Organic fluorine modified bio-based acrylate self-repairing emulsion as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of acrylate emulsion, and particularly relates to organic fluorine modified bio-based acrylate self-repairing emulsion as well as a preparation method and application thereof. The self-repairing emulsion is prepared from the following components in parts by mass: 25-55 parts of an unsaturated bio-based acrylate monomer, 14-31 parts of a composite functional monomer, 4-12 parts of a composite reactive emulsifier, 3-5 parts of potassium persulfate and 200-300 parts of deionized water, wherein the unsaturated bio-based acrylate monomer is prepared from the following components in parts by mass: 10 to 25 parts of bio-based 2-octyl acrylate and 15 to 30 parts of bio-based ethyl acrylate. The organic fluorine modified bio-based acrylate self-repairing emulsion is environmentally friendly in the production and use process, the stability of the emulsion is better than that of an emulsion prepared through a traditional method, and the emulsion has the self-repairing characteristic.

Description

Technical Field

[0001] This invention belongs to the field of acrylic emulsion technology, specifically relating to an organofluorine modified bio-based acrylic self-healing emulsion, its preparation method, and its application. Background Technology

[0002] Traditional acrylic emulsions rely on fossil-based raw materials, resulting in high energy consumption and significant environmental impact. Furthermore, their self-healing properties, weather resistance, and surface functionalities (such as fingerprint resistance and stain resistance) are insufficient, making it difficult to meet the high-performance, low-VOC emission requirements of modern environmentally friendly coatings. On the one hand, bio-based materials have become a research hotspot due to their renewability; on the other hand, the introduction of organofluorine groups can endow materials with properties such as low surface energy and high durability. However, purely bio-based emulsions suffer from low mechanical strength and insufficient crosslinking efficiency. In addition, the compatibility and controlled polymerization of fluorides with bio-based monomers remain technical challenges.

[0003] Chinese patent CN102250281A discloses a cationic acrylate emulsion, which includes deionized water, an initiator, an emulsifier, styrene, and C4-C. 12 alkyl acrylate unsaturated monomers, C4-C 20 Methacrylate unsaturated monomers, C7-C 12 The patent describes a process involving the preparation of a polymer emulsion using alkylamino (meth)acrylate cationic monomers, acrylamide functional monomers, and an acid, followed by acid neutralization of the polymer emulsion. However, the patented alkyl acrylate unsaturated monomers, methacrylate unsaturated monomers, and alkylamino (meth)acrylate cationic monomers are all petroleum-based raw materials with high carbon footprints, which do not align with the trend of green chemistry. Furthermore, the styrene used in the emulsion raw materials is a volatile and toxic monomer.

[0004] Chinese patent CN1869085A discloses a modified acrylate copolymer emulsion, mainly composed of olefin monomers, emulsifiers, initiators, pH adjusters, and deionized water. The emulsifiers are alkylphenol-free emulsifiers, including sodium alkyl ether succinate and alkyl polyoxyethylene ether, with their contents accounting for 0.8-1.5% and 0.5-1.5% of the total weight of the emulsion, respectively. The weight percentages of the remaining components in the emulsion are as follows: olefin monomers: styrene 5-25%, methyl methacrylate 2-16%, butyl acrylate 8-25%, diethylhexyl acrylate 5-12%, acrylic acid 0.3-1%, acrylamide 0.3-0.8%, vinyltrimethoxysilane 0.1-0.3%, γ-methacryloyloxytrimethoxysilane 0.1-0.3%; initiator: ammonium persulfate 0.05-0.5%; pH adjuster: sodium bicarbonate 0.05-0.08%; deionized water: 43-53%. The patent uses petroleum-based raw materials such as methyl methacrylate, butyl acrylate, diethylhexyl acrylate, and acrylic acid, which have a high carbon footprint. The high proportion of styrene and methyl methacrylate leads to increased brittleness of the paint film, making it prone to cracking at low temperatures. The low acrylic acid content results in insufficient adhesion of the paint film to metal or highly polar substrates. Summary of the Invention

[0005] The purpose of this invention is to provide an organofluorine modified bio-based acrylate self-healing emulsion, which is environmentally friendly in production and use, and has the advantages of low fossil energy consumption, high adhesion, long service life, self-healing, fingerprint resistance, stain resistance and washability; this invention also provides a method for preparing organofluorine modified bio-based acrylate self-healing emulsion and its application.

[0006] The organofluorine modified bio-based acrylate self-healing emulsion of the present invention is made of the following components in parts by weight: 25-55 parts of unsaturated bio-based acrylate monomer, 14-31 parts of composite functional monomer, 4-12 parts of composite reactive emulsifier, 3-5 parts of potassium persulfate, and 200-300 parts of deionized water; wherein, the unsaturated bio-based acrylate monomer is made of the following components in parts by weight: 10-25 parts of bio-based 2-octyl acrylate and 15-30 parts of bio-based ethyl acrylate.

[0007] The composite functional monomer is made from the following components in parts by weight: 3-7 parts of N-isopropylacrylamide, 5-11 parts of ethyl 2-(acryloyloxy)acetoacetate, 1-2 parts of ethyl 3-(trifluoromethyl)butenoate, and 5-11 parts of octamethylcyclotetrasiloxane.

[0008] The composite reactive emulsifier is made from the following components in parts by weight: 1-3 parts allyl polyoxyethylene polyoxypropylene ether, 1-3 parts polyether methacrylate, and 2-6 parts sodium allyl sulfonate.

[0009] The organic fluorine-modified bio-based acrylate self-healing emulsion has a solid content of 30-40 wt%, an average particle size of ≤100 nm, a surface energy of ≤20 mN / m, and a self-healing temperature of 40-60 ℃.

[0010] The preparation method of the organofluorine modified bio-based acrylate self-healing emulsion of the present invention includes the following steps: (1) Mix unsaturated bio-based acrylate monomers and composite functional monomers evenly to obtain a mixed monomer; (2) Mix deionized water, composite reactive emulsifier and potassium persulfate, pass nitrogen gas through to pre-emulsify, and heat to obtain pre-emulsion; (3) Add the mixed monomers obtained in step (1) to the pre-emulsion obtained in step (2) to obtain a mixed emulsion; (4) Heat and keep warm the mixed emulsion obtained in step (3), and then cool it to room temperature to obtain organofluorine modified bio-based acrylate self-healing emulsion.

[0011] In step (2), the pre-emulsification time is 1-2 hours and the heating temperature is 60-90℃.

[0012] In step (3), the temperature of the pre-emulsion is 60-90℃, and the time for adding the mixed monomers to the pre-emulsion is 2-3h.

[0013] In step (4), the heating temperature of the mixed emulsion is 90-95℃, and the holding time is 30-60min.

[0014] Application of the organofluorine modified bio-based acrylate self-healing emulsion described in this invention: The organic fluorine-modified bio-based acrylate self-healing emulsion and filler are mixed at a mass ratio of (8-9):1 and sprayed onto the substrate surface. The mixture is then dried at 80-90℃ for 20-30 minutes to form a film. Alternatively, the organic fluorine-modified bio-based acrylate self-healing emulsion is sprayed onto the substrate surface and dried at 80-90℃ for 20-30 minutes to form a film.

[0015] The filler is titanium dioxide, and the film thickness, i.e. the coating thickness, is 10-50μm.

[0016] The beneficial effects of this invention are as follows: (1) Improved environmental friendliness: Bio-based monomers replace some fossil raw materials, reducing carbon footprint and conforming to the concept of green chemistry; the water-based system reduces the volatilization of organic solvents, and the production and use process is low in toxicity and harmless, meeting environmental protection standards.

[0017] (2) Synergistic performance enhancement: Bio-based 2-octyl acrylate in the unsaturated bio-based acrylate monomers serves as the main chain monomer, which can reduce the dependence on fossil raw materials and provide molecular flexibility. Bio-based ethyl acrylate provides a rigid structure and enhances the adhesion of the coating.

[0018] N-isopropylacrylamide, a composite functional monomer, undergoes a free radical copolymerization reaction with ethyl 2-(acryloyloxy)acetoacetate, ethyl 3-(trifluoromethyl)butenoate, and unsaturated bio-based acrylate monomers to form a polymer thermosensitive network structure under the action of potassium persulfate initiator. The β-diketone group in ethyl 2-(acryloyloxy)acetoacetate can undergo tautomerism between keto and enol forms. The hydroxyl group in the enol form can form stable bonds with the carbonyl groups in the β-diketone groups of other chain segments through intermolecular hydrogen bonding, thus constructing the polymer thermosensitive network structure with N-isopropylacrylamide, ethyl 3-(trifluoromethyl)butenoate, and unsaturated bio-based acrylate monomers. When the coating is damaged by external forces (such as scratches or cracks), the local hydrogen bonds will break due to the external force. The polymer thermosensitive network structure formed by N-isopropylacrylamide works synergistically with the dynamic covalent bonds of ethyl acetoacetate, enabling the coating to undergo molecular chain rearrangement and repair at the scratches through temperature stimulation (such as 40-60℃), reforming hydrogen bonds and driving the material's self-repair.

[0019] The Si-O-Si bonds and symmetrical methyl structure of octamethylcyclotetrasiloxane, in conjunction with ethyl 3-(trifluoromethyl)butenoate, can effectively reduce steric hindrance and intermolecular forces, thereby reducing chain segment movement resistance, which in turn lowers the glass transition temperature and accelerates the diffusion of polymer chains at the scratches. The above synergistic effect enables the coating to achieve molecular chain rearrangement and repair at the scratches through temperature stimulation (e.g., 40-60℃), thus possessing a self-healing mechanism.

[0020] In the composite functional monomer, ethyl 3-(trifluoromethyl)butenoate is oriented on the coating surface to form a dense fluorinated layer, while octamethylcyclotetrasiloxane reduces intermolecular forces through Si-CH3. The two work synergistically to give the coating low surface energy properties, achieving anti-fingerprint and anti-oil adhesion.

[0021] The Si-O bond energy, bond length, and bond angle of the octamethylcyclotetrasiloxane in the composite functional monomer are all greater than those of the C-C bond, making it less prone to breakage during mechanical friction. This can improve the flexibility and washability of the coating (≥3000 times) and optimize the surface function of the coating.

[0022] The allyl polyoxyethylene polyoxypropylene ether in the composite reactive emulsifier possesses hydrophilic polyoxyethylene segments that form steric hindrance through hydrogen bonding with water, inhibiting emulsion particle aggregation and enhancing the dispersion stability of the emulsion. Methacrylate polyether phosphate, as an anionic emulsifier, enhances the mechanical stability of the emulsion through electrostatic repulsion generated by the negative charge of the phosphate groups. Sodium allyl sulfonate, as a reactive emulsifier, participates in the copolymerization reaction during polymerization through its allyl groups, reducing free emulsifier residue and VOCs release, while enhancing the charge stability of the emulsion through the ionization of the sulfonic acid groups. These three components synergistically provide both emulsification and anchoring functions, enhancing interfacial compatibility, resulting in emulsion particle sizes ≤100nm. The coating exhibits ISO 5B-level adhesion to metals (such as aluminum alloys) and plastics (such as ABS), and shows no corrosion in the salt spray test (500h), improving coating adhesion and durability.

[0023] (3) Process innovation: This invention realizes the controllable polymerization of bio-based monomers and fluorine-containing functional components. During the preparation process, the nucleation and growth process of latex particles is optimized by heating and dropping, which solves the problem of gel particles easily generated by traditional emulsion polymerization. While maintaining the stability of the emulsion (particle size ≤100nm), the organofluorine groups are uniformly grafted onto the molecular chain of bio-based acrylate. The resulting organofluorine modified bio-based acrylate self-healing emulsion has better stability than the emulsion prepared by traditional methods. Attached Figure Description

[0024] Figure 1 This is the infrared spectrum of the organofluorine modified bio-based acrylate self-healing emulsion of Example 1 of the present invention. Detailed Implementation

[0025] The present invention will be further described below with reference to embodiments.

[0026] Example 1 The organofluorine-modified bio-based acrylate self-healing emulsion was prepared using the following components in parts by weight: 40 parts of unsaturated bio-based acrylate monomers are made from the following components in parts by weight: 20 parts of bio-based 2-octyl acrylate and 20 parts of bio-based ethyl acrylate; The composite functional monomer is 14 parts, which is made from the following components in parts by weight: 3 parts of N-isopropylacrylamide, 5 parts of ethyl 2-(acryloyloxy)acetoacetate, 1 part of ethyl 3-(trifluoromethyl)butenoate and 5 parts of octamethylcyclotetrasiloxane. Six parts of a composite reactive emulsifier are made from the following components in parts by weight: 1.5 parts of allyl polyoxyethylene polyoxypropylene ether, 1.5 parts of polyether methacrylate, and 3 parts of sodium allyl sulfonate. 4 parts potassium persulfate and 250 parts deionized water.

[0027] The preparation steps are as follows: (1) Mix unsaturated bio-based acrylate monomers and composite functional monomers evenly to obtain mixed monomers; (2) Mix deionized water, composite reactive emulsifier and potassium persulfate, purge with nitrogen gas for 2 hours for pre-emulsification, and heat to 60°C to obtain a pre-emulsion; (3) The mixed monomers obtained in step (1) are added dropwise to the pre-emulsion obtained in step (2) at 60°C for 2 hours to obtain a mixed emulsion; (4) Heat the mixed emulsion obtained in step (3) to 90°C, keep it warm for 60 min, and then cool it to room temperature to obtain the organofluorine modified bio-based acrylate self-healing emulsion.

[0028] Organic fluorine-modified bio-based acrylate self-healing emulsion was mixed with titanium dioxide at a mass ratio of 8:1 and sprayed onto the surface of an aluminum alloy. The mixture was then dried at 80°C for 30 minutes to form a film with a thickness of 50 μm.

[0029] The performance test results are shown below: After heating at 60℃ for 30 minutes, the self-healing rate of the scratch (depth 50μm) was 92%. The surface energy is 18mN / m, and the fingerprint resistance test (grease contamination) shows a wiping residue rate of <5%. The adhesion (ASTM D3359) rating is 5B (cross-cut test), and the wash resistance (GB / T 9266) is 35,000 cycles without damage. No rust was observed after 750 hours of salt spray testing (ASTM B117); Color difference ΔE < 1.5 after 500h of UV aging resistance test (ASTM G154); VOC emissions <10g / L; The organofluorine modified bio-based acrylate self-healing emulsion has a solid content of 32% and an average particle size of 90 nm.

[0030] Infrared spectroscopy was performed on the organofluorine modified bio-based acrylate self-healing emulsion obtained in Example 1, showing successful polymerization. Figure 1 As shown.

[0031] The specific infrared testing steps are as follows: Take out 3g of self-healing emulsion, dry it in a vacuum drying oven to constant weight, then dissolve it with xylene and evenly coat it on a KBr pellet. After film formation and drying, infrared testing is performed using a Nicolet iS20 infrared spectrometer.

[0032] In the 3100-3000cm range - ¹No stretching vibration peak of =CH and 1650-1630cm -¹ The absence of C=C stretching vibration absorption peaks in this region indicates that the vast majority of vinyl groups (C=C) have participated in the copolymerization reaction, forming polymer chains; at 1740 cm⁻¹ - The extremely strong absorption peak observed at ¹ is attributed to the stretching vibration of the carbonyl (C=O) group of the acrylate unit; at 2933 cm⁻¹ - The absorption peak at ¹ is attributed to the CH stretching vibration in the saturated hydrocarbon of the acrylate unit; at 1454 cm⁻¹ - The absorption peak at ¹ is attributed to the CH bending vibration in the saturated hydrocarbon of the acrylate unit; at 3299 cm⁻¹ - The moderate-intensity broad absorption peak in region ¹ indicates the successful introduction of the isopropylacrylamide unit, providing a characteristic signal of the NH stretching vibration; while the 1183 cm⁻¹ region… - The extremely strong and broad absorption band in region ¹ clearly confirms the presence of fluorinated monomers, a typical characteristic of CF bonds; furthermore, the 1130 cm⁻¹ region… - The strong and broad absorption peak in region ¹ confirms the presence of polyether segments and siloxane structures, demonstrating the successful introduction of emulsifiers and siloxane monomers.

[0033] Example 2 The organofluorine-modified bio-based acrylate self-healing emulsion was prepared using the following components in parts by weight: 38 parts of unsaturated bio-based acrylate monomers are made from the following components in parts by weight: 15 parts of bio-based 2-octyl acrylate and 23 parts of bio-based ethyl acrylate. The composite functional monomer is composed of 24 parts by weight of the following components: 5 parts of N-isopropylacrylamide, 8 parts of ethyl 2-(acryloyloxy)acetoacetate, 2 parts of ethyl 3-(trifluoromethyl)butenoate and 9 parts of octamethylcyclotetrasiloxane. Eight parts of a composite reactive emulsifier are made from the following components in parts by weight: 2 parts of allyl polyoxyethylene polyoxypropylene ether, 2 parts of polyether methacrylate and 4 parts of sodium allyl sulfonate. 5 parts potassium persulfate and 280 parts deionized water.

[0034] The preparation steps are as follows: (1) Mix unsaturated bio-based acrylate monomers and composite functional monomers evenly to obtain mixed monomers; (2) Mix deionized water, composite reactive emulsifier and potassium persulfate, purge with nitrogen gas to pre-emulsify for 1 hour, heat to 90°C to obtain pre-emulsion; (3) The mixed monomers obtained in step (1) are added dropwise to the pre-emulsion obtained in step (2) at 90°C for 3 hours to obtain a mixed emulsion; (4) Heat the mixed emulsion obtained in step (3) to 95°C, keep it warm for 30 min, and then cool it to room temperature to obtain the organofluorine modified bio-based acrylate self-healing emulsion.

[0035] Organic fluorine-modified bio-based acrylate self-healing emulsion was mixed with titanium dioxide at a mass ratio of 9:1 and sprayed onto the surface of an outdoor wall. The mixture was then dried at 90°C for 20 minutes to form a film with a thickness of 30 μm.

[0036] The performance test results are shown below: After heating at 50℃ for 35 minutes, the self-healing rate of the scratch (depth 30μm) was 93%. The surface energy is 19mN / m, and the fingerprint resistance test (grease contamination) shows a wiping residue rate of <6%. The adhesion (ASTM D3359) rating is 5B (cross-cut test), and the wash resistance (GB / T 9266) is 34,000 cycles without damage. No rust was observed after 720 hours of salt spray testing (ASTM B117); Color difference ΔE < 1.5 after 450h UV aging (ASTM G154) test; VOC emissions <10g / L; The organofluorine modified bio-based acrylate self-healing emulsion has a solid content of 35% and an average particle size of 95nm.

[0037] Example 3 The organofluorine-modified bio-based acrylate self-healing emulsion was prepared using the following components in parts by weight: 55 parts of unsaturated bio-based acrylate monomers are made from the following components in parts by weight: 25 parts of bio-based 2-octyl acrylate and 30 parts of bio-based ethyl acrylate. The composite functional monomer is composed of 31 parts by mass of the following components: 7 parts of N-isopropylacrylamide, 11 parts of ethyl 2-(acryloyloxy)acetoacetate, 2 parts of ethyl 3-(trifluoromethyl)butenoate and 11 parts of octamethylcyclotetrasiloxane. Four parts of a composite reactive emulsifier are made from the following components in parts by weight: 1 part of allyl polyoxyethylene polyoxypropylene ether, 1 part of polyether methacrylate and 2 parts of sodium allyl sulfonate. 3 parts potassium persulfate and 200 parts deionized water.

[0038] The preparation steps are as follows: (1) Mix unsaturated bio-based acrylate monomers and composite functional monomers evenly to obtain mixed monomers; (2) Mix deionized water, composite reactive emulsifier and potassium persulfate, purge with nitrogen gas for 1.5 h, heat to 75 °C to obtain pre-emulsion; (3) The mixed monomers obtained in step (1) are added dropwise to the pre-emulsion obtained in step (2) at 75°C for 2.5 hours to obtain a mixed emulsion; (4) Heat the mixed emulsion obtained in step (3) to 91°C, keep it warm for 50 min, and then cool it to room temperature to obtain the organofluorine modified bio-based acrylate self-healing emulsion.

[0039] Organic fluorine-modified bio-based acrylate self-healing emulsion was mixed with titanium dioxide at a mass ratio of 8.5:1 and sprayed onto the surface of an interior wall. The mixture was then dried at 85°C for 25 minutes to form a film with a thickness of 40 μm.

[0040] The performance test results are shown below: Heating at 40℃ for 25 minutes resulted in a 91% self-healing rate for scratches (40μm depth). The surface energy is 17mN / m, and the fingerprint resistance test (grease contamination) shows a wiping residue rate of <4%. The adhesion (ASTM D3359) rating is 5B (cross-cut test), and the wash resistance (GB / T 9266) is 30,000 cycles without damage. No rust was observed after 740 hours of salt spray testing (ASTM B117); Color difference ΔE < 1.5 after 480h of UV aging resistance test (ASTM G154); VOC emissions <10g / L; The organofluorine modified bio-based acrylate self-healing emulsion has a solid content of 40% and an average particle size of 100nm.

[0041] Example 4 The organofluorine-modified bio-based acrylate self-healing emulsion was prepared using the following components in parts by weight: 25 parts of unsaturated bio-based acrylate monomers are made from the following components in parts by weight: 10 parts of bio-based 2-octyl acrylate and 15 parts of bio-based ethyl acrylate. The composite functional monomer is composed of 20 parts by weight of the following components: 4 parts of N-isopropylacrylamide, 7 parts of ethyl 2-(acryloyloxy)acetoacetate, 2 parts of ethyl 3-(trifluoromethyl)butenoate and 7 parts of octamethylcyclotetrasiloxane. 12 parts of a composite reactive emulsifier are made from the following components in parts by weight: 3 parts of allyl polyoxyethylene polyoxypropylene ether, 3 parts of polyether methacrylate and 6 parts of sodium allyl sulfonate. 5 parts potassium persulfate and 300 parts deionized water.

[0042] The preparation steps are as follows: (1) Mix unsaturated bio-based acrylate monomers and composite functional monomers evenly to obtain mixed monomers; (2) Mix deionized water, composite reactive emulsifier and potassium persulfate, purge with nitrogen gas for 2 hours for pre-emulsification, and heat to 60°C to obtain a pre-emulsion; (3) The mixed monomers obtained in step (1) are added dropwise to the pre-emulsion obtained in step (2) at 60°C for 3 hours to obtain a mixed emulsion; (4) Heat the mixed emulsion obtained in step (3) to 93°C, keep it warm for 40 min, and then cool it to room temperature to obtain the organofluorine modified bio-based acrylate self-healing emulsion.

[0043] Organic fluorine-modified bio-based acrylate self-healing emulsion was sprayed onto the surface of a mobile phone casing and dried at 80°C for 30 minutes to form a film with a thickness of 10 μm.

[0044] The performance test results are shown below: Heating at 60℃ for 15 minutes resulted in a 95% self-healing rate for scratches (10μm depth). The surface energy is 15mN / m, and the fingerprint resistance test (grease contamination) shows a wiping residue rate of <4%. The adhesion (ASTM D3359) rating is 5B (cross-cut test), and the wash resistance (GB / T 9266) is 31,000 cycles without damage. No rust was observed after 720 hours of salt spray testing (ASTM B117); Color difference ΔE < 1.5 after 460h of UV aging resistance (ASTM G154) test; VOC emissions <10g / L; The organofluorine modified bio-based acrylate self-healing emulsion has a solid content of 30% and an average particle size of 92nm. When used for mobile phone casings, the hardness (ASTM D3363) is 3H.

[0045] Example 5 The organofluorine-modified bio-based acrylate self-healing emulsion was prepared using the following components in parts by weight: 40 parts of unsaturated bio-based acrylate monomers are made from the following components in parts by weight: 18 parts of bio-based 2-octyl acrylate and 22 parts of bio-based ethyl acrylate. The composite functional monomer is composed of 22 parts by weight of the following components: 5 parts of N-isopropylacrylamide, 8 parts of ethyl 2-(acryloyloxy)acetoacetate, 1 part of ethyl 3-(trifluoromethyl)butenoate and 8 parts of octamethylcyclotetrasiloxane. Five parts of a composite reactive emulsifier are made from the following components in parts by weight: 1.3 parts of allyl polyoxyethylene polyoxypropylene ether, 1.2 parts of polyether methacrylate and 2.5 parts of sodium allyl sulfonate. 3.5 parts potassium persulfate and 220 parts deionized water.

[0046] The preparation steps are as follows: (1) Mix unsaturated bio-based acrylate monomers and composite functional monomers evenly to obtain mixed monomers; (2) Mix deionized water, composite reactive emulsifier and potassium persulfate, purge with nitrogen gas for 2 hours for pre-emulsification, and heat to 80°C to obtain a pre-emulsion; (3) The mixed monomers obtained in step (1) are added dropwise to the pre-emulsion obtained in step (2) at 80°C for 2 hours to obtain a mixed emulsion; (4) Heat the mixed emulsion obtained in step (3) to 92°C, keep it warm for 45 min, and then cool it to room temperature to obtain the organofluorine modified bio-based acrylate self-healing emulsion.

[0047] Organic fluorine-modified bio-based acrylate self-healing emulsion was sprayed onto the surface of ABS plastic and dried at 90°C for 20 minutes to form a film with a thickness of 20 μm.

[0048] The performance test results are shown below: Heating at 50℃ for 20 minutes resulted in a 90% self-healing rate for scratches (20μm depth). The surface energy is 18mN / m, and the fingerprint resistance test (grease contamination) shows a wiping residue rate of <5%. The adhesion (ASTM D3359) rating is 5B (cross-cut test), and the wash resistance (GB / T 9266) is 32,000 cycles without damage. No rust was observed after 730 hours of salt spray testing (ASTM B117); Color difference ΔE < 1.5 after 400h of UV aging resistance test (ASTM G154); VOC emissions <10g / L; The organofluorine modified bio-based acrylate self-healing emulsion has a solid content of 38% and an average particle size of 98nm.

[0049] Comparative Example 1 N-isopropylacrylamide was not used in the composite monomer, and the rest was the same as in Example 1; after heating at 60°C for 30 minutes, the self-healing rate of the scratch (depth 50μm) was 43%.

[0050] Comparative Example 2 Ethyl 2-(acryloyloxy)acetoacetate was not used in the composite monomer, and the rest was the same as in Example 1; after heating at 60°C for 30 minutes, the self-healing rate of the scratch (depth 50 μm) was 45%.

[0051] Comparative Example 3 Ethyl 3-(trifluoromethyl)butenoate was not used in the composite monomer, and the rest was the same as in Example 1; after heating at 60°C for 30 minutes, the self-healing rate of scratches (depth 50μm) was 74%; the surface energy was 25mN / m, and the wiping residue rate after fingerprint resistance test (grease contamination) was 22%.

[0052] Comparative Example 4 Octamethylcyclotetrasiloxane was not used in the composite monomer, and the rest was the same as in Example 1; after heating at 60°C for 30 minutes, the self-healing rate of scratches (depth 50μm) was 67%; the surface energy was 28mN / m, and the wiping residue rate after fingerprint resistance test (grease contamination) was 25%; the wash resistance (GB / T9266) was 25,000 cycles before damage occurred.

[0053] Comparative Example 5 The composite monomers do not use ethyl 3-(trifluoromethyl)butenoate or octamethylcyclotetrasiloxane, but are otherwise the same as in Example 1; after heating at 60°C for 30 minutes, the self-healing rate of the scratch (depth 50μm) is 58%.

[0054] Comparative Example 6 The composite monomers do not use ethyl 2-(acryloyloxy)acetoacetate or octamethylcyclotetrasiloxane, but are otherwise the same as in Example 1; Heating at 60℃ for 30 minutes resulted in a self-healing rate of 34% for scratches (50μm depth).

[0055] Comparative Example 7 The composite monomers did not use ethyl 2-(acryloyloxy)acetoacetate or ethyl 3-(trifluoromethyl)butenoate, but were otherwise the same as in Example 1; after heating at 60°C for 30 minutes, the self-healing rate of the scratch (depth 50 μm) was 36%.

[0056] Comparative Example 8 The composite monomers do not use N-isopropylacrylamide and octamethylcyclotetrasiloxane, but are otherwise the same as in Example 1; after heating at 60°C for 30 minutes, the self-healing rate of the scratch (depth 50μm) is 31%.

[0057] Comparative Example 9 The composite monomers did not use N-isopropylacrylamide or ethyl 3-(trifluoromethyl)butenoate, but were otherwise the same as in Example 1; after heating at 60°C for 30 minutes, the self-healing rate of the scratch (depth 50μm) was 33%.

[0058] Comparative Example 10 The composite monomers do not include N-isopropylacrylamide and ethyl 2-(acryloyloxy)acetoacetate, but are otherwise the same as in Example 1.

[0059] Comparative Example 11 The composite monomer used only N-isopropylacrylamide, and the rest were the same as in Example 1.

[0060] Comparative Example 12 The composite monomer used only ethyl 2-(acryloyloxy)acetoacetate, and the rest was the same as in Example 1.

[0061] Comparative Example 13 Only ethyl 3-(trifluoromethyl)butenoate was used in the composite monomer, and the rest were the same as in Example 1.

[0062] Comparative Example 14 The composite monomer uses only octamethylcyclotetrasiloxane, and the rest is the same as in Example 1.

[0063] After experiments, in Comparative Examples 10-14, the self-repair rate of scratches (depth 50μm) after heating at 60℃ for 30 minutes was less than 30%, so no further experiments were conducted.

[0064] For bio-based 2-octyl acrylate, products manufactured by BASF are preferred; for bio-based ethyl acrylate, products manufactured by BASF are preferred; for allyl polyoxyethylene polyoxypropylene ether, products manufactured by Hangzhou Danwei Technology Co., Ltd. are preferred; and for polyether methacrylate, products manufactured by Shanghai Youchuang Chemical Co., Ltd. are preferred.

Claims

1. An organofluoro-modified bio-based acrylate self-healing emulsion characterized in that The unsaturated bio-based acrylate monomer is prepared from components in the following mass fractions: bio-based 2-octyl acrylate 10-25 parts and bio-based ethyl acrylate 15-30 parts.

2. The organofluoro-modified bio-based acrylate self-healing emulsion according to claim 1, characterized in that The complex functional monomer is prepared from components in the following mass fractions: N-isopropyl acrylamide 3-7 parts, 2-(acryloyloxy)ethyl acetoacetate 5-11 parts, ethyl 3-(trifluoromethyl)butenoate 1-2 parts, and octamethylcyclotetrasiloxane 5-11 parts.

3. The organofluoro-modified bio-based acrylate self-healing emulsion of claim 1, wherein The complex reactive emulsifier is prepared from components in the following mass fractions: allyl polyoxyethylene polyoxypropylene ether 1-3 parts, methacrylic acid polyether phosphate 1-3 parts, and sodium allyl sulfonate 2-6 parts.

4. The organofluorine-modified bio-based acrylate self-healing emulsion of claim 1, wherein The solid content of the organic fluorine-modified bio-based acrylate self-repairing emulsion is 30-40 wt%, the average particle size is ≤100 nm, the surface energy is ≤20 mN / m, and the self-repairing temperature is 40-60℃.

5. A process for the preparation of the bio-based acrylate self-repairing emulsion modified with organofluorine according to any one of claims 1 to 4, characterized in that The method comprises the following steps: (1) uniformly mixing the unsaturated bio-based acrylate monomer and the complex functional monomer to obtain a mixed monomer; (2) mixing the deionized water, the complex reactive emulsifier, and the potassium persulfate, pre-emulsifying under nitrogen, and heating to obtain a pre-emulsion; (3) adding the mixed monomer obtained in step (1) to the pre-emulsion obtained in step (2) to obtain a mixed emulsion; (4) heating and incubating the mixed emulsion obtained in step (3), and then cooling to room temperature to obtain the organic fluorine-modified bio-based acrylate self-repairing emulsion.

6. The method for preparing the organofluorine modified bio-based acrylate self-healing emulsion according to claim 5, characterized in that... The pre-emulsification time in step (2) is 1-2 h, and the heating temperature is 60-90℃.

7. The method for preparing the organofluorine modified bio-based acrylate self-healing emulsion according to claim 5, characterized in that... The temperature of the pre-emulsion in step (3) is 60-90℃, and the time for adding the mixed monomer to the pre-emulsion is 2-3 h.

8. The method for preparing the organofluorine modified bio-based acrylate self-healing emulsion according to claim 5, characterized in that... The heating temperature of the mixed emulsion in step (4) is 90-95℃, and the incubation time is 30-60 min.

9. Use of the bio-based acrylate self-repairing emulsion modified with organofluorine according to any one of claims 1 to 4, characterized in that The organic fluorine-modified bio-based acrylate self-repairing emulsion is mixed with the filler at a mass ratio of (8-9):1, sprayed on the surface of the substrate, and dried at 80-90℃ for 20-30 min to form a film; or the organic fluorine-modified bio-based acrylate self-repairing emulsion is sprayed on the surface of the substrate, and dried at 80-90℃ for 20-30 min to form a film.

10. Use of an organofluoro-modified bio-based acrylate self-healing emulsion according to claim 9, characterized in that The filler is titanium dioxide, and the film thickness is 10-50 μm.

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