High-tolerance water-based hydroxy acrylic acid secondary dispersion as well as preparation method and application thereof

Abstract

The invention discloses a high-tolerance water-based hydroxy acrylic acid secondary dispersion and a preparation method thereof. The water-based adhesive is prepared from the following components in percentage by mass: 10%-20% of methyl methacrylate, 3%-5% of isobornyl methacrylate, 5%-10% of hydroxyethyl methylacrylate, 5%-15% of butyl acrylate, 3%-5% of glycidyl methacrylate, 3%-8% of glycidyl tertiary carboxylic ester, 1%-5% of acrylic acid, 1%-10% of fluorinated acrylate, 0.1%-2% of an initiator, 40%-50% of water, 1%-5% of a neutralizer, 1%-5% of ethylene glycol butyl ether and 1%-5% of propylene glycol butyl ether. According to the experiment, the optimal raw material composition and proportion and the optimal synthesis process are screened through a large number of experiments, and the conversion rate reaches up to 99%. The acrylic resin disclosed by the invention has excellent water resistance, solvent resistance and acid and alkali resistance, meanwhile, a coating film has the advantages of high adhesive force, high hardness, high gloss and the like, and a very good technical effect is achieved in comprehensive performance.

Description

Technical Field

[0001] This invention relates to a highly resistant waterborne hydroxy acrylic acid secondary dispersion, specifically to a highly resistant waterborne hydroxy acrylic acid secondary dispersion with good water resistance, good solvent resistance, good acid and alkali resistance, high adhesion, high gloss, and easy application, as well as its preparation method, belonging to the field of polymer resin technology. Background Technology

[0002] Hydroxypropyl secondary dispersions, as one type of waterborne hydroxypropyl acrylic resin, have received widespread attention in recent years. Hydroxypropyl dispersions are produced through a self-emulsification process, eliminating the need for small-molecule emulsifiers, and allowing for control of relative molecular mass and distribution during solution polymerization. Therefore, compared to hydroxypropyl acrylic latexes, hydroxypropyl dispersions offer higher gloss, better fullness, and superior surface finish, and are currently widely used in waterborne industrial coatings. However, the water resistance and chemical resistance of hydroxypropyl dispersions are still slightly inferior to solvent-based hydroxypropyl resins, failing to meet the requirements of applications with high resistance demands and thus limiting their use. Summary of the Invention

[0003] Purpose of the invention: The purpose of this invention is to address the shortcomings of existing technologies by optimizing the monomer, solvent, and initiator composition of the hydroxy acrylic acid dispersion, and by adding fluorinated acrylate, thereby preparing a secondary dispersion of hydroxy acrylic acid with excellent comprehensive properties such as good water resistance, excellent solvent resistance, good acid and alkali resistance, high adhesion, and high hardness.

[0004] Technical solution: To achieve the above objectives, the technical solution adopted by this invention is as follows: A highly resistant waterborne hydroxy acrylic acid secondary dispersion is characterized in that it is made from the following raw materials: methyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, glycidyl methacrylate, glycidyl tert-carbonate, acrylic acid, fluorinated acrylate, initiator, water, neutralizer, ethylene glycol butyl ether, and propylene glycol butyl ether.

[0005] As a preferred embodiment, the high-durability waterborne hydroxy acrylic secondary dispersion is made from the following raw materials in the indicated mass percentages: 10-20% methyl methacrylate, 3-5% isobornyl methacrylate, 5-10% hydroxyethyl methacrylate, 5-15% butyl acrylate, 3-5% glycidyl methacrylate, 3-8% glycidyl tert-carbonate, 1-5% acrylic acid, 1-10% fluorinated acrylate, 0.1-2% initiator, 40-50% water, 1-5% neutralizer, 1-5% ethylene glycol butyl ether, and 1-5% propylene glycol butyl ether.

[0006] As a preferred embodiment, the above-described high-durability waterborne hydroxy acrylic secondary dispersion is made from the following raw materials in the indicated mass percentages: 13% methyl methacrylate, 4% isobornyl methacrylate, 6% hydroxyethyl methacrylate, 5% butyl acrylate, 2% glycidyl methacrylate, 6% glycidyl tert-carbonate, 3% acrylic acid, 5% fluorinated acrylate, 1% initiator, 45% water, 2% neutralizer, 4% ethylene glycol butyl ether, and 4% propylene glycol butyl ether.

[0007] As a preferred embodiment, the initiator of the above-mentioned high-durability waterborne hydroxy acrylic acid secondary dispersion is ditert-pentyl peroxide.

[0008] As a preferred embodiment, the fluorinated acrylate in the above-described high-durability waterborne hydroxy acrylic secondary dispersion is 2-(perfluorooctyl)ethyl methacrylate.

[0009] The present invention discloses a method for preparing a highly durable waterborne hydroxyacrylic acid secondary dispersion, comprising the following steps: (1) Add ethylene glycol butyl ether, propylene glycol butyl ether and glycidyl tert-carbonate to the reaction apparatus and heat to 140~145℃; (2) Mix a portion of methyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, glycidyl methacrylate, acrylic acid, fluorinated acrylate and initiator evenly and add them to a dropping funnel; (3) When the temperature of the reaction apparatus in step (1) reaches 140~145℃, start adding the mixture in step (2) dropwise. The addition is completed in 2.5~3 hours. After the addition is completed, keep the mixture warm for 0.5~1 hours. (4) Then, mix the remaining methyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, glycidyl methacrylate, acrylic acid, fluorinated acrylate and initiator evenly and add them to the dropping funnel. (5) After the heat preservation in step (3) is completed, start adding the mixed monomers from step (4) dropwise. The dropwise addition time is 1-2 hours. After dripping, keep warm for 0.5 to 1 hour, add the first initiator, keep warm again for 0.5 to 1 hour, then add the second initiator, and keep warm again for 0.5 to 1 hour.

[0010] After the heat preservation is completed, cool down to 90~100℃, add neutralizing agent and stir for 15~30 minutes, then add water and stir at high speed for 2~3 hours to disperse, and the product is ready.

[0011] The preferred embodiment of the method for preparing a high-durability waterborne hydroxy acrylic secondary dispersion is characterized in that, in step (2), the monomer ratio is 10% methyl methacrylate, 3% isobornyl methacrylate, 4% hydroxyethyl methacrylate, 2% butyl acrylate, 1% glycidyl methacrylate, 1% acrylic acid, 5% fluorinated acrylate, and 0.6% initiator.

[0012] As a preferred embodiment, the method for preparing a high-durability waterborne hydroxy acrylic acid secondary dispersion described above is characterized in that when the temperature of the reaction device in step (1) reaches 145~145℃, the mixture in step (2) is added dropwise, and the addition is completed in 3 hours, and then kept warm for 0.5 hours after the addition is completed.

[0013] As a preferred embodiment, the method for preparing a high-durability waterborne hydroxy acrylic acid secondary dispersion described above is characterized in that, in step 4, the monomer ratio is 3% methyl methacrylate, 1% isobornyl methacrylate, 2% hydroxyethyl methacrylate, 3% butyl acrylate, 1% glycidyl methacrylate, 2% acrylic acid, and 0.3% initiator.

[0014] As a preferred embodiment, the method for preparing a high-durability waterborne hydroxy acrylic acid secondary dispersion described above is characterized in that, in step (5), the dripping time is 2 hours, after dripping is completed, the temperature is maintained for 1 hour, then the first part of the initiator is added, the temperature is maintained for 1 hour again, then the second part of the initiator is added, and the temperature is maintained for 1 hour again.

[0015] As a preferred embodiment, the preparation method of the above-described high-durability waterborne hydroxy acrylic acid secondary dispersion is characterized in that, in step (6), after the heat preservation is completed, the temperature is lowered to 90°C, a neutralizing agent is added and stirred for 20 minutes, and then water is added and stirred at high speed for 2.5 hours to obtain the final product.

[0016] Beneficial effects: Compared with the prior art, the present invention has the following advantages: This invention, through extensive experimental screening, employs a two-step dropwise addition process, simultaneously optimizing the composition of the acrylic monomer, solvent, fluorinated acrylate, and initiator system. The fluorinated acrylate used in this invention is 2-(perfluorooctyl)ethyl methacrylate, and the initiator is diterpenoid peroxide. At a relatively high reaction temperature of 140°C, by adjusting the ratio and composition of the monomers added in the two steps, as well as the addition time, a secondary dispersion of hydroxyacrylic acid is obtained. The secondary dispersion of hydroxyacrylic acid prepared by this invention exhibits good water resistance, excellent solvent resistance, and acid and alkali resistance, while also possessing excellent comprehensive properties such as high adhesion and high hardness. Detailed Implementation

[0017] Example 1 A highly resistant waterborne hydroxy acrylic acid secondary dispersion is made from the following raw materials in the indicated weight percentages: 13% methyl methacrylate, 4% isobornyl methacrylate, 6% hydroxyethyl methacrylate, 5% butyl acrylate, 2% glycidyl methacrylate, 6% glycidyl tert-carbonate, 3% acrylic acid, 5% 2-(perfluorooctyl)ethyl methacrylate, 1% initiator (dipentyl peroxide), 45% water, 2% neutralizer, 4% ethylene glycol butyl ether, and 4% propylene glycol butyl ether.

[0018] 2. The preparation method of the high-durability waterborne hydroxy acrylic acid secondary dispersion of the present invention includes the following steps: (1) Add 40 g of ethylene glycol butyl ether, 40 g of propylene glycol butyl ether and 60 g of glycidyl tert-carbonate to the reaction apparatus, and start stirring and heat to 140~145℃. (2) Mix 100g of methyl methacrylate, 30g of isobornyl methacrylate, 40g of hydroxyethyl methacrylate, 20g of butyl acrylate, 10g of glycidyl methacrylate, 10g of acrylic acid, 50g of 2-(perfluorooctyl)ethyl methacrylate and 6g of diterpenoid peroxide (DTAP) evenly and add them to a dropping funnel; (3) When the temperature of the reaction apparatus in step (1) reaches 140~145℃, start adding the mixture in step (2) dropwise. The addition is completed in 3 hours, and the mixture is kept warm for 0.5 hours after the addition is completed. (4) Then mix 30g of methyl methacrylate, 10g of isobornyl methacrylate, 20g of hydroxyethyl methacrylate, 30g of butyl acrylate, 10g of glycidyl acrylate, 20g of acrylic acid, and 3g of diammonium peroxide (DTAP) evenly and add them to the dropping funnel. (5) After the heat preservation in step (3) is completed, start to add the mixed monomer in step (4) for 2 hours. After the addition is completed, keep warm for 1 hour, add 0.5 g of dapramyl peroxide (DTAP), keep warm for another 1 hour, and then add 0.5 g of dapramyl peroxide (DTAP) and keep warm for another 1 hour.

[0019] (6) After the heat preservation is completed, the temperature is reduced to 90°C. 20g of dimethylethanolamine is added and stirred for 20 minutes to neutralize. Then 450g of water is added and stirred at high speed for 2.5 hours to disperse. The product is then discharged.

[0020] The final reaction conversion rate can reach 99%, the dispersion has a solid content of 44.6%, and the particle size is 110 nm.

[0021] Comparative Example 1 (different initiator) A method for preparing a highly durable waterborne hydroxyacrylic acid secondary dispersion includes the following steps: (1) Add 40 g of ethylene glycol butyl ether, 40 g of propylene glycol butyl ether and 60 g of glycidyl tert-carbonate to the reaction apparatus, and start stirring and heat to 140~145℃. (2) Mix 100g of methyl methacrylate, 30g of isobornyl methacrylate, 40g of hydroxyethyl methacrylate, 20g of butyl acrylate, 10g of glycidyl methacrylate, 10g of acrylic acid, 50g of 2-(perfluorooctyl)ethyl methacrylate and 6g of benzoyl peroxide (BPO) evenly and add them to a dropping funnel. (3) When the temperature of the reaction apparatus in step (1) reaches 140~145℃, start adding the mixture in step (2) dropwise. The addition is completed in 3 hours, and the mixture is kept warm for 0.5 hours after the addition is completed. (4) Then mix 30g of methyl methacrylate, 10g of isobornyl methacrylate, 20g of hydroxyethyl methacrylate, 30g of butyl acrylate, 10g of glycidyl acrylate, 20g of acrylic acid and 3g of benzoyl peroxide (BPO) evenly and add them to the dropping funnel. (5) After the heat preservation in step (3) is completed, start to add the mixed monomer in step (4) for 2 hours. After the addition is completed, keep warm for 1 hour, add 0.5 g of benzoyl peroxide (BPO), keep warm for another 1 hour, and then add 0.5 g of benzoyl peroxide (BPO) and keep warm for another 1 hour.

[0022] After the heat preservation is completed, the temperature is lowered to 90℃. 20 grams of dimethylethanolamine is added and stirred for 20 minutes to neutralize. Then, 450 grams of water is added and stirred at high speed for 2.5 hours to disperse. The product is then ready to be discharged.

[0023] The final reaction conversion rate can reach 95%, the dispersion has a solid content of 42.7%, and the particle size is 120 nm.

[0024] Comparative Example 2 (Stepwise addition of 2-(perfluorooctyl)ethyl methacrylate) A method for preparing a highly durable waterborne hydroxyacrylic acid secondary dispersion includes the following steps: (1) Add 40 g of ethylene glycol butyl ether, 40 g of propylene glycol butyl ether and 60 g of glycidyl tert-carbonate to the reaction apparatus, and start stirring and heat to 140~145℃. (2) Mix 100g of methyl methacrylate, 30g of isobornyl methacrylate, 40g of hydroxyethyl methacrylate, 20g of butyl acrylate, 10g of glycidyl methacrylate, 10g of acrylic acid, 30g of 2-(perfluorooctyl)ethyl methacrylate and 6g of diterpenoid peroxide (DTAP) evenly and add them to a dropping funnel; (3) When the temperature of the reaction apparatus in step (1) reaches 140~145℃, start adding the mixture in step (2) dropwise. The addition is completed in 3 hours, and the mixture is kept warm for 0.5 hours after the addition is completed. (4) Then mix 30g of methyl methacrylate, 10g of isobornyl methacrylate, 20g of hydroxyethyl methacrylate, 30g of butyl acrylate, 10g of glycidyl acrylate, 20g of acrylic acid, 20g of 2-(perfluorooctyl)ethyl methacrylate and 3g of diterpenoid peroxide (DTAP) evenly and add them to the dropping funnel. (5) After the heat preservation in step (3) is completed, start to add the mixed monomer in step (4) for 2 hours. After the addition is completed, keep warm for 1 hour, add 0.5 g of dapramyl peroxide (DTAP), keep warm for another 1 hour, and then add 0.5 g of dapramyl peroxide (DTAP) and keep warm for another 1 hour.

[0025] After the heat preservation is completed, the temperature is lowered to 90℃. 20 grams of dimethylethanolamine is added and stirred for 20 minutes to neutralize. Then, 450 grams of water is added and stirred at high speed for 2.5 hours to disperse. The product is then ready to be discharged.

[0026] The final reaction conversion rate can reach 98%, the dispersion has a solid content of 44.1%, and the particle size is 122 nm.

[0027] Comparative Example 3 (without 2-(perfluorooctyl)ethyl methacrylate) A method for preparing a highly durable waterborne hydroxyacrylic acid secondary dispersion includes the following steps: (1) Add 40 g of ethylene glycol butyl ether, 40 g of propylene glycol butyl ether and 60 g of glycidyl tert-carbonate to the reaction apparatus, and start stirring and heat to 140~145℃. (2) Mix 130g of methyl methacrylate, 30g of isobornyl methacrylate, 40g of hydroxyethyl methacrylate, 20g of butyl acrylate, 10g of glycidyl methacrylate, 10g of acrylic acid, and 6g of diterpenoid peroxide (DTAP) evenly and add them to a dropping funnel. (3) When the temperature of the reaction apparatus in step (1) reaches 140~145℃, start adding the mixture in step (2) dropwise. The addition is completed in 3 hours, and the mixture is kept warm for 0.5 hours after the addition is completed. (4) Then mix 50g of methyl methacrylate, 10g of isobornyl methacrylate, 20g of hydroxyethyl methacrylate, 30g of butyl acrylate, 10g of glycidyl acrylate, 20g of acrylic acid, and 3g of diammonium peroxide (DTAP) evenly and add them to the dropping funnel. (5) After the heat preservation in step (3) is completed, start adding the mixed monomers from step (4) over a period of 2 hours. After dripping, keep warm for 1 hour, add 0.5 g of dapramethylene peroxide (DTAP), keep warm for another hour, then add another 0.5 g of dapramethylene peroxide (DTAP), and keep warm for another hour.

[0028] After the heat preservation is completed, the temperature is lowered to 90℃. 20 grams of dimethylethanolamine is added and stirred for 20 minutes to neutralize. Then, 450 grams of water is added and stirred at high speed for 2.5 hours to disperse. The product is then ready to be discharged.

[0029] The final reaction conversion rate can reach 98%, the dispersion has a solid content of 44.1%, and the particle size is 118 nm.

[0030] Comparative Example 4 (without the addition of isobornyl methacrylate) A method for preparing a highly durable waterborne hydroxyacrylic acid secondary dispersion includes the following steps: (1) Add 40 g of ethylene glycol butyl ether, 40 g of propylene glycol butyl ether and 60 g of glycidyl tert-carbonate to the reaction apparatus, and start stirring and heat to 140~145℃. (2) Mix 130g of methyl methacrylate, 40g of hydroxyethyl methacrylate, 20g of butyl methacrylate, 10g of glycidyl methacrylate, 10g of acrylic acid, 50g of 2-(perfluorooctyl)ethyl methacrylate and 6g of diterpenoid peroxide (DTAP) evenly and add it to a dropping funnel. (3) When the temperature of the reaction apparatus in step (1) reaches 140~145℃, start adding the mixture in step (2) dropwise. The addition is completed in 3 hours, and the mixture is kept warm for 0.5 hours after the addition is completed. (4) Then mix 40g of methyl methacrylate, 20g of hydroxyethyl methacrylate, 30g of butyl acrylate, 10g of glycidyl acrylate, 20g of acrylic acid and 3g of diterpenoid peroxide (DTAP) evenly and add them to the dropping funnel. (5) After the heat preservation in step (3) is completed, start adding the mixed monomers from step (4) over a period of 2 hours. After dripping, keep warm for 1 hour, add 0.5 g of dapramethylene peroxide (DTAP), keep warm for another hour, then add another 0.5 g of dapramethylene peroxide (DTAP), and keep warm for another hour.

[0031] After the heat preservation is completed, the temperature is lowered to 90℃. 20 grams of dimethylethanolamine is added and stirred for 20 minutes to neutralize. Then, 450 grams of water is added and stirred at high speed for 2.5 hours to disperse. The product is then ready to be discharged.

[0032] The final reaction conversion rate can reach 98%, the dispersion has a solid content of 44.1%, and the particle size is 122 nm.

[0033] Application Example 1 1. The aqueous hydroxy acrylic acid secondary dispersions prepared in Example 1 and Comparative Examples 1, 2, 3 and 4 above were formulated into white paint according to the formulations in Table 1 below.

[0034] Table 1. Composition of two-component white paint formulation for hydroxyacrylic acid secondary dispersion. .

[0035] Paint film testing The white paints prepared from the dispersions of Example 1 and Comparative Examples 1, 2, 3 and 4 were subjected to the following tests: Among them, hardness (pencil scratch) was determined according to GB / T6739-1996 Test of Pencil Hardness of Coating; impact (recoil) was determined according to GB / T1732-93 Test of Impact Resistance of Paint Film; adhesion (circle scratch method) was determined according to GB / T1720-79 (89) Test of Adhesion of Paint Film; gloss was determined according to GB / T 9754-2007 Test of 20°, 60° and 85° Specular Gloss of Paint Film without Metallic Pigment (60° is the standard); water resistance was determined according to GB / T 1733-1993 Test of Water Resistance of Paint Film; solvent resistance and acid and alkali resistance were determined according to GB / T 9274-1988 Test of Resistance to Liquid Media of Paint and Varnish. The specific test results of the paint are shown in Tables 2 and 3: Table 2 Results of mechanical properties and contact angle tests of the coating film

[0036] Table 3. Test results of water resistance, acid and alkali resistance, and ethanol resistance of the coating film. .

[0037] The above experimental results demonstrate that this invention, through extensive experimentation and screening of various reactant compositions, particularly the formulation of isobornyl methacrylate, glycidyl methacrylate, and 2-(perfluorooctyl)ethyl methacrylate, yields a highly resistant waterborne hydroxy acrylic secondary dispersion. This dispersion not only possesses excellent water resistance, superior acid and alkali resistance, solvent resistance, and high adhesion, but also exhibits high gloss and excellent mechanical properties. It overcomes the shortcomings of existing technologies and achieves unexpected and significant technical benefits.

[0038] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A highly durable waterborne hydroxyl acrylic acid secondary dispersion, characterized in that, It is made from the following raw materials: methyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, glycidyl methacrylate, glycidyl tert-carbonate, acrylic acid, fluorinated acrylate, initiator, water, neutralizer, ethylene glycol butyl ether and propylene glycol butyl ether.

2. The highly durable waterborne hydroxyl acrylic acid secondary dispersion according to claim 1, characterized in that, It is made from the following raw materials in the following weight percentages: 10-20% methyl methacrylate, 3-5% isobornyl methacrylate, 5-10% hydroxyethyl methacrylate, 5-15% butyl acrylate, 3-5% glycidyl methacrylate, 3-8% glycidyl tert-carbonate, 1-5% acrylic acid, 1-10% fluorinated acrylate, 0.1-2% initiator, 40-50% water, 1-5% neutralizer, 1-5% ethylene glycol butyl ether and 1-5% propylene glycol butyl ether.

3. The highly durable waterborne hydroxyl acrylic acid secondary dispersion according to claim 1, characterized in that, It is made from the following raw materials in the following weight percentages: 13% methyl methacrylate, 4% isobornyl methacrylate, 6% hydroxyethyl methacrylate, 5% butyl acrylate, 2% glycidyl methacrylate, 6% glycidyl tert-carbonate, 3% acrylic acid, 5% fluorinated acrylate, 1% initiator, 45% water, 2% neutralizer, 4% ethylene glycol butyl ether and 4% propylene glycol butyl ether.

4. The highly durable waterborne hydroxyl acrylic acid secondary dispersion according to claims 1-3, characterized in that, The initiator is dipentyl peroxide; the fluorinated acrylate is preferably 2-(perfluorooctyl)ethyl methacrylate.

5. A method for preparing a highly durable waterborne hydroxyl acrylic acid secondary dispersion according to any one of claims 1 to 4, characterized in that, Includes the following steps: (1) Add ethylene glycol butyl ether, propylene glycol butyl ether and glycidyl tert-carbonate to the reaction apparatus and heat to 140~145℃; (2) Mix a portion of methyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, glycidyl methacrylate, acrylic acid, fluorinated acrylate and initiator evenly and add them to a dropping funnel; (3) When the temperature of the reaction apparatus in step (1) reaches 140~145℃, start adding the mixture in step (2) dropwise. The addition is completed in 2.5~3 hours. After the addition is completed, keep the mixture warm for 0.5~1 hours. (4) Then, mix the remaining methyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, glycidyl methacrylate, acrylic acid, fluorinated acrylate and initiator evenly and add them to the dropping funnel. (5) After the heat preservation in step (3) is completed, start adding the mixed monomers from step (4) dropwise. The dropwise addition time is 1-2 hours. After dripping, keep warm for 0.5 to 1 hour, add the first part of the initiator, keep warm again for 0.5 to 1 hour, then add the second part of the initiator, and keep warm again for 0.5 to 1 hour. (6) After the heat preservation is completed, cool down to 90~100℃, add neutralizing agent and stir for 15~30 minutes, then add water and stir at high speed for 2~3 hours to disperse, and the product is obtained.

6. The method for preparing a highly durable waterborne hydroxy acrylic acid secondary dispersion according to claim 5, characterized in that, In step (2), the monomer ratio is 10% methyl methacrylate, 3% isobornyl methacrylate, 4% hydroxyethyl methacrylate, 2% butyl acrylate, 1% glycidyl methacrylate, 1% acrylic acid, 5% fluorinated acrylate, and 0.6% initiator.

7. The method for preparing a highly durable waterborne hydroxyacrylic acid secondary dispersion according to claim 5, characterized in that, When the temperature of the reaction apparatus in step (1) reaches 145~145℃, the mixture in step (2) is added dropwise over 3 hours. After the addition is complete, the mixture is kept warm for 0.5 hours.

8. The method for preparing a highly durable waterborne hydroxyacrylic acid secondary dispersion according to claim 5, characterized in that, In step (4), the monomer ratio is 3% methyl methacrylate, 1% isobornyl methacrylate, 2% hydroxyethyl methacrylate, 3% butyl acrylate, 1% glycidyl methacrylate, 2% acrylic acid, and 0.3% initiator.

9. The method for preparing a highly durable waterborne hydroxy acrylic acid secondary dispersion according to claim 5, characterized in that, In step (5), the dripping time is 2 hours. After dripping, keep warm for 1 hour, then add the first part of the initiator, keep warm for another 1 hour, then add the second part of the initiator, and keep warm for another 1 hour. In step (6), after the heat preservation is completed, the temperature is lowered to 90°C, a neutralizing agent is added and stirred for 20 minutes, and then water is added and stirred at high speed for 2.5 hours to disperse the mixture.

10. The use of the aqueous hydroxyacrylic acid secondary dispersion according to any one of claims 1 to 4 in the preparation of a high-durability coating film.

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