High-corrosion-resistance acrylic resin composition and preparation method thereof

Abstract

The invention discloses a high-corrosion-resistance acrylic resin composition and a preparation method thereof. The high-corrosion-resistance acrylic resin composition is prepared from the following components in percentage by mass: 25 to 35 percent of methyl methacrylate, 10 to 20 percent of butyl acrylate, 5 to 10 percent of 2-perfluorodecyl ethyl methacrylate, 5 to 10 percent of hexamethylene diisocyanate, 0.5 to 2 percent of initiator, 2 to 5 percent of nano zinc oxide and 20 to 40 percent of xylene. The optimal raw material composition and proportion are screened through a large number of experiments, the optimal synthesis process is preferably obtained through a large number of experiments, the conversion rate is up to 99%, and the solid content of the resin reaches 67% or above. The high-corrosion-resistance acrylic resin composition disclosed by the invention has the advantages of excellent adhesive force, corrosion resistance, salt fog resistance and the like, and has a very good technical effect in comprehensive performance.

Description

Technical Field

[0001] This invention relates to a highly corrosion-resistant acrylic resin composition, specifically to a high-performance, easily applicable, highly corrosion-resistant acrylic resin composition and its preparation method, belonging to the field of polymer resin technology. Background Technology

[0002] Acrylic resins are widely used in industrial coatings due to their excellent film-forming properties, weather resistance, and mechanical properties. However, traditional acrylic resins are prone to swelling and degradation in strong acid, strong alkali, or high salt spray environments, leading to coating failure. Existing technologies typically involve adding inorganic fillers or fluorine modification to improve corrosion resistance, but these methods suffer from high costs, complex processes, or reduced adhesion. Therefore, developing an acrylic resin that combines high corrosion resistance, low cost, and ease of processing is of great significance.

[0003] This invention provides a method for preparing a highly corrosion-resistant acrylic resin composition. Summary of the Invention

[0004] Objective of the Invention: The objective of this invention is to address the shortcomings of existing technologies by optimizing the composition of acrylic resin monomers and initiator, as well as their specific dosage ratios, to obtain a highly corrosion-resistant acrylic resin composition with high conversion rate and excellent comprehensive properties such as adhesion and corrosion resistance. The highly corrosion-resistant acrylic resin composition of this invention has the following advantages: (1) Fluorine-containing monomers and nanofillers were used to improve the chemical inertness and physical shielding performance of the resin through molecular design.

[0005] (2) One-step polymerization simplifies the production process and is suitable for industrial-scale production.

[0006] (3) The introduction of multifunctional crosslinking agents significantly improves the corrosion resistance of the resin coating, making it suitable for long-term protection in harsh environments.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A highly corrosion-resistant acrylic resin composition is made from the following raw materials: methyl methacrylate, butyl acrylate, ethyl 2-perfluorodecyl methacrylate, hexamethylene diisocyanate, initiator, nano zinc oxide, and xylene.

[0008] As a preferred embodiment, the above-described highly corrosion-resistant acrylic resin composition is made from the following raw materials in the indicated weight percentages: 25-35% methyl methacrylate, 10-20% butyl acrylate, 5-10% ethyl 2-perfluorodecyl methacrylate, 5-10% hexamethylene diisocyanate, 0.5-2% initiator, 2-5% nano zinc oxide, and 20-40% xylene.

[0009] As a preferred embodiment, the above-described highly corrosion-resistant acrylic resin composition is made from the following raw materials in the indicated weight percentages: 32% methyl methacrylate, 16% butyl acrylate, 8% ethyl 2-perfluorodecyl methacrylate, 6.5% hexamethylene diisocyanate, 1.5% initiator, 4% nano zinc oxide, and 32% xylene.

[0010] As a preferred embodiment, in the above-described highly corrosion-resistant acrylic resin composition, the initiator is azobisisobutyronitrile (AIBN).

[0011] A method for preparing a highly corrosion-resistant acrylic resin composition includes the following steps: (1) Add xylene to a four-necked flask, introduce nitrogen gas, and heat to the controlled temperature; (2) Mix methyl methacrylate, butyl acrylate, ethyl 2-perfluorodecyl methacrylate and initiator evenly according to mass percentage and add them to the dropping pump; (3) After the temperature of the four-necked flask in step (1) is reached, keep it warm and then start adding the mixture from step (2). After adding all the mixture, keep it warm for a period of time. (4) When the heat preservation in step (3) is completed, cool down, add hexamethylene diisocyanate and nano zinc oxide, stir, and you will get the product.

[0012] As a preferred embodiment, in the preparation method of the above-described highly corrosion-resistant acrylic resin composition, the temperature in step (1) is controlled at 75~85℃.

[0013] As a preferred embodiment, in the above-described method for preparing a highly corrosion-resistant acrylic resin composition, the initiator is azobisisobutyronitrile (AIBN).

[0014] As a preferred embodiment, in the preparation method of the high corrosion resistant acrylic resin composition described above, in step (3), when the temperature of the four-necked flask in step (1) reaches the controlled temperature of 75~85℃, after keeping it warm for 0.5 hours, the mixture in step (2) is added dropwise, and the addition is completed in 5 hours. After the addition is completed, the mixture is kept warm for 1 hour.

[0015] As a preferred embodiment, in the preparation method of the above-described high corrosion resistant acrylic resin composition, in step (4), after the heat preservation in step (3) is completed, the temperature is lowered to 60°C, hexamethylene diisocyanate and nano zinc oxide are added, and the mixture is stirred for 2 hours to obtain the final product.

[0016] Beneficial effects: Compared with the prior art, the present invention has the following advantages: Through extensive experimental screening, this invention optimizes and adjusts the composition and optimal dosage ratio of the acrylic resin monomer and initiator system. By copolymerizing the functional monomer ethyl 2-perfluorodecyl methacrylate during resin synthesis, a dense hydrophobic film layer can be formed in the resin. The addition of nano zinc oxide can improve the resin's impermeability. The addition of hexamethylene diisocyanate can improve the resin's adhesion.

[0017] This invention uses azobisisobutyronitrile (AIBN) as an initiator. At a reaction temperature of 75℃-85℃, a uniform dropwise addition method achieves a high resin conversion rate, reaching 99%. The suitable reaction temperature and dropwise addition time allow for high resin molecular weight control without affecting film-forming properties. The higher molecular weight also results in higher resin viscosity, enabling the preparation of high-solids resins. The resin of this invention achieves a solids content of over 67%.

[0018] This invention provides a highly corrosion-resistant acrylic resin composition with suitable viscosity. The coating film exhibits comprehensive properties such as salt spray resistance, corrosion resistance, high adhesion, and high weather resistance, making it suitable for applications such as metal protective coatings, marine engineering coatings, and surface treatment of chemical equipment. Detailed Implementation

[0019] Example 1 1. A highly corrosion-resistant acrylic resin composition, made from the following raw materials in the indicated weight percentages: 32% methyl methacrylate, 16% butyl acrylate, 8% ethyl 2-perfluorodecyl methacrylate, 6.5% hexamethylene diisocyanate, 1.5% initiator, 4% nano zinc oxide, and 32% xylene.

[0020] 2. The preparation method of the highly corrosion-resistant acrylic resin composition of the present invention includes the following steps: (1) Add a measured amount of 192 g xylene to a four-necked flask, introduce nitrogen gas, and heat to 75-85 °C; (2) Mix 192g of methyl methacrylate, 96g of butyl acrylate, 48g of ethyl 2-perfluorodecyl methacrylate and 9g of azobisisobutyronitrile evenly and add them to a drop pump. (3) When the temperature of the four-necked flask in step (1) reaches the control temperature and is kept warm for 0.5 hours, start adding the mixture from step (2) dropwise. The addition is completed in 5 hours, and then kept warm for 1 hour after the addition is completed. (4) When the heat preservation in step (3) is completed, cool down to 60°C, add a certain amount of 39 g of hexamethylene diisocyanate and 24 g of nano zinc oxide, and stir for 2 hours to obtain the product.

[0021] The resin has a solid content of 67.32% and a viscosity of 8000 mPa·s (rotational viscosity / 25℃). Dividing the resin solid content of 67.32% by the theoretical solid content of 68% yields a conversion rate of 99%.

[0022] The resin obtained in Example 1 was mixed according to the proportions of the ingredients in Table 1 below, and baked at 80°C for 20 minutes to prepare a metal protective paint with a film thickness of 20 μm. The performance is shown in Table 2.

[0023] Table 1 Composition of Metal Protective Coating Formulation Raw material name Weight (g) Example 1: High Weather Resistance Acrylic Resin 55 Titanium dioxide 15 Tinuvin 1130, a UV absorber 1 Light stabilizer Tinuvin 292 0.5 Anti-corrosion filler mica powder 8 Leveling agent BYK-306 0.5 xylene 15

[0024] Table 2. Results of Resin and Coating Film Performance Tests Appearance Smooth and free of particles Salt spray resistant (2000 hours of salt spray) No bubbling or peeling Adhesion (cross-cut test) Level 0

[0025] Salt spray resistance was determined according to GB / T31588.1-2015 Determination of resistance to cyclic corrosion in paints and varnishes; adhesion (cross-cut test) was determined according to GB / T9286-1998 Cross-cut test of paint and varnish films.

[0026] Comparative Example 1 A method for preparing a highly corrosion-resistant acrylic resin composition, comprising the following steps: (1) Add a measured amount of 192 g xylene to a four-necked flask, introduce nitrogen gas, and heat to 75-85 °C; (2) Mix 192g of methyl methacrylate, 96g of butyl acrylate, 48g of isobornyl acrylate and 9g of azobisisobutyronitrile evenly and add them to the drop pump. (3) When the temperature of the four-necked flask in step (1) reaches the control temperature and is kept warm for 0.5 hours, start adding the mixture from step (2) dropwise. The addition is completed in 5 hours, and then kept warm for 1 hour after the addition is completed. (4) When the heat preservation in step (3) is completed, cool down to 60°C, add a certain amount of 39 g of hexamethylene diisocyanate and 24 g of nano zinc oxide, and stir for 2 hours to obtain the product.

[0027] The resin has a solid content of 66.98% and a viscosity of 6400 mPa·s (rotational viscosity / 25℃). Dividing the actual solid content of 66.98% by the theoretical solid content of 68% yields a resin conversion rate of 98.5%.

[0028] The resin obtained in Comparative Example 1 was mixed with the various ingredients listed in Table 3 below in the specified proportions, and then baked at 80°C for 20 minutes to prepare a metallic protective paint with a film thickness of 20 μm. The performance tests are shown in Table 4.

[0029] Table 3 Composition of Metal Protective Coating Formulation Raw material name Weight (g) Comparative Example 1 Resin 55 Titanium dioxide 15 Tinuvin 1130, a UV absorber 1 Light stabilizer Tinuvin 292 0.5 Anti-corrosion filler mica powder 8 Leveling agent BYK-306 0.5 xylene 15

[0030] Table 4. Results of Resin and Coating Film Performance Tests Appearance Smooth and free of particles Salt spray resistant (2000 hours of salt spray) Bubbling and peeling Adhesion (cross-cut test) Level 0

[0031] Salt spray resistance was determined according to GB / T31588.1-2015 Determination of resistance to cyclic corrosion in paints and varnishes; adhesion (cross-cut test) was determined according to GB / T9286-1998 Cross-cut test of paint and varnish films.

[0032] As can be seen from the comparison of the components of Example 1 and Comparative Example 1, the present invention uses a specific solvent and methyl methacrylate, butyl acrylate, hexamethylene diisocyanate, initiator, and nano zinc oxide. Comparative Example 1 adjusts the functional monomers of the resin based on Example 1, replacing ethyl 2-perfluorodecyl methacrylate with isobornyl acrylate. From the salt spray resistance results, the lack of fluorine-containing monomers in the resin has a significant impact on the corrosion resistance of the resin.

[0033] Comparative Example 2 A method for preparing a highly corrosion-resistant acrylic resin composition, comprising the following steps: (1) Add a measured amount of 192 g xylene to a four-necked flask, introduce nitrogen gas, and heat to 75-85 °C; (2) Mix 192g of methyl methacrylate, 96g of styrene, 48g of ethyl 2-perfluorodecyl methacrylate and 9g of azobisisobutyronitrile evenly and add them to a drop pump; (3) When the temperature of the four-necked flask in step (1) reaches the control temperature and is kept warm for 0.5 hours, start adding the mixture from step (2) dropwise. The addition is completed in 5 hours, and then kept warm for 1 hour after the addition is completed. (4) When the heat preservation in step (3) is completed, cool down to 60°C, add a certain amount of 39 g of hexamethylene diisocyanate and 24 g of nano zinc oxide, stir for 2 hours, and the product is obtained.

[0034] The resin has a solid content of 67.4% and a viscosity of 9800 mPa·s (rotational viscosity / 25°C). Dividing the resin solid content of 67.4% by the actual solid content of 68% yields a conversion rate of 99%. The resin obtained in Comparative Example 2 was mixed with the various ingredients listed in Table 5 below in the specified proportions, and then baked at 80°C for 20 minutes to prepare a metallic protective coating with a film thickness of 20 μm. The performance tests are shown in Table 6.

[0035] Table 5 Composition of Metal Protective Coating Formulation Raw material name Weight (g) Comparative Example 2 Resin 55 Titanium dioxide 15 Tinuvin 1130, a UV absorber 1 Light stabilizer Tinuvin 292 0.5 Anti-corrosion filler mica powder 8 Leveling agent BYK-306 0.5 xylene 15

[0036] Table 6. Test results of resin and coating properties Appearance Smooth and free of particles Salt spray resistant (2000 hours of salt spray) No bubbling or peeling Adhesion (cross-cut test) Level 2

[0037] Salt spray resistance was determined according to GB / T31588.1-2015 Determination of resistance to cyclic corrosion in paints and varnishes; adhesion (cross-cut test) was determined according to GB / T9286-1998 Cross-cut test of paint and varnish films.

[0038] As can be seen from the comparison of components in Example 1 and Comparative Example 2 above, the present invention uses a specific solvent and methyl methacrylate, hexamethylene diisocyanate, ethyl 2-perfluorodecyl methacrylate, initiator, and nano zinc oxide. The results regarding resin adhesion show that replacing butyl acrylate with styrene increases the glass transition temperature of the resin, thereby leading to a decrease in resin adhesion. The glass transition temperature of the resin has a significant impact on its adhesion.

[0039] Comparative Example 3 A method for preparing a highly corrosion-resistant acrylic resin composition, comprising the following steps: (1) Add a measured amount of 192 g xylene to a four-necked flask, introduce nitrogen gas, and heat to 85-90 °C; (2) Mix 192g of methyl methacrylate, 96g of butyl acrylate, 48g of ethyl 2-perfluorodecyl methacrylate and 9g of azobisisobutyronitrile evenly and add them to a drop pump. (3) When the temperature of the four-necked flask in step (1) reaches the control temperature and is kept warm for 0.5 hours, start adding the mixture from step (2) dropwise. The addition is completed in 3 hours, and then kept warm for 1 hour after the addition is completed. (4) When the heat preservation in step (3) is completed, cool down to 60°C, add a certain amount of 39 g of hexamethylene diisocyanate and 24 g of nano zinc oxide, and stir for 2 hours to obtain the product.

[0040] The resin has a solid content of 62.5% and a viscosity of 11500 mPa·s (rotational viscosity / 25℃). Dividing the actual solid content of 62.5% by the theoretical solid content of 68% yields a resin conversion rate of 91.9%. As can be seen from the comparison of the three components in Example 1 above, the present invention uses a specific solvent and methyl methacrylate, hexamethylene diisocyanate, ethyl 2-perfluorodecyl methacrylate, initiator, nano zinc oxide, and butyl propylene glycol, and changes the control temperature and dropping time (from 5 hours to 3 hours). The conversion rate decreases from 99% to 91.9%, which shows that the appropriate reaction temperature and dropping time have a significant impact on the conversion rate of the resin.

[0041] Based on Example 1 and Comparative Examples 1, 2 and 3, the addition of the functional monomer fluorodecyl methacrylate through copolymerization can enhance the corrosion resistance of the resin; a reasonable glass transition temperature can improve the adhesion of the resin; and an appropriate dropping time can improve the conversion rate of the resin.

[0042] 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 corrosion-resistant acrylic resin composition, characterized in that, It is made from the following raw materials: methyl methacrylate, butyl acrylate, ethyl 2-perfluorodecyl methacrylate, hexamethylene diisocyanate, initiator, nano zinc oxide, and xylene.

2. The highly corrosion-resistant acrylic resin composition according to claim 1, characterized in that, It is made from the following raw materials in the following weight percentages: 25-35% methyl methacrylate, 10-20% butyl acrylate, 5-10% ethyl 2-perfluorodecyl methacrylate, 5-10% hexamethylene diisocyanate, 0.5-2% initiator, 2-5% nano zinc oxide, and 20-40% xylene.

3. The highly corrosion-resistant acrylic resin composition according to claim 1, characterized in that, It is made from the following raw materials in the following weight percentages: 32% methyl methacrylate, 16% butyl acrylate, 8% ethyl 2-perfluorodecyl methacrylate, 6.5% hexamethylene diisocyanate, 1.5% initiator, 4% nano zinc oxide, and 32% xylene.

4. A highly corrosion-resistant acrylic resin composition according to any one of claims 1 to 3, characterized in that, The initiator is azobisisobutyronitrile.

5. A method for preparing a highly corrosion-resistant acrylic resin composition according to any one of claims 1 to 3, characterized in that, Includes the following steps: (1) Add xylene to a four-necked flask, introduce nitrogen gas, and heat to the controlled temperature; (2) Mix methyl methacrylate, butyl acrylate, ethyl 2-perfluorodecyl methacrylate and initiator evenly according to mass percentage and add them to the dropping pump; (3) After the temperature of the four-necked flask in step (1) is reached, keep it warm and then start adding the mixture from step (2). After adding all the mixture, keep it warm for a period of time. (4) When the heat preservation in step (3) is completed, cool down, add hexamethylene diisocyanate and nano zinc oxide, stir, and you will get the product.

6. The method for preparing a highly corrosion-resistant acrylic resin composition according to claim 5, characterized in that, Step (1) Control the temperature to 75~85℃.

7. The method for preparing a highly corrosion-resistant acrylic resin composition according to claim 5, characterized in that, The initiator is azobisisobutyronitrile.

8. The method for preparing a highly corrosion-resistant acrylic resin composition according to claim 5, characterized in that, In step (3), when the temperature of the four-necked flask in step (1) reaches the controlled temperature of 75~85℃, after keeping it warm for 0.5 hours, the mixture from step (2) is added dropwise. The addition is completed in 5 hours, and then kept warm for 1 hour.

9. The method for preparing a highly corrosion-resistant acrylic resin composition according to claim 5, characterized in that, In step (4), after the heat preservation in step (3) is completed, the temperature is lowered to 60°C, hexamethylene diisocyanate and nano zinc oxide are added, and the mixture is stirred for 2 hours to obtain the final product.

10. A metal protective paint formulation, characterized in that, It is made from the following raw materials: 55 parts of resin prepared by any one of claims 5 to 9, 15 parts of titanium dioxide, 1 part of ultraviolet absorber Tinuvin 1130, 0.5 parts of light stabilizer Tinuvin 292, 8 parts of anti-corrosion filler mica powder, 0.5 parts of leveling agent BYK-306, and 15 parts of xylene.