High-wear-resistance acrylic resin and preparation method thereof

Abstract

The invention discloses high-wear-resistance HFBMA (hexafluorobutyl methacrylate) acrylic resin and a preparation method thereof. The high-wear-resistance HFBMA acrylic resin is prepared from the following components in percentage by mass: 30 to 40 percent of styrene, 8 to 15 percent of hydroxypropyl ester, 8 to 15 percent of propyl butyl ester, 0.3 to 1.5 percent of methacrylic acid, 0.5 to 2 percent of initiator, 3 to 10 percent of hexafluorobutyl methacrylate (HFBMA), 2 to 8 percent of organic silicon monomer or POSS (polyhedral oligomeric silsesquioxane) and 25 to 35 percent of xylene. According to the experiment, the optimal raw material composition and proportion are obtained through screening of a large number of experiments, the optimal synthesis process is obtained through optimization of a large number of experiments, and the conversion rate reaches 98.8% or above. The acrylic resin disclosed by the invention has excellent wear resistance, weather resistance, chemical resistance, high hardness, high adhesive force and excellent hydrophobicity and anti-fouling performance, and the comprehensive performance is remarkably and technically improved.

Description

Technical Field

[0001] This invention relates to a high abrasion-resistant acrylic resin, specifically to a high abrasion-resistant acrylic resin with strong abrasion resistance, good weather resistance, chemical resistance, hydrophobicity and antifouling properties, and excellent thermal stability, as well as its preparation method, belonging to the field of polymer resin technology. Background Technology

[0002] Acrylic resins possess characteristics such as good transparency, glossy color, good adhesion, and good toughness, making them widely used in coating materials. However, under certain conditions, the use of ordinary acrylic resins exhibits certain performance defects, primarily poor performance in water resistance, stain resistance, weather resistance, and chemical resistance, which hinders the development and application of acrylic resins. Therefore, developing a high-performance acrylic resin with superior overall performance is of significant application value. Summary of the Invention

[0003] Purpose of the invention: The purpose of this invention is to address the shortcomings of existing technologies by introducing hexafluorobutyl methacrylate (HFBMA) and organosilicon monomers / POSS, optimizing the composition of acrylic resin monomers and initiators, and preparing acrylic resins with strong wear resistance, good weather resistance, chemical resistance, hydrophobicity and antifouling properties, and excellent thermal stability.

[0004] Technical solution: To achieve the above objectives, the technical solution adopted by this invention is as follows: A high abrasion-resistant acrylic resin is made from the following raw materials in the following weight percentages: styrene, hydroxypropyl ester, butyl propylene ester, methacrylic acid, initiator, hexafluorobutyl methacrylate (HFBMA), organosilicon monomer or POSS, and xylene.

[0005] As a preferred embodiment, the high abrasion-resistant acrylic resin described above is made from the following raw materials in the indicated weight percentages: 30-40% styrene, 8-15% hydroxypropyl ester, 8-15% propylbutyl ester, 0.3-1.5% methacrylic acid, 0.5-2% initiator, 3-10% hexafluorobutyl methacrylate (HFBMA), 2-8% organosilicon monomer or POSS, and 25-35% xylene.

[0006] As a preferred embodiment, the high abrasion-resistant acrylic resin described above is made from the following raw materials in the indicated weight percentages: 35.0% styrene, 11.0% hydroxypropyl ester, 11.0% butyl propylene ester, 0.6% methacrylic acid, 1.8% initiator, 6.0% hexafluorobutyl methacrylate (HFBMA), 4.6% POSS, and 30.0% xylene.

[0007] As a preferred embodiment, the initiator of the above-described high abrasion-resistant acrylic resin is dicumyl peroxide. As a preferred embodiment, in the above-described method for preparing a high abrasion-resistant acrylic resin, the organosilicon monomer or POSS significantly improves the resin's abrasion resistance, heat resistance, and hydrophobicity.

[0008] The present invention discloses a method for preparing a high abrasion-resistant acrylic resin, comprising the following steps: (1) Add xylene solvent to the reaction apparatus and heat to reflux; (2) Mix styrene, hydroxypropyl ester, propylbutyl ester, methacrylic acid, hexafluorobutyl methacrylate (HFBMA), organosilicon monomer or POSS, and initiator evenly, and then add them to the dropping funnel. (3) When the temperature of the reaction apparatus in step (1) reaches reflux, start adding the mixture in step (2) dropwise. After the dropwise addition is complete, keep it warm for a period of time, then add the initiator and keep it warm for a period of time to obtain the final product.

[0009] As a preferred embodiment, the initiator of the above-described high abrasion-resistant acrylic resin is dicumyl peroxide. As a preferred embodiment, in the above-described method for preparing a high abrasion-resistant acrylic resin, the organosilicon monomer or POSS significantly improves the resin's abrasion resistance, heat resistance, and hydrophobicity.

[0010] As a preferred embodiment, a method for preparing a high wear-resistant acrylic resin is characterized in that, in step (3), when the temperature of the reaction device in step (1) reaches 137-140°C and reflux is started, the mixture in step (2) is added dropwise, and the dropwise addition is completed in 3.5-4 hours. After the dropwise addition is completed, the mixture is kept warm for 1 hour, and then an initiator is added and kept warm for 1-1.5 hours to obtain the final product.

[0011] Beneficial effects: Compared with the prior art, the present invention has the following advantages: This invention significantly improves the overall performance of acrylic resins by introducing hexafluorobutyl methacrylate (HFBMA) and organosilicon monomers / POSS. HFBMA imparts excellent chemical resistance, hydrophobicity, and thermal stability to the resin; the introduction of POSS or organosilicon monomers further enhances the resin's abrasion resistance, hardness, and heat resistance. The acrylic resin prepared by this invention exhibits high conversion rate (≥98.8%), high coating adhesion, high hardness, good flexibility, and excellent abrasion resistance, while also possessing good weather resistance, stain resistance, and solvent resistance. Detailed Implementation

[0012] Example 1 (Example of the present invention) 1. A high abrasion-resistant acrylic resin, which is made from the following raw materials in the following weight percentages: 35.0% styrene, 11.0% hydroxypropyl ester, 11.0% butyl propylene ester, 0.6% methacrylic acid, 1.8% initiator (diisopropylbenzene peroxide), 6.0% hexafluorobutyl methacrylate (HFBMA), 4.6% POSS (octa(methacryloyloxypropyl)silsesquioxane), and 30.0% xylene.

[0013] 2. The preparation method of the high abrasion resistance acrylic resin of the present invention includes the following steps: (1) Add 540 g of xylene to the reaction apparatus, start stirring and heat to reflux (137-140 °C). (2) Mix 10.8 g of methacrylic acid, 198 g of hydroxypropyl ester, 198 g of propyl butyl ester, 630 g of styrene, 108 g of hexafluorobutyl methacrylate, 82.8 g of POSS (octa(methacryloyloxypropyl)silsesquioxane), and 32.4 g of initiator dicumyl peroxide (DCP) evenly and add them to a dropping funnel; (3) When the temperature of the reaction apparatus in step (1) reaches 137-140℃ and is refluxed, the mixed monomer and initiator in step (2) are added dropwise. The addition is completed in 4 hours. After the addition is completed, the temperature is maintained for 1 hour. Then, 0.6 g of dicumyl peroxide (DCP) is added and the temperature is maintained for another 1.5 hours. The final reaction conversion rate can reach 99.0%, and the resin solid content is 66.0%.

[0014] 3. Mix the obtained high-abrasion-resistant acrylic resin with the various ingredients listed in Table 1 according to the specified proportions, and stir using a high-speed disperser for 30 minutes to prepare an acrylic resin industrial varnish with a film thickness of approximately 50 micrometers. The performance test results are shown in Table 2.

[0015] Table 1. Composition of Acrylic Resin Industrial Varnish Formulation Raw material name Weight (g) Example 1 Acrylic Resin 69 Curing agent N3390 2 Toluene 10 Ethyl acetate 19 Defoamer AX3301 0.1 Leveling agent FM5410 0.1 Table 2 Results of Coating Film Performance Tests Performance indicators result Appearance Smooth and free of particles Hardness (pencil scratch) 4H Impact (recoil) (kg.cm) 55 Adhesion (circle test) Level 1 luster 96 Wear Index 42 Contact angle (°) 108 Ethanol wiping resistance (times) ≥500 The above test methods are as follows: Hardness (pencil scratch) is determined according to GB / T6739-1996; Impact (recoil) is determined according to GB / T1732-93; Adhesion (circle method) is determined according to GB / T1720-79 (89); Gloss is determined according to GB / T 9754-2007 (60°); Abrasion index is determined according to GB / T1768-79 (89); Contact angle is determined according to GB / T 30693-2014; Ethanol wiping resistance is determined according to GB / T 23989-2009.

[0016] Comparative Example 1 (HFBMA only, without POSS) 1. An acrylic resin made from the following raw materials in weight percentages: 36.0% styrene, 12.0% hydroxypropyl ester, 12.0% butyl propylene ester, 0.6% methacrylic acid, 1.8% initiator (dicumyl peroxide), 8.6% hexafluorobutyl methacrylate (HFBMA), and 29.0% xylene.

[0017] 2. The preparation method is the same as in Example 1, but without the addition of POSS.

[0018] 3. The prepared acrylic resin was mixed with the same ingredients and proportions as in Table 1 of Example 1, and stirred for 30 minutes using a high-speed disperser to prepare an acrylic resin industrial varnish with a film thickness of approximately 50 micrometers. The performance was tested as shown in Table 3.

[0019] Table 3 Performance test results Performance indicators result Appearance Smooth and free of particles Hardness (pencil scratch) 2H Impact (recoil) (kg.cm) 45 Adhesion (circle test) Level 1-2 luster 92 Wear Index 68 Contact angle (°) 98 Ethanol wiping resistance (times) 300

[0020] Comparative Example 2 (with POSS only, without HFBMA) 1. An acrylic resin made from the following raw materials in weight percentages: 37.0% styrene, 11.5% hydroxypropyl ester, 11.5% butyl propylene ester, 0.6% methacrylic acid, 1.8% initiator (diisopropylbenzene peroxide), 7.6% POSS (octa(methacryloyloxypropyl)silsesquioxane), and 30.0% xylene.

[0021] 2. The preparation method is the same as in Example 1, but HFBMA is not added.

[0022] 3. The prepared acrylic resin was mixed with the same ingredients and proportions as in Table 1 of Example 1, and stirred for 30 minutes using a high-speed disperser to prepare an acrylic resin industrial varnish with a film thickness of approximately 50 micrometers. The performance was tested as shown in Table 4.

[0023] Table 4 Performance Test Results Performance indicators result Appearance Smooth and free of particles Hardness (pencil scratch) 3H Impact (recoil) (kg.cm) 50 Adhesion (circle test) Level 1 luster 94 Wear Index 58 Contact angle (°) 92 Ethanol wiping resistance (times) 250

[0024] Comparative Example 3 (excluding HFBMA and POSS) 1. An acrylic resin made from the following raw materials in weight percentages: 37.0% styrene, 13.0% hydroxypropyl ester, 13.0% butyl propylene ester, 0.6% methacrylic acid, 1.8% initiator (diisopropylbenzene peroxide), and 34.6% xylene.

[0025] 2. The preparation method is the same as in Example 1, but HFBMA and POSS are not added.

[0026] 3. The prepared acrylic resin was mixed with the same ingredients and proportions as those in Table 1 of Example 1, and stirred for 30 minutes using a high-speed disperser to prepare an acrylic resin industrial varnish with a film thickness of approximately 50 micrometers. The performance was tested as shown in Table 5.

[0027] Table 5 Performance Test Results Performance indicators result Appearance Smooth and free of particles Hardness (pencil scratch) H Impact (recoil) (kg.cm) 35 Adhesion (circle test) Level 2 luster 88 Wear Index 95 Contact angle (°) 78 Ethanol wiping resistance (times) 120

[0028] The above embodiments show that Embodiment 1 of the present invention (containing both HFBMA and POSS) is significantly superior to the comparative example in terms of hardness, wear resistance, hydrophobicity, and chemical resistance, demonstrating the synergistic enhancement effect of HFBMA and POSS.

[0029] 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 high abrasion-resistant acrylic resin, characterized in that, It is made from the following raw materials: styrene, hydroxypropyl ester, propylbutyl ester, methacrylic acid, initiator, hexafluorobutyl methacrylate, organosilicon monomer or POSS, and xylene.

2. The high abrasion-resistant acrylic resin according to claim 1, characterized in that, It is made from the following raw materials in the following weight percentages: 30-40% styrene, 8-15% hydroxypropyl ester, 8-15% propylbutyl ester, 0.3-1.5% methacrylic acid, 0.5-2% initiator, 3-10% hexafluorobutyl methacrylate, 2-8% organosilicon monomer or POSS, and 25-35% xylene.

3. The high abrasion-resistant acrylic resin according to claim 1, characterized in that, It is made from the following raw materials in the following weight percentages: 35.0% styrene, 11.0% hydroxypropyl ester, 11.0% propylbutyl ester, 0.6% methacrylic acid, 1.8% initiator, 6.0% hexafluorobutyl methacrylate (HFBMA), 4.6% organosilicon monomer or POSS, and 30.0% xylene.

4. The high abrasion-resistant acrylic resin according to claim 1, characterized in that, The initiator is dicumyl peroxide.

5. A high abrasion-resistant acrylic resin according to any one of claims 1-4, characterized in that, The organosilicon monomer is vinyltrimethoxysilane, and the POSS is octa(methacryloyloxypropyl)silsesquioxane.

6. A method for preparing a high abrasion-resistant acrylic resin according to any one of claims 1 to 5, characterized in that, Includes the following steps: (1) Add xylene solvent to the reaction apparatus and heat to reflux; (2) Mix styrene, hydroxypropyl ester, propylbutyl ester, methacrylic acid, hexafluorobutyl methacrylate, organosilicon monomer or POSS, and initiator evenly, and then add them to the dropping funnel; (3) When the temperature of the reaction apparatus in step (1) reaches reflux, start adding the mixture in step (2) dropwise. After the dropwise addition is complete, keep it warm for a period of time, then add the initiator and keep it warm for a period of time to obtain the final product.

7. The method for preparing a high abrasion-resistant acrylic resin according to claim 6, characterized in that, The initiator is dicumyl peroxide.

8. The method for preparing a high abrasion-resistant acrylic resin according to claim 6, characterized in that, In step (3), when the temperature of the reaction apparatus in step (1) reaches 137-140℃, reflux begins, and the mixture from step (2) is added dropwise. The dropwise addition is completed in 3.5-4 hours. After the dropwise addition is completed, the mixture is kept warm for 1 hour. Then, the initiator is added and kept warm for 1-1.5 hours to obtain the final product.

9. The method for preparing a high abrasion-resistant acrylic resin according to claim 6, characterized in that, The POSS is octa(methacryloyloxypropyl)silsesquioxane.