Super-hydrophobic nano SiO2 modified epoxy acrylic resin coating and preparation method thereof
阅读说明：本技术 一种超疏水纳米SiO2改性环氧丙烯酸树脂涂料及其制法 (Super-hydrophobic nano SiO2 modified epoxy acrylic resin coating and preparation method thereof ) 是由 郑明光 于 2020-05-11 设计创作，主要内容包括：本发明涉及丙烯酸树脂材料技术领域,且公开了一种超疏水纳米SiO<Sub>2</Sub>改性环氧丙烯酸树脂涂料,包括以下配方原料及组分：环氧树脂、丙烯酸、甲基丙烯酸十七氟癸酯、1,12-二氨基十二烷、引发剂、改性SiO<Sub>2</Sub>修饰聚多巴胺。该一种超疏水纳米SiO<Sub>2</Sub>改性环氧丙烯酸树脂涂料,环氧树脂与甲基丙烯酸十七氟癸酯和丙烯酸中的烯烃交联聚合形成环氧丙烯酸树脂,1,12-二氨基十二烷为扩链剂,柔性亚甲基长烷基链,增强了环氧丙烯酸树脂的柔韧性,降低了涂膜的脆性,甲基丙烯酸十七氟癸酯中的全氟碳链和1,12-二氨基十二烷长碳链具有很强的疏水性能,赋予了环氧丙烯酸树脂优异的超疏水性能,纳米SiO<Sub>2</Sub>在环氧丙烯酸树脂中具有良好的相容性和分散性。(The inventionRelates to the technical field of acrylic resin materials, and discloses super-hydrophobic nano SiO 2 The modified epoxy acrylic resin coating comprises the following formula raw materials and components: epoxy resin, acrylic acid, heptadecafluorodecyl methacrylate, 1, 12-diaminododecane, initiator and modified SiO 2 Modifying polydopamine. The super-hydrophobic nano SiO 2 The modified epoxy acrylic resin coating is characterized in that epoxy resin, heptadecafluorodecyl methacrylate and olefin in acrylic acid are subjected to cross-linking polymerization to form epoxy acrylic resin, 1, 12-diaminododecane is used as a chain extender, and a flexible methylene long alkyl chain is adopted, so that the flexibility of the epoxy acrylic resin is enhanced, the brittleness of a coating film is reduced, the perfluorinated carbon chain and the 1, 12-diaminododecane long carbon chain in the heptadecafluorodecyl methacrylate have strong hydrophobic performance, the epoxy acrylic resin is endowed with excellent super-hydrophobic performance, and the nano SiO has the advantages of high hydrophobicity 2 Has good compatibility and dispersibility in epoxy acrylic resin.)
1. Super-hydrophobic nano SiO2The modified epoxy acrylic resin coating comprises the following formula raw materials and components in parts by weight, and is characterized in that: 12-16 parts of epoxy resin, 32-38 parts of acrylic acid, 15-21 parts of heptadecafluorodecyl methacrylate, 4-10 parts of 1, 12-diaminododecane, 1-3 parts of initiator and 12-36 parts of modified SiO2Modifying polydopamine.
2. The super-hydrophobic nano SiO of claim 12The modified epoxy acrylic resin coating is characterized in that: the initiator is dibenzoyl peroxide.
3. The super-hydrophobic nano SiO of claim 12The modified epoxy acrylic resin coating is characterized in that: the modified SiO2The preparation method of the modified polydopamine comprises the following steps:
(1) adding ammonia water into a mixed solvent of distilled water and ethanol with a volume ratio of 2-3:1 to adjust the pH of the solution to 8-10, adding dopamine hydrochloride, heating the solution to 35-45 ℃ in a constant-temperature water bath kettle, stirring at a constant speed to react for 25-30h, adding an acetone solvent into the solution, standing and settling until a large amount of precipitate is separated out, removing the solvent from the solution, washing a solid product and drying to prepare nano poly-dopa;
(2) adding nano SiO into the mixed solvent of distilled water and ethanol with the volume ratio of 20-30:12And silane coupling agent vinyl triethoxysilane, subjecting the solution to ultra-dispersion treatment at 30-50 deg.C for 1-2h with ultrasonic frequency of 20-30KHz, heating the solution to 40-80 deg.C in a constant temperature water bath, stirring at uniform speed for 8-15h, removing solvent from the solution, washing the solid product, and drying to obtain vinyl triethoxysilaneAlkyl grafted modified nano SiO2；
(3) Adding nano poly-dopa and modified nano SiO into N, N-dimethylformamide solvent2Performing ultra-dispersion treatment on the solution at 40-60 ℃ for 1-3h with ultrasonic frequency of 25-35KHz, heating the solution to 60-80 ℃ in a constant-temperature water bath kettle, reacting for 3-5h, adding distilled water into the solution until a large amount of precipitate is separated out, washing a solid product and drying to prepare the modified SiO2Modifying polydopamine.
4. The super-hydrophobic nano SiO of claim 32The modified epoxy acrylic resin coating is characterized in that: the constant-temperature water bath kettle comprises a kettle body, wherein a through hole is formed in the bottom of the kettle body, a water valve is fixedly connected with the through hole, a U-shaped circulating pipe is arranged inside the kettle body, the U-shaped circulating pipe is movably connected with a sleeve, and the sleeve is clamped with the through hole.
5. The super-hydrophobic nano SiO of claim 32The modified epoxy acrylic resin coating is characterized in that: the nano SiO2And the mass ratio of the vinyltriethoxysilane is 8-15: 1.
6. The super-hydrophobic nano SiO of claim 32The modified epoxy acrylic resin coating is characterized in that: the nano poly-dopa and the modified nano SiO2The mass ratio of (A) to (B) is 2-4: 1.
7. The super-hydrophobic nano SiO of claim 12The modified epoxy acrylic resin coating is characterized in that: the super-hydrophobic nano SiO2The preparation method of the modified epoxy acrylic resin coating comprises the following steps:
(1) adding 32-38 parts of acrylic acid, 12-16 parts of epoxy resin, 15-21 parts of heptadecafluorodecyl methacrylate and 10-34 parts of modified SiO into an acetone solvent2Modifying polydopamine, adding 1-3 parts of initiator dibenzoyl peroxide after uniformly stirring, heating the solution to 60-80 ℃ in a constant-temperature water bath kettle, and reacting for 3-6 h;
(2) adding 4-10 parts of 1, 12-diaminododecane into the solution, heating to 90-120 ℃, carrying out chain extension reaction for 2-5h, carrying out high-speed emulsification process on the solution, controlling the solid-to-liquid ratio to be 55-70%, and preparing to obtain the super-hydrophobic nano SiO2Modified epoxy acrylic resin paint.
Technical Field
The invention relates to the technical field of acrylic resin materials, in particular to super-hydrophobic nano SiO2Modified epoxy acrylic resin paint and a preparation method thereof.
Background
The super-hydrophobic material is a novel material with super-strong hydrophobicity, the stable contact angle of the surface of the super-hydrophobic material is more than 150 degrees, the rolling contact angle is less than 10 degrees, the super-hydrophobic material has good self-cleaning performance and metal corrosion resistance, and the super-hydrophobic material has development potential in the fields of outdoor building rain and snow prevention, ship corrosion prevention, glass, transparent plastic material pollution prevention and the like.
The acrylic resin comprises polymers of polyacrylic acid, polymethacrylic acid and derivatives thereof, and is a thermoplastic or thermosetting resin coating, wherein the thermosetting acrylic resin has functional groups such as amino groups or carboxyl groups in the structure, can be added into polyurethane, epoxy resin and the like, and reacts with the functional groups to form a network structure, the thermosetting acrylic resin coating has good gloss, high temperature resistance, solvent resistance and weather resistance, the thermoplastic acrylic resin does not further crosslink in the film forming process, has excellent light and color retention and chemical resistance, and has wide application in the fields of automobile engineering, electronic appliances, mechanical buildings and the like, but the current acrylic resin coating has insufficient toughness, larger brittleness, easy cracking and cracking, and does not have super-hydrophobic performance.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a super-hydrophobic nano SiO2The modified epoxy acrylic resin coating and the preparation method thereof solve the problems of insufficient toughness and larger brittleness of the epoxy acrylic resin and simultaneously solve the problem that the acrylic resin coating does not have super-hydrophobic property.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: super-hydrophobic nano SiO2The modified epoxy acrylic resin coating comprises the following formula raw materials in parts by weight: 12-16 parts of epoxy resin, 32-38 parts of acrylic acid,15-21 parts of heptadecafluorodecyl methacrylate, 4-10 parts of 1, 12-diaminododecane, 1-3 parts of initiator and 12-36 parts of modified SiO2Modifying polydopamine.
Preferably, the initiator is dibenzoyl peroxide.
Preferably, the modified SiO2The preparation method of the modified polydopamine comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2-3:1, adding ammonia water to adjust the pH value of the solution to 8-10, adding dopamine hydrochloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 35-45 ℃, stirring at a constant speed for reaction for 25-30h, placing the solution into an ice water bath for cooling, adding an acetone solvent into the reaction bottle, stirring at a constant speed, standing for settling until a large amount of precipitate is separated out, centrifugally separating the solution to remove the solvent, washing the solid product with distilled water, and fully drying to prepare the nano poly-dopa.
(2) Adding nano SiO2 and silane coupling agent vinyl triethoxysilane into a reaction bottle with a volume ratio of 20-30:1, placing the reaction bottle in an ultrasonic disperser, performing ultra-dispersion treatment at 30-50 ℃ for 1-2h with an ultrasonic frequency of 20-30KHz, placing the reaction bottle in a constant-temperature water bath kettle, heating to 40-80 ℃, stirring at a constant speed for 8-15h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to obtain the vinyl triethoxysilane grafted modified nano SiO2。
(3) Adding N, N-dimethylformamide solvent into a reaction bottle, and adding nano poly-dopa and modified nano SiO2Carrying out ultra-dispersion treatment on a reaction bottle at 40-60 ℃ for 1-3h with ultrasonic frequency of 25-35KHz, placing the reaction bottle in a constant-temperature water bath, heating to 60-80 ℃, stirring at constant speed for reaction for 3-5h, placing the solution in an ice water bath for cooling, adding distilled water into the reaction bottle until a large amount of precipitate is separated out, using distilled water to form a washing solid product, and fully drying to prepare the modified SiO2Modifying polydopamine.
Preferably, the constant-temperature water bath kettle comprises a kettle body, a through hole is formed in the bottom of the kettle body, a water valve is fixedly connected with the through hole, a U-shaped circulating pipe is arranged inside the kettle body, a sleeve is movably connected with the U-shaped circulating pipe, and the sleeve is clamped with the through hole.
Preferably, the nano SiO2And the mass ratio of the vinyltriethoxysilane is 8-15: 1.
Preferably, the nano poly-dopa and the modified nano SiO2The mass ratio of (A) to (B) is 2-4: 1.
Preferably, the super-hydrophobic nano SiO2The preparation method of the modified epoxy acrylic resin coating comprises the following steps:
(1) adding an acetone solvent, 32-38 parts of acrylic acid, 12-16 parts of epoxy resin, 15-21 parts of heptadecafluorodecyl methacrylate and 10-34 parts of modified SiO into a reaction bottle2Modifying polydopamine, adding 1-3 parts of initiator dibenzoyl peroxide after uniformly stirring, placing a reaction bottle in a constant-temperature water bath kettle, heating to 60-80 ℃, and reacting for 3-6h under uniform stirring.
(2) Adding 4-10 parts of 1, 12-diaminododecane into a reaction bottle, heating to 90-120 ℃, carrying out chain extension reaction for 2-5h, cooling the solution to room temperature, carrying out high-speed emulsification process, controlling the solid-liquid ratio to be 55-70%, and preparing to obtain the super-hydrophobic nano SiO2Modified epoxy acrylic resin paint.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the super-hydrophobic nano SiO2 modified epoxy acrylic resin coating has the advantages that the carbon atoms adjacent to the oxygen atoms of the benzene ring in the epoxy resin, under the action of an initiator dibenzoyl peroxide, carbon free radicals are formed to perform free radical polymerization with heptadecafluorodecyl methacrylate and olefin in acrylic acid, so that the epoxy acrylic resin is formed by crosslinking polymerization, 1, 12-diaminododecane is taken as a chain extender, amino and epoxy groups are subjected to ring-opening reaction, the flexible methylene long alkyl chain of the 1, 12-diaminododecane can freely rotate around a symmetry axis, the flexibility of the epoxy acrylic resin is enhanced, the brittleness of a coating film is reduced, the toughening modification effect is achieved, the perfluoro carbon chain and the 1, 12-diaminododecane long carbon chain in the heptadecafluorodecyl methacrylate have strong hydrophobic performance, and the epoxy acrylic resin is endowed with excellent super-hydrophobic performance.
The super-hydrophobic nano SiO2Modified epoxy acrylic resin coating, modified nano SiO grafted by vinyl triethoxysilane2Then modifying modified nano poly dopamine, vinyl in vinyl triethoxy silane and acrylic acid cross-linking polymerization to improve nano SiO2Dispersion in epoxy acrylic resins, nano SiO2As an inorganic nano material, the nano SiO film can obviously enhance the mechanical properties of the film coating material, such as wear resistance, tensile strength and the like, and simultaneously further improves the ring opening reaction of hydroxyl and amino in the polydopamine and an epoxy group2Compatibility and dispersibility in epoxy acrylic resin, and avoids nano SiO2The mechanical properties of the coating material are affected by the uneven dispersion.
Drawings
FIG. 1 is a schematic front view of the oil bath pan of the present invention;
FIG. 2 is a left side view of the U-shaped circulation tube of the present invention;
FIG. 3 is a top view of the U-shaped circulation tube of the present invention.
1. A pan body; 2. a via hole; 3. a water valve; 4. a U-shaped circulating pipe; 5. a sleeve; 6. and a through hole.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: super-hydrophobic nano SiO2The modified epoxy acrylic resin coating comprises the following formula raw materials in parts by weight: 12-16 parts of epoxy resin, 32-38 parts of acrylic acid, 15-21 parts of heptadecafluorodecyl methacrylate, 4-10 parts of 1, 12-diaminododecane, 1-3 parts of initiator and 12-36 parts of modified SiO2Modifying polydopamine, wherein the initiator is dibenzoyl peroxide.
Modified SiO2The preparation method of the modified polydopamine comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2-3:1, adding ammonia water to adjust the pH value of the solution to 8-10, adding dopamine hydrochloride, placing the reaction bottle into a constant-temperature water bath kettle, heating to 35-45 ℃, wherein the constant-temperature water bath kettle comprises a kettle body, a through hole is formed in the bottom of the kettle body, a water valve is fixedly connected with the through hole, a U-shaped circulating pipe is arranged inside the kettle body, the U-shaped circulating pipe is movably connected with a sleeve pipe, the sleeve pipe is clamped with the through hole, stirring at a constant speed for 25-30 hours, placing the solution into an ice water bath for cooling, adding an acetone solvent into the reaction bottle, stirring at a constant speed, standing for settling until a large amount of precipitate is separated out, centrifugally separating the solution.
(2) Adding nano SiO into the mixed solvent of distilled water and ethanol in the volume ratio of 20-30:1 in the reaction bottle2And a silane coupling agent vinyl triethoxysilane with a mass ratio of 8-15:1, placing the reaction bottle in an ultrasonic disperser, carrying out ultra-dispersion treatment at 30-50 ℃ for 1-2h with an ultrasonic frequency of 20-30KHz, placing the reaction bottle in a constant-temperature water bath kettle, heating to 40-80 ℃, stirring at a constant speed for 8-15h, filtering the solution to remove the solvent, washing the solid product with distilled water, and fully drying to obtain the vinyl triethoxysilane grafted modified nano SiO2。
(3) Adding N, N-dimethylformamide solvent into a reaction bottle, and adding nano poly-dopa and modified nano SiO2The mass ratio of the two is 2-4:1, carrying out ultra-dispersion treatment on a reaction bottle at the temperature of 40-60 ℃ for 1-3h, wherein the ultrasonic frequency is 25-35KHz, placing the reaction bottle in a constant-temperature water bath kettle, heating to 60-80 ℃, stirring at a constant speed for reaction for 3-5h, placing the solution in an ice water bath for cooling, adding distilled water into the reaction bottle until a large amount of precipitate is separated out, using the distilled water to form a washing solid product, and fully drying to prepare the modified SiO2Modifying polydopamine.
Super-hydrophobic nano SiO2The preparation method of the modified epoxy acrylic resin coating comprises the following steps:
(1) adding an acetone solvent, 32-38 parts of acrylic acid, 12-16 parts of epoxy resin, 15-21 parts of heptadecafluorodecyl methacrylate and 10-34 parts of modified SiO into a reaction bottle2Modifying polydopamine, stirring, adding 1-3 parts of initiator dibenzoyl peroxidePlacing the reaction bottle in a constant-temperature water bath kettle, heating to 60-80 ℃, and stirring at a constant speed for reaction for 3-6 h.
(2) Adding 4-10 parts of 1, 12-diaminododecane into a reaction bottle, heating to 90-120 ℃, carrying out chain extension reaction for 2-5h, cooling the solution to room temperature, carrying out high-speed emulsification process, controlling the solid-liquid ratio to be 55-70%, and preparing to obtain the super-hydrophobic nano SiO2Modified epoxy acrylic resin paint.