefore, how to improve the high weather resistance of the aqueous acrylic resin coating is a matter of concern.

Disclosure of Invention

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The embodiment of the invention provides high weather-resistant steel structure water-based acrylic resin, aiming at solving the problem that the existing water-based acrylic resin is poor in weather resistance.

The embodiment of the invention is realized in such a way that the high weather-resistant steel structure water-based acrylic resin comprises the following raw materials in parts by weight: 10-16 parts of a compound solvent, 6-12 parts of acrylic acid, 15-25 parts of acrylate, 15-23 parts of modified bismuth oxyhalide microspheres, 2-10 parts of vinyl versatate, 30-38 parts of hydroxyl-containing methacrylate, 6-12 parts of methacrylic laurate, 8-14 parts of methyl methacrylate, 2-7 parts of a coupling agent, 1-3 parts of a chain transfer agent, 2-5 parts of an initiator and 2-6 parts of a neutralizer;

the preparation method of the modified bismuth oxyhalide microspheres comprises the following steps: pouring 25ml of glacial acetic acid and 0.1mol of bismuth nitrate into 35ml of distilled water, stirring and mixing, slowly pouring a solution of 25wt% of cetyltrimethyl ammonium bromide and cetyltrimethyl ammonium chloride while stirring, adding 3 x 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at 25 ℃ and room temperature for 10min, filtering, vacuum-drying at 60 ℃ for 24h, grinding to obtain bismuth oxyhalide microspheres, mixing each gram of bismuth oxyhalide microspheres with 10ml of n-hexane, stirring for 30min to obtain uniformly dispersed suspension, then adding one fourth of hydrophobic modifier with low surface energy and micro weight of bismuth oxyhalide, continuing stirring for 2h, vacuum-drying at 60 ℃ for 24h, and grinding to obtain the modified bismuth oxyhalide microspheres.

As a further scheme of the invention: the compound solvent is a composition of ethanol, n-butanol, isopropanol and ethylene glycol monobutyl ether.

As a further scheme of the invention: the initiator is azobisisobutyronitrile or dicumyl peroxide.

As a further scheme of the invention: the coupling agent is methacryloxy trimethoxy silane.

As a further scheme of the invention: the chain transfer agent is thioglycolic acid.

As a further scheme of the invention: the neutralizing agent is any one of N, N-dimethylethanolamine, N-methyldiethanolamine and triethanolamine

As a further scheme of the invention: the feed comprises the following raw materials in parts by weight: 12-15 parts of compound solvent, 6-10 parts of acrylic acid, 17-23 parts of acrylate, 16-20 parts of modified bismuth oxyhalide microspheres, 4-9 parts of ethylene versatate, 31-36 parts of hydroxyl-containing methacrylate, 7-11 parts of methacrylic laurate, 8-12 parts of methyl methacrylate, 2-5 parts of coupling agent, 1-3 parts of chain transfer agent, 2-4 parts of initiator and 2-4 parts of neutralizer.

As a further scheme of the invention: the feed comprises the following raw materials in parts by weight: 13 parts of compound solvent, 9 parts of acrylic acid, 21 parts of acrylate, 17 parts of modified bismuth oxyhalide microspheres, 5 parts of vinyl versatate, 34 parts of hydroxyl-containing methacrylate, 9 parts of methacrylic laurate, 11 parts of methyl methacrylate, 4 parts of coupling agent, 2 parts of chain transfer agent, 4 parts of initiator and 3 parts of neutralizer.

A preparation method of high weather-resistant steel structure water-based acrylic resin comprises the following steps:

1) preparing modified bismuth oxyhalide microspheres for later use; preparing a compound solvent for later use;

2) taking the following raw materials in parts by weight: 10-16 parts of a compound solvent, 6-12 parts of acrylic acid, 15-25 parts of acrylate, 15-23 parts of modified bismuth oxyhalide microspheres, 2-10 parts of vinyl versatate, 30-38 parts of hydroxyl-containing methacrylate, 6-12 parts of methacrylic laurate, 8-14 parts of methyl methacrylate, 2-7 parts of a coupling agent, 1-3 parts of a chain transfer agent, 2-5 parts of an initiator and 2-6 parts of a neutralizer;

3) adding 90% of compound solvent and 90% of initiator into a reaction kettle, and heating to 85 ℃ to obtain a solution A;

4) uniformly stirring acrylic acid, acrylic ester, ethylene versatate, hydroxyl-containing methacrylate, methacrylic laurate, methyl methacrylate, a coupling agent and a chain transfer agent to obtain a mixed solution B;

5) adding 25% of mixed solution B into the solution A for priming, keeping the temperature at 82 ℃ for 30min, then beginning to dropwise add the rest mixed solution B, finishing dropwise adding after 2-3h, keeping the temperature at 82 ℃ for 1-2h, then adding the rest compound solvent and initiator, heating to 87 ℃, keeping the temperature at 87 ℃ for 2-3 h;

6) and cooling to 45 ℃, adding a neutralizing agent and the modified bismuth oxyhalide microspheres, stirring for 30min, adding 180 parts of deionized water, cooling to room temperature, discharging, and filtering to obtain the acrylic resin.

The high weather-resistant steel structure water-based acrylic resin provided by the embodiment of the invention has a transparent, bright and flat film surface, good water resistance, weather resistance and corrosion resistance, improves the surface hardness, keeps high impact resistance and high toughness, is a microsphere with a flower cluster structure formed by self-assembling nano-scale nano-sheets, is modified and mutually cooperated with other components, can enhance the surface self-cleaning capability, improves the water resistance, the corrosion resistance and the weather resistance, and is worthy of popularization.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The technical effects of the water-based acrylic resin with high weather resistance for steel structure of the present invention will be further described with reference to the following specific examples, but the specific implementation methods mentioned in these examples are only illustrative and explanatory of the technical solution of the present invention, and do not limit the implementation scope of the present invention, and all modifications and substitutions based on the above principles should be within the protection scope of the present invention.

Example 1

Pouring 25ml of glacial acetic acid and 0.1mol of bismuth nitrate into 35ml of distilled water, stirring and mixing, slowly pouring a solution of 25wt% of cetyltrimethyl ammonium bromide and cetyltrimethyl ammonium chloride while stirring, adding 3 x 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at 25 ℃ and room temperature for 10min, filtering, vacuum-drying at 60 ℃ for 24h, grinding to obtain bismuth oxyhalide microspheres, mixing each gram of bismuth oxyhalide microspheres with 10ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, then adding one fourth of hydrophobic modifier with low surface energy and micro weight of bismuth oxyhalide, continuing stirring for 2h, vacuum-drying at 60 ℃ for 24h, grinding to obtain modified bismuth oxyhalide microspheres for later use; mixing ethanol, n-butanol, isopropanol and ethylene glycol monobutyl ether according to the ratio of 1:1:1:1 to prepare a compound solvent for later use; taking the following raw materials in parts by weight: 10-16 parts of a compound solvent, 6-12 parts of acrylic acid, 15-25 parts of acrylate, 15-23 parts of modified bismuth oxyhalide microspheres, 2-10 parts of vinyl versatate, 30-38 parts of hydroxyl-containing methacrylate, 6-12 parts of methacrylic laurate, 8-14 parts of methyl methacrylate, 2-7 parts of methacryloxy trimethoxy silane, 1-3 parts of thioglycolic acid, 2-5 parts of azobisisobutyronitrile and 2-6 parts of N, N-dimethylethanolamine; adding 90% of compound solvent and 90% of azodiisobutyronitrile into a reaction kettle, and heating to 85 ℃ to obtain a solution A; uniformly stirring acrylic acid, acrylic ester, vinyl versatate, hydroxyl-containing methacrylate, methacrylic laurate, methyl methacrylate, methacryloxy trimethoxy silane and thioglycolic acid to obtain a mixed solution B; adding 25% of mixed solution B into the solution A for priming, keeping the temperature at 82 ℃ for 30min, then beginning to dropwise add the rest mixed solution B, after finishing dropwise adding for 2-3h, keeping the temperature at 82 ℃ for 1-2h, then adding the rest compound solvent and azobisisobutyronitrile, heating to 87 ℃, and keeping the temperature at 87 ℃ for 2-3 h; and cooling to 45 ℃, adding N, N-dimethylethanolamine and modified bismuth oxyhalide microspheres, stirring for 30min, adding 180 parts of deionized water, cooling to room temperature, discharging, and filtering to obtain the acrylic resin.

Example 2

Pouring 25ml of glacial acetic acid and 0.1mol of bismuth nitrate into 35ml of distilled water, stirring and mixing, slowly pouring a solution of 25wt% of cetyltrimethyl ammonium bromide and cetyltrimethyl ammonium chloride while stirring, adding 3 x 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at 25 ℃ and room temperature for 10min, filtering, vacuum-drying at 60 ℃ for 24h, grinding to obtain bismuth oxyhalide microspheres, mixing each gram of bismuth oxyhalide microspheres with 10ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, then adding one fourth of hydrophobic modifier with low surface energy and micro weight of bismuth oxyhalide, continuing stirring for 2h, vacuum-drying at 60 ℃ for 24h, grinding to obtain modified bismuth oxyhalide microspheres for later use; mixing ethanol, n-butanol, isopropanol and ethylene glycol monobutyl ether according to the ratio of 1:1:1:1 to prepare a compound solvent for later use; taking the following raw materials in parts by weight: 10-16 parts of a compound solvent, 6-12 parts of acrylic acid, 15-25 parts of acrylate, 15-23 parts of modified bismuth oxyhalide microspheres, 2-10 parts of vinyl versatate, 30-38 parts of hydroxyl-containing methacrylate, 6-12 parts of methacrylic laurate, 8-14 parts of methyl methacrylate, 2-7 parts of methacryloxy trimethoxy silane, 1-3 parts of thioglycolic acid, 2-5 parts of azobisisobutyronitrile and 2-6 parts of triethanolamine; adding 90% of compound solvent and 90% of azodiisobutyronitrile into a reaction kettle, and heating to 85 ℃ to obtain a solution A; uniformly stirring acrylic acid, acrylic ester, vinyl versatate, hydroxyl-containing methacrylate, methacrylic laurate, methyl methacrylate, methacryloxy trimethoxy silane and thioglycolic acid to obtain a mixed solution B; adding 25% of mixed solution B into the solution A for priming, keeping the temperature at 82 ℃ for 30min, then beginning to dropwise add the rest mixed solution B, after finishing dropwise adding for 2-3h, keeping the temperature at 82 ℃ for 1-2h, then adding the rest compound solvent and azobisisobutyronitrile, heating to 87 ℃, and keeping the temperature at 87 ℃ for 2-3 h; and cooling to 45 ℃, adding triethanolamine and modified bismuth oxyhalide microspheres, stirring for 30min, adding 180 parts of deionized water, cooling to room temperature, discharging, and filtering to obtain the acrylic resin.

Example 3

Pouring 25ml of glacial acetic acid and 0.1mol of bismuth nitrate into 35ml of distilled water, stirring and mixing, slowly pouring a solution of 25wt% of cetyltrimethyl ammonium bromide and cetyltrimethyl ammonium chloride while stirring, adding 3 x 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at 25 ℃ and room temperature for 10min, filtering, vacuum-drying at 60 ℃ for 24h, grinding to obtain bismuth oxyhalide microspheres, mixing each gram of bismuth oxyhalide microspheres with 10ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, then adding one fourth of hydrophobic modifier with low surface energy and micro weight of bismuth oxyhalide, continuing stirring for 2h, vacuum-drying at 60 ℃ for 24h, grinding to obtain modified bismuth oxyhalide microspheres for later use; mixing ethanol, n-butanol, isopropanol and ethylene glycol monobutyl ether according to the ratio of 1:1:1:1 to prepare a compound solvent for later use; taking the following raw materials in parts by weight: 12-15 parts of a compound solvent, 6-10 parts of acrylic acid, 17-23 parts of acrylate, 16-20 parts of modified bismuth oxyhalide microspheres, 4-9 parts of vinyl versatate, 31-36 parts of hydroxyl-containing methacrylate, 7-11 parts of methacrylic laurate, 8-12 parts of methyl methacrylate, 2-5 parts of methacryloyloxytrimethoxysilane, 1-3 parts of thioglycolic acid, 2-4 parts of dicumyl peroxide and 2-4 parts of triethanolamine, adding 90% of the compound solvent and 90% of the dicumyl peroxide into a reaction kettle, and heating to 85 ℃ to obtain a solution A; uniformly stirring acrylic acid, acrylic ester, vinyl versatate, hydroxyl-containing methacrylate, methacrylic laurate, methyl methacrylate, methacryloxy trimethoxy silane and thioglycolic acid to obtain a mixed solution B; adding 25% of mixed solution B into the solution A for priming, keeping the temperature at 82 ℃ for 30min, then beginning to dropwise add the rest mixed solution B, finishing dropwise adding after 2-3h, keeping the temperature at 82 ℃ for 1-2h, then adding the rest compound solvent and dicumyl peroxide, heating to 87 ℃, and keeping the temperature at 87 ℃ for 2-3 h; and cooling to 45 ℃, adding triethanolamine and modified bismuth oxyhalide microspheres, stirring for 30min, adding 180 parts of deionized water, cooling to room temperature, discharging, and filtering to obtain the acrylic resin.

Example 4

Pouring 25ml of glacial acetic acid and 0.1mol of bismuth nitrate into 35ml of distilled water, stirring and mixing, slowly pouring a solution of 25wt% of cetyltrimethyl ammonium bromide and cetyltrimethyl ammonium chloride while stirring, adding 3 x 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at 25 ℃ and room temperature for 10min, filtering, vacuum-drying at 60 ℃ for 24h, grinding to obtain bismuth oxyhalide microspheres, mixing each gram of bismuth oxyhalide microspheres with 10ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, then adding one fourth of hydrophobic modifier with low surface energy and micro weight of bismuth oxyhalide, continuing stirring for 2h, vacuum-drying at 60 ℃ for 24h, grinding to obtain modified bismuth oxyhalide microspheres for later use; mixing ethanol, n-butanol, isopropanol and ethylene glycol monobutyl ether according to the ratio of 1:1:1:1 to prepare a compound solvent for later use; taking the following raw materials in parts by weight: 12-15 parts of a compound solvent, 6-10 parts of acrylic acid, 17-23 parts of acrylate, 16-20 parts of modified bismuth oxyhalide microspheres, 4-9 parts of vinyl versatate, 31-36 parts of hydroxyl-containing methacrylate, 7-11 parts of methacrylic laurate, 8-12 parts of methyl methacrylate, 2-5 parts of methacryloxy trimethoxy silane, 1-3 parts of thioglycolic acid, 2-4 parts of dicumyl peroxide and 2-4 parts of N-methyldiethanolamine; adding 90% of compound solvent and 90% of dicumyl peroxide into a reaction kettle, and heating to 85 ℃ to obtain a solution A; uniformly stirring acrylic acid, acrylic ester, vinyl versatate, hydroxyl-containing methacrylate, methacrylic laurate, methyl methacrylate, methacryloxy trimethoxy silane and thioglycolic acid to obtain a mixed solution B; adding 25% of mixed solution B into the solution A for priming, keeping the temperature at 82 ℃ for 30min, then beginning to dropwise add the rest mixed solution B, finishing dropwise adding after 2-3h, keeping the temperature at 82 ℃ for 1-2h, then adding the rest compound solvent and dicumyl peroxide, heating to 87 ℃, and keeping the temperature at 87 ℃ for 2-3 h; and cooling to 45 ℃, adding N-methyldiethanolamine and modified bismuth oxyhalide microspheres, stirring for 30min, adding 180 parts of deionized water, cooling to room temperature, discharging, and filtering to obtain the acrylic resin.

Example 5

Pouring 25ml of glacial acetic acid and 0.1mol of bismuth nitrate into 35ml of distilled water, stirring and mixing, slowly pouring a solution of 25wt% of cetyltrimethyl ammonium bromide and cetyltrimethyl ammonium chloride while stirring, adding 3 x 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring at 25 ℃ and room temperature for 10min, filtering, vacuum-drying at 60 ℃ for 24h, grinding to obtain bismuth oxyhalide microspheres, mixing each gram of bismuth oxyhalide microspheres with 10ml of n-hexane, stirring for 30min to obtain a uniformly dispersed suspension, then adding one fourth of hydrophobic modifier with low surface energy and micro weight of bismuth oxyhalide, continuing stirring for 2h, vacuum-drying at 60 ℃ for 24h, grinding to obtain modified bismuth oxyhalide microspheres for later use; mixing ethanol, n-butanol, isopropanol and ethylene glycol monobutyl ether according to the ratio of 1:1:1:1 to prepare a compound solvent for later use; taking the following raw materials in parts by weight: 13 parts of a compound solvent, 9 parts of acrylic acid, 21 parts of acrylate, 17 parts of modified bismuth oxyhalide microspheres, 5 parts of vinyl versatate, 34 parts of hydroxyl-containing methacrylate, 9 parts of methacrylic laurate, 11 parts of methyl methacrylate, 4 parts of methacryloxy trimethoxy silane, 2 parts of thioglycolic acid, 4 parts of dicumyl peroxide and 3 parts of N, N-dimethylethanolamine; adding 90% of compound solvent and 90% of dicumyl peroxide into a reaction kettle, and heating to 85 ℃ to obtain a solution A; uniformly stirring acrylic acid, acrylic ester, vinyl versatate, hydroxyl-containing methacrylate, methacrylic laurate, methyl methacrylate, methacryloxy trimethoxy silane and thioglycolic acid to obtain a mixed solution B; adding 25% of mixed solution B into the solution A for priming, keeping the temperature at 82 ℃ for 30min, then beginning to dropwise add the rest mixed solution B, finishing dropwise adding after 2-3h, keeping the temperature at 82 ℃ for 1-2h, then adding the rest compound solvent and dicumyl peroxide, heating to 87 ℃, and keeping the temperature at 87 ℃ for 2-3 h; and cooling to 45 ℃, adding N, N-dimethylethanolamine and modified bismuth oxyhalide microspheres, stirring for 30min, adding 180 parts of deionized water, cooling to room temperature, discharging, and filtering to obtain the acrylic resin.

Comparative example 1

Pouring 25ml of glacial acetic acid and 0.1mol of bismuth nitrate into 35ml of distilled water, stirring and mixing, slowly pouring a solution of 25wt% of hexadecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium chloride while stirring, adding 3 x 10-4mol of 1mol of sodium borohydride and 20ml of ethanol, stirring for 10min at 25 ℃ and room temperature, filtering, drying in vacuum at 60 ℃ for 24h, and grinding to obtain bismuth oxyhalide microspheres for later use; mixing ethanol, n-butanol, isopropanol and ethylene glycol monobutyl ether according to the ratio of 1:1:1:1 to prepare a compound solvent for later use; taking the following raw materials in parts by weight: 13 parts of a compound solvent, 9 parts of acrylic acid, 21 parts of acrylate, 17 parts of bismuth oxyhalide microspheres, 5 parts of vinyl versatate, 34 parts of hydroxyl-containing methacrylate, 9 parts of methacrylic laurate, 11 parts of methyl methacrylate, 4 parts of methacryloyloxytrimethoxysilane, 2 parts of thioglycolic acid, 4 parts of dicumyl peroxide and 3 parts of N, N-dimethylethanolamine; adding 90% of compound solvent and 90% of dicumyl peroxide into a reaction kettle, and heating to 85 ℃ to obtain a solution A; uniformly stirring acrylic acid, acrylic ester, vinyl versatate, hydroxyl-containing methacrylate, methacrylic laurate, methyl methacrylate, methacryloxy trimethoxy silane and thioglycolic acid to obtain a mixed solution B; adding 25% of mixed solution B into the solution A for priming, keeping the temperature at 82 ℃ for 30min, then beginning to dropwise add the rest mixed solution B, finishing dropwise adding after 2-3h, keeping the temperature at 82 ℃ for 1-2h, then adding the rest compound solvent and dicumyl peroxide, heating to 87 ℃, and keeping the temperature at 87 ℃ for 2-3 h; cooling to 45 ℃, adding N, N-dimethylethanolamine and bismuth oxyhalide microspheres, stirring for 30min, adding 180 parts of deionized water, cooling to room temperature, discharging, and filtering to obtain the acrylic resin.

Comparative example 2

Mixing ethanol, n-butanol, isopropanol and ethylene glycol monobutyl ether according to the ratio of 1:1:1:1 to prepare a compound solvent for later use; taking the following raw materials in parts by weight: 13 parts of a compound solvent, 9 parts of acrylic acid, 21 parts of acrylic ester, 5 parts of vinyl versatate, 34 parts of hydroxyl-containing methacrylate, 9 parts of methacrylic laurate, 11 parts of methyl methacrylate, 4 parts of methacryloxy trimethoxy silane, 2 parts of thioglycolic acid, 4 parts of dicumyl peroxide and 3 parts of N, N-dimethylethanolamine; adding 90% of compound solvent and 90% of dicumyl peroxide into a reaction kettle, and heating to 85 ℃ to obtain a solution A; uniformly stirring acrylic acid, acrylic ester, vinyl versatate, hydroxyl-containing methacrylate, methacrylic laurate, methyl methacrylate, methacryloxy trimethoxy silane and thioglycolic acid to obtain a mixed solution B; adding 25% of mixed solution B into the solution A for priming, keeping the temperature at 82 ℃ for 30min, then beginning to dropwise add the rest mixed solution B, finishing dropwise adding after 2-3h, keeping the temperature at 82 ℃ for 1-2h, then adding the rest compound solvent and dicumyl peroxide, heating to 87 ℃, and keeping the temperature at 87 ℃ for 2-3 h; and cooling to 45 ℃, adding N, N-dimethylethanolamine, stirring for 30min, adding 180 parts of deionized water, cooling to room temperature, discharging, and filtering to obtain the acrylic resin.

Experimental example 1

The acrylic resins prepared in examples 1 to 5 and comparative examples 1 to 2 were coated on a steel plate to form a film, and the obtained paint film was subjected to a performance test, the test results of which are shown in Table 1.

TABLE 1

The acrylic resin prepared in the embodiments 1-5 of the invention has a transparent, bright and flat film surface, has good water resistance, weather resistance and corrosion resistance, improves the surface hardness, and maintains high impact resistance and high toughness, compared with the acrylic resin prepared in the comparative examples 1-2, bismuth oxyhalide is a microsphere with a flower cluster structure formed by self-assembling nano-scale nano-sheets, and the modified bismuth oxyhalide cooperates with other components to enhance the self-cleaning capability of the surface and improve the water resistance, corrosion resistance and weather resistance.

In conclusion, the high weather-resistant steel structure water-based acrylic resin provided by the embodiment of the invention has a transparent, bright and flat film surface, good water resistance, weather resistance and corrosion resistance, improved surface hardness, and high impact resistance and high toughness, wherein the bismuth oxyhalide is a microsphere with a flower cluster structure formed by self-assembling nano-sheets, and is synergistic with other components after modification, so that the surface self-cleaning capability can be enhanced, the water resistance, the corrosion resistance and the weather resistance are improved, and the high weather-resistant steel structure water-based acrylic resin is worthy of popularization.

The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.