High-durability acrylic emulsion as well as preparation method and application thereof

Abstract

The invention relates to the technical field of functional coatings, and particularly discloses a high-durability acrylic emulsion which comprises the following components in parts by weight: 50-70 parts of an acrylate monomer, 10-15 parts of styrene, 5-15 parts of a functional monomer, 3-5 parts of methacrylic acid, 2-4 parts of a cross-linking agent, 1.5-3 parts of an anti-aging agent, 0.4-0.7 part of an emulsifier and 0.4-0.7 part of an initiator. The acrylate monomer is selected from one or more of n-octyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate and isobornyl methacrylate; the functional monomer is prepared from glycidyl methacrylate, 2-(perfluorooctyl) ethyl methacrylate and methacrylic acid-2, 2, 6, 6-tetramethyl-4-piperidyl ester according to the weight ratio of 1: (0.3 to 0.8): (2 to 5). When the acrylic emulsion is coated on the surface of a protective product, good wear resistance, solvent resistance and aging resistance can be obtained.

Description

Technical Field

[0001] This application relates to the field of functional coatings technology, specifically to a high-durability acrylic emulsion, its preparation method, and its application. Background Technology

[0002] Gloves are a common protective, work, and everyday wear item, and their surface coating is key to improving their performance. Acrylic emulsions are widely used in the preparation of glove surface coatings due to their good film-forming properties, moderate cost, and excellent weather resistance.

[0003] Currently, the main types of coatings for gloves on the market are as follows: First, pure acrylic emulsions, which are polymerized from pure acrylate monomers. These emulsions have good film-forming properties and excellent weather resistance, forming a uniform and continuous film on the glove surface. This effectively blocks the penetration of external liquids, dust, and other substances, and has good resistance to ultraviolet rays and oxidation. However, their resistance to organic solvents is relatively weak. When in contact with organic solvents such as gasoline and alcohol, swelling and dissolution may occur, affecting the performance and protective effect of the gloves. Second, styrene-acrylate emulsions, which are emulsions copolymerized from styrene and acrylate monomers. Compared to pure acrylic emulsions, styrene-acrylate emulsions have higher hardness after film formation, providing better support and abrasion resistance for gloves, making them less prone to deformation and wear during use. However, their aging resistance is poor. Under long-term ultraviolet radiation and oxidation, styrene segments are prone to degradation, leading to a decline in the performance of the emulsion, such as yellowing and chalking, affecting the appearance and service life of the gloves.

[0004] Therefore, there is an urgent need to develop an acrylic emulsion for gloves with good wear resistance, excellent solvent protection, and superior aging resistance, so that the coating formed on the glove surface can still maintain good wear resistance and protection under frequent wearing and folding, and significantly extend the service life of the gloves. Summary of the Invention

[0005] To overcome the problem that existing acrylic emulsions cannot simultaneously achieve multiple effects, this application provides a high-durability acrylic emulsion, its preparation method, and its application.

[0006] In a first aspect, this application provides a high-durability acrylic emulsion, employing the following technical solution: A high-durability acrylic emulsion comprises the following components in parts by weight: 50-70 parts of acrylate monomers, 10-15 parts of styrene, 5-15 parts of functional monomers, 3-5 parts of methacrylic acid, 2-4 parts of crosslinking agent, 1.5-3 parts of anti-aging agent, 0.4-0.7 parts of emulsifier, and 0.4-0.7 parts of initiator; The acrylate monomers are selected from one or more of n-octyl acrylate, isooctyl acrylate, n-butyl methacrylate, and isobornyl methacrylate; The functional monomer is a mixture of glycidyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate in a weight ratio of 1:(0.3-0.8):(2-5).

[0007] This application utilizes the screening of acrylic monomers and the combination with specific functional monomers to prepare an acrylic emulsion exhibiting excellent wear resistance, solvent protection, and aging resistance. Specifically, acrylate monomers possess both good flexibility and high hardness, enabling them to synergistically enhance the coating's structural strength with styrene. Combined with the dense three-dimensional network formed by the crosslinking agent, this effectively improves the coating's density and mechanical stability, thereby enhancing its wear resistance and solvent resistance. The functional monomers form a low-surface-energy hydrophobic and oleophobic layer on the coating surface, significantly reducing the wettability of water and organic solvents. Furthermore, the dense structure constructed by the crosslinking agent reduces coating porosity, effectively blocking solvent molecule penetration and achieving highly efficient protection against water and various organic solvents, preventing swelling and peeling of the coating due to solvent erosion. In addition, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate ester synergistically works with anti-aging agents to efficiently and cyclically capture free radicals generated by polymer degradation, fundamentally inhibiting photo-oxidative aging, delaying yellowing, embrittlement, and cracking of the coating, and significantly improving long-term stability. In summary, the acrylic emulsion provided in this application achieves excellent wear resistance, reliable solvent protection, and long-lasting aging resistance in its coating through structural complementarity and functional synergy among its components, thus fully meeting the long-term stability requirements of protective equipment such as gloves in complex environments.

[0008] Optionally, the weight ratio of glycidyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate is 1:(0.5-0.8):(3-4).

[0009] The acrylate monomer is a mixture of isooctyl acrylate and isobornyl methacrylate.

[0010] Optionally, the weight ratio of isooctyl acrylate to isobornyl methacrylate is 2:(0.8-1.5).

[0011] Optionally, the weight ratio of glycidyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate is 1:0.5:3.

[0012] Optionally, the crosslinking agent is melamine-formaldehyde resin and a blocked isocyanate crosslinking agent.

[0013] Optionally, the anti-aging agent is ultraviolet absorber UV-531 and antioxidant 1010.

[0014] Optionally, the emulsifier is a nonionic emulsifier or anionic emulsifier; the initiator is ammonium persulfate.

[0015] Secondly, this application provides a method for preparing a high-durability acrylic emulsion, comprising the following steps: dissolving an initiator in water and refluxing and heating to 80-85°C under stirring; maintaining the above reaction temperature; preparing monomer pre-emulsions by separately preparing acrylate monomers, styrene, functional monomers, and methacrylic acid with emulsifiers and water, and then adding them dropwise to the above initiator aqueous solution, controlling the dropwise addition time to 1-2 hours; then adding crosslinking agents and anti-aging agents, and continuing the reaction for 5-12 hours; finally adjusting the pH to 7-8 to obtain a high-durability acrylic emulsion.

[0016] Thirdly, this application provides the application of a high-durability acrylic emulsion in gloves and protective equipment.

[0017] In summary, this application has the following beneficial effects: 1. This application uses one or more acrylate monomers selected from n-octyl acrylate, isooctyl acrylate, n-butyl methacrylate, and isobornyl methacrylate as the main components, and selects a mixture of glycidyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate in a weight ratio of 1:(0.3-0.8):(2-5) as the functional monomers, thereby obtaining an acrylic emulsion with good wear resistance, excellent solvent protection effect, and excellent aging resistance. When coated on the surface of gloves and other protective products, it can form a dense protective film, significantly improving the wear resistance, solvent resistance, and high temperature UV aging resistance of gloves, and ensuring the long-term stability requirements of gloves and other protective products in complex environments.

[0018] 2. This application further selects a mixture of isooctyl acrylate and isobornyl methacrylate in a weight ratio of 2:(0.8-1.5) as acrylate monomers, and glycidyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate in a weight ratio of 1:(0.5-0.8):(3-4). The resulting high-durability acrylic emulsion has better abrasion resistance and solvent resistance. After being coated on gloves, the abrasion amount after abrasion resistance test is only 7.5-9.6 mg (<10 mg), the water contact angle is 131.4-135.6° (>130°), the swelling rate after ethanol / acetone immersion is only 0.59-0.81% (≤0.80%), and the swelling rate after toluene / ethyl acetate immersion is 1.81-1.93% (≤1.95%). Detailed Implementation

[0019] This application provides a high-durability acrylic emulsion comprising the following components in parts by weight: 50-70 parts of acrylate monomers, 10-15 parts of styrene, 5-15 parts of functional monomers, 2-4 parts of crosslinking agent, 1.5-3 parts of anti-aging agent, 0.4-0.7 parts of emulsifier, and 0.4-0.7 parts of initiator; The acrylate monomers are selected from one or more of n-octyl acrylate, isooctyl acrylate, n-butyl methacrylate, and isobornyl methacrylate; the functional monomers are a mixture of glycidyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate in a weight ratio of 1:(0.3-0.8):(2-5). Further, the acrylate monomers are a mixture of isooctyl acrylate and isobornyl methacrylate; the weight ratio of isooctyl acrylate to isobornyl methacrylate is 2:(0.8-1.5).

[0020] The method for preparing a high-durability acrylic emulsion provided in this application includes the following steps: dissolving an initiator in water and refluxing and heating it to 80-85°C under stirring; maintaining the above reaction temperature; preparing monomer pre-emulsions by separately preparing acrylate monomers, styrene, functional monomers, and methacrylic acid with emulsifiers and water, and then adding them dropwise to the above initiator aqueous solution, controlling the dropwise addition time to 1-2 hours; then adding crosslinking agents and anti-aging agents, and continuing the reaction for 5-12 hours; finally adjusting the pH to 7-8 to obtain a high-durability acrylic emulsion.

[0021] In this application, the CAS number of glycidyl methacrylate is 106-91-2, and that of 2-(perfluorooctyl)ethyl methacrylate is 1996-88-9; the CAS number of 2,2,6,6-tetramethyl-4-piperidinyl methacrylate is 31582-45-3; the raw materials, reagents, solvents, etc. used in this application are all commercially available.

[0022] The present application will be further described in detail below with reference to embodiments and performance testing. Example 1

[0023] Example 1 provides a highly durable acrylic emulsion.

[0024] The preparation method of the above-mentioned high-durability acrylic emulsion includes the following steps: 0.5g of ammonium persulfate is added to 50mL of water, and under stirring, the mixture is refluxed and heated to 80℃, maintaining the above reaction temperature; then 60g of acrylate monomer (n-octyl acrylate), 0.1g of emulsifier SDBS, 0.1g of emulsifier 061 (nonionic emulsifier, purchased from Jingzhijie Beijing Technology Co., Ltd.) and 50g of water are mixed to obtain an acrylate monomer pre-emulsion; 13g of styrene, 0.05g of emulsifier SDBS, 0.05g of emulsifier 061 and 10g of water are mixed to obtain a styrene pre-emulsion; 10g of... A functional monomer (a mixture of glycidyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate in a weight ratio of 1:0.5:3), 0.1 g of emulsifier SDBS, 0.1 g of emulsifier 061, and 20 g of water were mixed to obtain a functional monomer preemulsion. A methacrylic acid preemulsion was obtained by mixing 4 g of methacrylic acid, 0.02 g of emulsifier SDBS, 0.03 g of emulsifier 061, and 5 g of water. The above preemulsions were then added dropwise to an aqueous solution of a thermal initiator, with the total addition time controlled at approximately 1.5 h. Then, 0.5 g of [a specific type of preemulsion] was added. Melamine-formaldehyde resin (Yadina 0003), 1g of blocked isocyanate crosslinking agent (JL-WEB), 1g of ultraviolet absorber UV-531 and 1g of antioxidant 1010 were reacted for 10 hours. Finally, the pH was adjusted to 7.5 with ammonia water to obtain a high-durability acrylic emulsion. Examples 2-6

[0025] Examples 2-6 each provide a highly durable acrylic emulsion.

[0026] The difference between the above embodiments and Embodiment 1 is that the types and ratios of acrylate monomers are as shown in Table 1 below.

[0027] Table 1. Types and proportions of acrylate monomers in Examples 1-6 Examples 7-11

[0028] Examples 7-11 each provide a highly durable acrylic emulsion.

[0029] The difference between the above embodiments and Embodiment 1 is that the proportions of the functional units are as shown in Table 2 below.

[0030] Table 2. Ratios of functional monomers in Examples 5 and 7-11 Comparative Example 1

[0031] Comparative Example 1 provides a highly durable acrylic emulsion.

[0032] The difference between the above comparative example and Example 1 is that the acrylate monomers are methyl methacrylate and butyl acrylate in a weight ratio of 1:1. Comparative Example 2

[0033] Comparative Example 2 provides a highly durable acrylic emulsion.

[0034] The difference between the above comparative example and Example 1 is that the functional monomers are glycidyl methacrylate and 2-(perfluorooctyl)ethyl methacrylate in a weight ratio of 1:3.5. Comparative Example 3

[0035] Comparative Example 3 provides a highly durable acrylic emulsion.

[0036] The difference between the above comparative example and Example 1 is that the functional monomers are glycidyl methacrylate and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate in a weight ratio of 1:3.5. Comparative Example 4

[0037] Comparative Example 4 provides a highly durable acrylic emulsion.

[0038] The difference between the above comparative example and Example 1 is that the functional monomers are 1.5:3 of 2-(perfluorooctyl)ethyl methacrylate and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate. Performance testing

[0039] The high-durability acrylic emulsions obtained in Examples 1-11 and Comparative Examples 1-4 were coated on the outer surface of PVC gloves with a coating thickness of 1.5±0.2μm to obtain gloves to be tested. The following performance tests were performed on each sample, and the results are shown in Table 3 below.

[0040] (1) Abrasion resistance: ASTM D4060; Taber abrasion resistant, CS-10 wheel 1000g, 1000 revolutions; (2) Water resistance: Using a contact angle meter, deionized water was dropped onto the coating surface of the glove to test the static water contact angle.

[0041] (3) Resistance to organic solvents: After coating, the open end of the gloves to be tested is tied with a rubber band, and then they are immersed in a 1:1 ethanol / acetone mixture (immersion for 24 hours) and a 1:1 toluene / ethyl acetate mixture (immersion for 8 hours). After immersion, the gloves are taken out, the surface solvent is dried and weighed, and the swelling rate is calculated.

[0042] (4) Aging resistance: Place each glove to be tested in an aging chamber and age it at 80°C and under ultraviolet light for 1000 hours. Observe whether there are yellowing, powdering or other phenomena on the surface of the gloves, and test the adhesion level of the coating after the gloves are aged.

[0043] Table 3 Performance test results of various acrylic emulsions after coating gloves

[0044] According to the test results in Table 3, after the high-durability acrylic emulsions obtained in Examples 1-11 were coated onto the gloves, the wear amount after the abrasion resistance test was only 7.5-12.1 mg, the water contact angle was 117.4-135.6°, the swelling rate after immersion in ethanol / acetone was 0.59-1.43%, and the swelling rate after immersion in toluene / ethyl acetate was 1.81-2.76%. After high-temperature ultraviolet aging, the surface coating of the gloves did not show yellowing or chalking, and the adhesion grade of the coating was 0-1. When the high-durability acrylic emulsions obtained in Comparative Examples 1-4 were coated onto gloves, the wear amount after abrasion resistance tests was only 16.7-28.3 mg, the water contact angle was 97.2-105.6°, the swelling rate after immersion in ethanol / acetone was 2.53-3.12%, and the swelling rate after immersion in toluene / ethyl acetate was 4.28-5.53%. After high-temperature UV aging, the surface coating of the gloves showed slight yellowing or chalking, and the adhesion grade of the coating was 1-2. Therefore, this application uses one or more acrylate monomers selected from n-octyl acrylate, isooctyl acrylate, n-butyl methacrylate, and isobornyl methacrylate as the main components, and selects a mixture of glycidyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate in a weight ratio of 1:(0.3-0.8):(2-5) as the functional monomers, thereby obtaining an acrylic emulsion with good wear resistance, excellent solvent protection effect, and excellent aging resistance. When coated on the surface of gloves and other protective products, it can form a dense protective film, significantly improving the wear resistance, solvent resistance, and high temperature UV aging resistance of gloves, and ensuring the long-term stability requirements of gloves and other protective products in complex environments.

[0045] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A high-durability acrylic emulsion, characterized in that, It includes the following components in parts by weight: 50-70 parts of acrylate monomers, 10-15 parts of styrene, 5-15 parts of functional monomers, 3-5 parts of methacrylic acid, 2-4 parts of crosslinking agent, 1.5-3 parts of anti-aging agent, 0.4-0.7 parts of emulsifier, and 0.4-0.7 parts of initiator; The acrylate monomers are selected from one or more of n-octyl acrylate, isooctyl acrylate, n-butyl methacrylate, and isobornyl methacrylate; The functional monomer is a mixture of glycidyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate in a weight ratio of 1:(0.3-0.8):(2-5).

2. The high-durability acrylic emulsion according to claim 1, characterized in that, The acrylate monomer is a mixture of isooctyl acrylate and isobornyl methacrylate.

3. The high-durability acrylic emulsion according to claim 2, characterized in that, The weight ratio of isooctyl acrylate to isobornyl methacrylate is 2:(0.8-1.5).

4. The high-durability acrylic emulsion according to claim 1, characterized in that, The weight ratio of glycidyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate and 2,2,6,6-tetramethyl-4-piperidinyl methacrylate is 1:0.5:

3.

5. The high-durability acrylic emulsion according to claim 1, characterized in that, The crosslinking agent is melamine-formaldehyde resin and a blocked isocyanate crosslinking agent.

6. The high-durability acrylic emulsion according to claim 1, characterized in that, The anti-aging agents are UV absorber UV-531 and antioxidant 1010.

7. The high-durability acrylic emulsion according to claim 1, characterized in that, The emulsifier is a nonionic emulsifier and anionic emulsifier; the initiator is ammonium persulfate.

8. The method for preparing the high-durability acrylic emulsion according to any one of claims 1-7, characterized in that, The process includes the following steps: dissolving the initiator in water and refluxing to 80-85°C with stirring; maintaining the above reaction temperature; preparing monomer pre-emulsions by separately preparing acrylate monomers, styrene, functional monomers, and methacrylic acid with emulsifiers and water, and then adding them dropwise to the above initiator aqueous solution, controlling the dropwise addition time to 1-2 hours; then adding crosslinking agents and anti-aging agents, and continuing the reaction for 5-12 hours; finally adjusting the pH to 7-8 to obtain a high-durability acrylic emulsion.

9. The use of the high-durability acrylic emulsion as described in any one of claims 1-7 in gloves and protective equipment.

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