Hydrophobic anti-adhesion acrylic acid copolymer emulsion as well as preparation method and application thereof
By preparing a hydrophobic and anti-blocking acrylic copolymer emulsion, the problem of balancing hydrophobicity, anti-blocking and adhesion of acrylic emulsions has been solved, achieving a highly efficient protective effect, suitable for plastic, metal and wood surfaces.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-31
- Publication Date
- 2026-04-14
AI Technical Summary
Existing acrylic emulsions struggle to balance hydrophobicity, anti-blocking properties, and adhesion, resulting in coatings that are prone to peeling and have poor abrasion resistance during use, especially in their ineffective anti-sticking effect against highly adhesive substances.
Hydrophobic and anti-blocking acrylic copolymer emulsions are prepared by copolymerization using raw materials such as methyl methacrylate, fluorinated hydrophobic functional monomers, pentaerythritol triacrylate monoesterified with lauric acid, and triisopropylsilyl methacrylate. This forms a dense surface structure that is chemically bonded to the substrate, thereby improving the hydrophobicity and adhesion of the coating.
It achieves high hydrophobicity, long-lasting anti-blocking and strong adhesion. The coating is not easy to stick together when stacked, heated or pressured, and is suitable for high-performance waterproof coatings and high-end packaging films.
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Abstract
Description
Technical Field
[0001] This application relates to the field of functional coatings technology, specifically to a hydrophobic, anti-blocking acrylic copolymer emulsion, its preparation method, and its application. Background Technology
[0002] Acrylic ester emulsions are the core film-forming materials for preparing functional coatings on substrate surfaces in industrial and civilian fields due to their advantages such as good film-forming properties, excellent adhesion, environmental friendliness, convenient construction, and controllable cost. They have been widely used for surface protection of substrates such as metals, plastics, wood, and non-woven fabrics. Hydrophobicity, antifouling, and anti-adhesion are important surface protection requirements.
[0003] Currently, the main types of acrylic emulsions used to prepare hydrophobic anti-blocking coatings are as follows: First, pure acrylic emulsions prepared by emulsion polymerization of acrylic monomers. These emulsions have advantages such as good film-forming properties, excellent weather resistance, and low cost. However, their hydrophobicity is poor, and their anti-blocking effect is only effective for low-viscosity substances, with extremely poor anti-blocking effect on strongly adhesive substances such as tapes and self-adhesive labels. Second, silicone-modified acrylic emulsions. These emulsions combine the flexibility of acrylic esters with the hydrophobicity of silicone. However, the introduction of silicone groups leads to a decrease in the crosslinking density of the acrylic ester molecular chains. The coating's hardness, abrasion resistance, and solvent resistance deteriorate, and its adhesion to the substrate decreases significantly, leading to problems such as coating peeling and flaking. Thirdly, there are nanoparticle composite acrylic emulsions, which enhance the hydrophobicity of the emulsion by introducing inorganic particles such as nano-silica and titanium dioxide into the acrylic matrix. However, the inorganic particles in the above emulsions are prone to agglomeration, resulting in poor long-term stability of the emulsion. Moreover, after film formation, inorganic particles are prone to migrate and precipitate from the coating surface, causing poor time-dependent hydrophobic and anti-adhesion properties of the coating. After washing, wiping, or aging, the hydrophobic and anti-adhesion effects rapidly decay.
[0004] Therefore, there is an urgent need to develop an acrylic emulsion that can achieve high hydrophobicity, long-lasting anti-blocking properties, and high substrate adhesion to meet the industry's needs. Summary of the Invention
[0005] In order to overcome the problem that existing acrylic emulsions cannot simultaneously achieve hydrophobicity, anti-blocking properties, and adhesion, this application provides a hydrophobic and anti-blocking acrylic copolymer emulsion, its preparation method, and its application.
[0006] In a first aspect, this application provides a hydrophobic, anti-blocking acrylic copolymer emulsion, employing the following technical solution: A hydrophobic and anti-blocking acrylic copolymer emulsion comprises the following components in parts by weight: 50-70 parts of methyl methacrylate, 5-15 parts of fluorinated hydrophobic functional monomer, 3-8 parts of pentaerythritol triacrylate monoesterified with lauric acid, 3-5 parts of triisopropylsilyl methacrylate, 1-3 parts of emulsifier, and 0.5-1 parts of initiator.
[0007] This application utilizes the aforementioned raw materials to obtain an acrylic copolymer emulsion that combines excellent hydrophobicity, anti-blocking properties, and good substrate adhesion. This effectively solves the problem of existing acrylic emulsions struggling to achieve multiple properties simultaneously, making it particularly suitable for high-performance waterproof coatings, antifouling coatings, and high-end packaging films, with promising application prospects. Specifically: the fluorine in the fluorinated hydrophobic functional monomers can accumulate on the polymer film surface, thus endowing the coating with excellent hydrophobicity; the silicon-containing monomers in triisopropylsilyl methacrylate not only enhance the hydrophobic effect, but their silyl groups also help form a dense surface structure during film formation, effectively blocking water penetration and achieving durable hydrophobic properties; furthermore, the silyl groups can chemically bond with or form strong physical adsorption on the hydroxyl groups on the surface of various substrates (such as metals, glass, and certain plastics), thus firmly anchoring the material to the substrate while imparting hydrophobicity, overcoming the problem of easy detachment of traditional hydrophobic materials. Lauric acid monoesterified pentaerythritol triacrylate, as a multifunctional crosslinking agent, can form a moderately crosslinked network structure during polymerization, significantly improving the surface hardness, heat resistance, and compression set resistance of the coating. This makes it less likely for the coating or film to stick together when stacked, heated, or under pressure.
[0008] Optionally, the hydrophobic and anti-blocking acrylic copolymer emulsion comprises the following components in parts by weight: 50-70 parts of methyl methacrylate, 5-10 parts of fluorinated hydrophobic functional monomer, 5-8 parts of pentaerythritol triacrylate monoesterified with lauric acid, 3-5 parts of triisopropylsilyl methacrylate, 1-3 parts of emulsifier, and 0.5-1 parts of initiator.
[0009] Optionally, the hydrophobic and anti-blocking acrylic copolymer emulsion comprises the following components in parts by weight: 60 parts methyl methacrylate, 10 parts fluorinated hydrophobic functional monomer, 8 parts pentaerythritol triacrylate monoesterified with lauric acid, 4 parts triisopropylsilyl methacrylate, 2 parts emulsifier, and 0.8 parts initiator.
[0010] Optionally, the emulsifier is an anionic emulsifier and a nonionic emulsifier.
[0011] Optionally, the fluorinated hydrophobic functional monomer is selected from one or more of 1H,1H,2H,2H-perfluorodecyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, 2,2,2-trifluoroethyl methacrylate and tridecylfluorooctyl methacrylate.
[0012] Optionally, the fluorinated hydrophobic functional monomer is a mixture of 2,2,2-trifluoroethyl methacrylate and tridecylfluorooctyl methacrylate.
[0013] Optionally, the weight ratio of 2,2,2-trifluoroethyl methacrylate to tridecyl fluorooctyl methacrylate is 1:(0.5-2).
[0014] Secondly, this application provides a method for preparing a hydrophobic and anti-blocking acrylic copolymer emulsion, comprising the following steps: dissolving an initiator in water and refluxing and heating it to 80-85°C under stirring; preparing a pre-emulsion by mixing methyl methacrylate, fluorinated hydrophobic functional monomers, pentaerythritol triacrylate monoesterified with lauric acid, triisopropylsilyl methacrylate, and an emulsifier; adding the pre-emulsion dropwise to the above thermal initiator solution, completing the addition in 1-1.5 hours, continuing the reaction for 5-12 hours, finally adjusting the pH to 7-8, and filtering to obtain a hydrophobic and anti-blocking acrylic copolymer emulsion.
[0015] Thirdly, this application provides an application of a hydrophobic, anti-blocking acrylic copolymer emulsion in the surface protection of plastics, metals, and wood.
[0016] In summary, this application has the following beneficial effects: This application uses methyl methacrylate, fluorinated hydrophobic functional monomers, pentaerythritol triacrylate monoesterified with lauric acid, and triisopropylsilyl methacrylate as raw materials to prepare an acrylic copolymer emulsion with high hydrophobicity, long-lasting anti-blocking and strong adhesion. When coated on the surface of substrates such as plastics, metals, plastics, and wood, it can achieve long-lasting protection of the substrate surface. Detailed Implementation
[0017] This application provides a hydrophobic, anti-blocking acrylic copolymer emulsion comprising the following components in parts by weight: 50-70 parts methyl methacrylate, 5-15 parts fluorinated hydrophobic functional monomers, 3-8 parts pentaerythritol triacrylate monoesterified with laurate, 3-5 parts triisopropylsilyl methacrylate, 1-3 parts emulsifier, and 0.5-1 part initiator. Further, the hydrophobic, anti-blocking acrylic copolymer emulsion comprises the following components in parts by weight: 50-70 parts methyl methacrylate, 5-10 parts fluorinated hydrophobic functional monomers, 5-8 parts pentaerythritol triacrylate monoesterified with laurate, 3-5 parts triisopropylsilyl methacrylate, 1-3 parts emulsifier, and 0.5-1 part initiator.
[0018] The fluorinated hydrophobic functional monomer is selected from one or more of 1H,1H,2H,2H-perfluorodecyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and tridecylfluorooctyl methacrylate; further, the fluorinated hydrophobic functional monomer is a mixture of 2,2,2-trifluoroethyl methacrylate and tridecylfluorooctyl methacrylate; and even further, the weight ratio of 2,2,2-trifluoroethyl methacrylate to tridecylfluorooctyl methacrylate is 1:(0.5-2).
[0019] The method for preparing the hydrophobic and anti-blocking acrylic copolymer emulsion provided in this application includes the following steps: dissolving an initiator in water and refluxing and heating to 80-85°C under stirring; preparing a pre-emulsion by mixing methyl methacrylate, fluorinated hydrophobic functional monomers, pentaerythritol triacrylate monoesterified with lauric acid, triisopropylsilyl methacrylate, and an emulsifier; adding the pre-emulsion dropwise to the above thermal initiator solution, completing the addition in 1-1.5 hours, continuing the reaction for 5-12 hours, finally adjusting the pH to 7-8, and filtering to obtain the hydrophobic and anti-blocking acrylic copolymer emulsion.
[0020] In this application, the CAS number of triisopropylsilyl methacrylate is 134652-60-1, and the fluorinated hydrophobic functional monomers are selected from 1H,1H,2H,2H-perfluorodecyl acrylate (CAS number 27905-45-9), 2-(perfluorooctyl)ethyl methacrylate (CAS number 1996-88-9), 2,2,2-trifluoroethyl methacrylate (CAS number 407-47-6), and tridecafluorooctyl methacrylate (CAS number 2144-53-8). The raw materials, reagents, solvents, etc. used in this application are all commercially available.
[0021] The following describes this application in further detail with reference to preparation examples, embodiments, and performance testing. Preparation Example 1
[0022] Preparation Example 1 provides a pentaerythritol triacrylate monoesterified with lauric acid.
[0023] The preparation method of the above-mentioned pentaerythritol triacrylate monoesterified with lauric acid includes the following steps: 59.7g of pentaerythritol triacrylate, 21.0g of lauric acid, 1.0g of p-toluenesulfonic acid and 0.3g of hydroquinone are added to a 250mL three-necked flask equipped with a condenser and a thermometer; then nitrogen gas is introduced and the system is heated to 135℃ and reacted for 8h; then the reaction solution is cooled to 30℃, washed 3 times with saturated sodium carbonate aqueous solution, and then washed 2 times with deionized water; the organic phase is dried and rotary evaporated to obtain a transparent viscous liquid pentaerythritol triacrylate monoesterified with lauric acid. Example 1
[0024] Example 1 provides a hydrophobic, anti-blocking acrylic copolymer emulsion.
[0025] The preparation method of the above-mentioned hydrophobic and anti-blocking acrylic copolymer emulsion includes the following steps: First, 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 methyl methacrylate, 10g of fluorinated hydrophobic functional monomer (1H,1H,2H,2H-perfluorodecyl acrylate), 5g of pentaerythritol triacrylate monoesterified with lauric acid (Preparation Example 1), 4g of triisopropylsilyl methacrylate, 1.5g of emulsifier SDBS, 0.5g of emulsifier 061 (nonionic emulsifier, purchased from Jingzhijie Beijing Technology Co., Ltd.), and 50g of water are mixed to prepare a pre-emulsion; the pre-emulsion is added dropwise to the above-mentioned thermal initiator solution, and the addition is completed in about 1.5h, and the reaction continues for 10h; finally, the pH is adjusted to 7.5 with ammonia water, and after filtration, the hydrophobic and anti-blocking acrylic copolymer emulsion is obtained. Example 2
[0026] Example 2 provides a hydrophobic, anti-blocking acrylic copolymer emulsion.
[0027] The difference between the above embodiments and Embodiment 1 is that the amount of fluorinated hydrophobic functional monomer (1H,1H,2H,2H-perfluorodecyl acrylate) added is 5g, and the amount of pentaerythritol triacrylate monoesterified with lauric acid added is 8g. Example 3
[0028] Example 3 provides a hydrophobic, anti-blocking acrylic copolymer emulsion.
[0029] The difference between the above embodiment and Example 1 is that the amount of fluorinated hydrophobic functional monomer (1H,1H,2H,2H-perfluorodecyl acrylate) added is 15g, and the amount of pentaerythritol triacrylate monoesterified with lauric acid added is 3g. Example 4-11
[0030] Examples 4-11 provide a hydrophobic, anti-blocking acrylic copolymer emulsion.
[0031] The difference between the above embodiments and Embodiment 1 is that the types and ratios of fluorinated hydrophobic functional monomers are as shown in Table 1 below.
[0032] Table 1. Types and proportions of fluorinated hydrophobic functional monomers used in Examples 4-11 Comparative Example 1
[0033] Comparative Example 1 provides a hydrophobic, anti-blocking acrylic copolymer emulsion.
[0034] The difference between the above comparative example and Example 1 is that pentaerythritol triacrylate monoesterified laurate was replaced with an equal amount of methyl methacrylate. Comparative Example 2
[0035] Comparative Example 2 provides a hydrophobic, anti-blocking acrylic copolymer emulsion.
[0036] The difference between the above comparative example and Example 1 is that the fluorinated hydrophobic functional monomer is replaced with an equal amount of methyl methacrylate. Comparative Example 3
[0037] Comparative Example 3 provides a hydrophobic, anti-blocking acrylic copolymer emulsion.
[0038] The difference between the above comparative example and Example 1 is that triisopropylsilyl methacrylate was replaced with an equal amount of methyl methacrylate. Performance testing
[0039] The hydrophobic, anti-adhesion acrylic copolymer emulsions obtained in Examples 1-11 and Comparative Examples 1-2 were coated on the outer surface of PVC gloves, with a coating thickness of 1.5 ± 0.2 μm. The following performance tests were performed, and the results are shown in Table 3 below.
[0040] (1) Hydrophobicity: Deionized water was dropped onto the coating surface of the glove using a contact angle meter to test the static water contact angle.
[0041] (2) Anti-adhesion: Overlap the coated surfaces of two gloves and apply 0.5 kg / cm² of coating. 2 The pressure was applied, and then the film was placed in a constant temperature chamber at 50°C for 24 hours. After cooling to room temperature, the two gloves were manually peeled off, and the film was rated from 1 to 5 based on the ease of peeling and the damage to the film surface (Level 1: completely adhered and cannot be peeled off; Level 2: completely adhered but can be peeled off, with a large amount of damage to the film surface; Level 3: moderately adhered and can be peeled off, with a small amount of damage to the film surface; Level 4: slightly adhered and can be easily peeled off without damage; Level 5: no adhesion).
[0042] (3) Adhesion: The cross-cut method is used to draw a grid with a spacing of 1 mm on the fully cured coating surface. The special pressure-sensitive adhesive tape is firmly adhered and quickly peeled off. The peeling of the coating in the grid area is observed and rated from 0 to 5 (0B is the best, no peeling; 5B is the worst, peeling area >65%).
[0043] Table 2 Performance test results of various hydrophobic and anti-blocking acrylic copolymer emulsions
[0044] According to the test results in Table 2, the water contact angle of the hydrophobic and anti-adhesion acrylic copolymer emulsions obtained in Examples 1-11 after coating the gloves was 112.5-132.6°, the anti-adhesion grade was 4-5, and the adhesion grade on the substrate surface was 0B. In contrast, the water contact angle of the hydrophobic and anti-adhesion acrylic copolymer emulsions obtained in Comparative Examples 1-3 after coating the gloves was 81.9-105.7°, the anti-adhesion grade was 2-4, and the adhesion grade on the substrate surface was 0-2B. Therefore, this application demonstrates that the use of methyl methacrylate, fluorinated hydrophobic functional monomers, pentaerythritol triacrylate monoesterified with laurate, and triisopropylsilyl methacrylate can prepare acrylic copolymer emulsions with high hydrophobicity, long-lasting anti-adhesion, and strong adhesion. Coating these emulsions onto substrates such as plastics, metals, and wood can achieve surface protection.
[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 hydrophobic, anti-blocking acrylic copolymer emulsion, characterized in that, It includes the following components in parts by weight: 50-70 parts of methyl methacrylate, 5-15 parts of fluorinated hydrophobic functional monomer, 3-8 parts of pentaerythritol triacrylate monoesterified with lauric acid, 3-5 parts of triisopropylsilyl methacrylate, 1-3 parts of emulsifier and 0.5-1 part of initiator.
2. The hydrophobic, anti-blocking acrylic copolymer emulsion according to claim 1, characterized in that, The hydrophobic and anti-blocking acrylic copolymer emulsion comprises the following components in parts by weight: 50-70 parts of methyl methacrylate, 5-10 parts of fluorinated hydrophobic functional monomers, 5-8 parts of pentaerythritol triacrylate monoesterified with lauric acid, 3-5 parts of triisopropylsilyl methacrylate, 1-3 parts of emulsifier, and 0.5-1 parts of initiator.
3. The hydrophobic, anti-blocking acrylic copolymer emulsion according to claim 2, characterized in that, The hydrophobic and anti-adhesion acrylic copolymer emulsion comprises the following components in parts by weight: 60 parts methyl methacrylate, 10 parts fluorinated hydrophobic functional monomer, 8 parts pentaerythritol triacrylate monoesterified with lauric acid, 4 parts triisopropylsilyl methacrylate, 2 parts emulsifier, and 0.8 parts initiator.
4. The hydrophobic, anti-blocking acrylic copolymer emulsion according to claim 3, characterized in that, The fluorinated hydrophobic functional monomer is selected from one or more of 1H,1H,2H,2H-perfluorodecyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, 2,2,2-trifluoroethyl methacrylate and tridecylfluorooctyl methacrylate.
5. The hydrophobic, anti-blocking acrylic copolymer emulsion according to claim 1, characterized in that, The fluorinated hydrophobic functional monomer is a mixture of 2,2,2-trifluoroethyl methacrylate and tridecylfluorooctyl methacrylate.
6. The hydrophobic, anti-blocking acrylic copolymer emulsion according to claim 1, characterized in that, The weight ratio of 2,2,2-trifluoroethyl methacrylate to tridecyl fluorooctyl methacrylate is 1:(0.5-2).
7. The method for preparing the hydrophobic, anti-blocking acrylic copolymer emulsion according to any one of claims 1-6, characterized in that, The process includes the following steps: dissolving the initiator in water and refluxing to 80-85°C with stirring; preparing a pre-emulsion by mixing methyl methacrylate, fluorinated hydrophobic functional monomers, pentaerythritol triacrylate monoesterified with lauric acid, triisopropylsilyl methacrylate, and an emulsifier; adding the pre-emulsion dropwise to the above thermal initiator solution over 1-1.5 hours, continuing the reaction for 5-12 hours, adjusting the pH to 7-8, and filtering to obtain a hydrophobic, anti-blocking acrylic copolymer emulsion.
8. The application of the hydrophobic, anti-blocking acrylic copolymer emulsion as described in any one of claims 1-6 in the surface protection of plastics, metals, and wood.