A fluorine-containing super-hydrophobic coating and its preparation process

Abstract

The present invention discloses a kind of fluorine-containing super-hydrophobic coating and preparation technology thereof, relate to hydrophobic coating technology field.A kind of fluorine-containing super-hydrophobic coating, including following mass components:60 80 parts of composite fluorine-containing resins, 5 15 parts of fillers, 5 10 parts of curing agents;The composite fluorine-containing resin is obtained by epoxy resin and fluorine-containing esterified epoxy compound blending.The present invention passes through epoxy resin and fluorine-containing esterified epoxy compound blending, obtains composite fluorine-containing resin;Utilizing the low surface energy of fluorine-containing esterified epoxy compound and the good adhesion of epoxy resin, during coating curing, fluorine segment migrates to coating surface, reduces the surface energy of coating, epoxy resin undergoes cross-linking reaction under the action of curing agent, solves the problem of poor coating adhesion, epoxy esterified compound and epoxy resin blend, form tighter, strong three-dimensional network structure after curing, improve the cross-linking strength of coating, comprehensively improve the hydrophobicity and anti-cracking performance of coating.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrophobic coatings, and in particular to a fluorine-containing super-hydrophobic coating and a preparation process thereof. Background Art

[0002] The inspiration for hydrophobic coatings originated from the "lotus effect." The micro-nanostructure of the lotus leaf's surface gives it self-cleaning capabilities, allowing water droplets to roll away surface contaminants. By mimicking this phenomenon, hydrophobic coatings were developed. The technical principle is to reduce the coating's surface energy by constructing a microstructure or introducing low-surface-energy substances, such as silicon and fluorine, into the raw materials, making it difficult for water droplets to wet the surface, thus achieving the desired hydrophobic effect.

[0003] Chinese patent CN105602411A discloses a fluorine-containing hydrophobic coating material and its preparation method, which includes the following components: epoxy resin, dendritic fluorine-containing curing agent, other curing agents, solvent, and silane coupling agent; this method has a low curing temperature and a short curing time, but the physical properties of the coating are not mentioned.

[0004] Therefore, we propose a fluorine-containing super-hydrophobic coating and its preparation process to solve the above problems. Summary of the Invention

[0005] The object of the present invention is to provide a fluorine-containing super-hydrophobic coating and a preparation process thereof to solve the problems raised in the prior art.

[0006] To achieve the above-mentioned object, the present invention provides the following technical solution: a fluorine-containing super-hydrophobic coating, comprising the following components by mass: 60-80 parts of a composite fluorine-containing resin, 5-15 parts of a filler, and 5-10 parts of a curing agent.

[0007] Furthermore, the composite fluorine-containing resin is obtained by blending an epoxy resin with a fluorine-containing esterified epoxy compound;

[0008] The filler is obtained by surface modification of the filler by a coupling agent;

[0009] The filler is SiO2 (silicon dioxide).

[0010] Furthermore, the coupling agent is obtained by reacting cardanol with γ-glycidyloxypropyltrimethoxysilane.

[0011] Furthermore, epoxy resin: brand E44, epoxy equivalent weight 210-230 g / mol, sourced from Jiangyin Wanqian Chemicals Co., Ltd.

[0012] SiO2, product number: 104014, 200-300 nm, sourced from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.

[0013] A preparation process of a fluorine-containing super-hydrophobic coating comprises the following steps:

[0014] The composite fluorine-containing resin, filler and curing agent are mixed and stirred for 0.5-2 hours to obtain a fluorine-containing hydrophobic rubber material. The rubber material is applied to a substrate, dried and cured to obtain a fluorine-containing super-hydrophobic coating.

[0015] Furthermore, the mass ratio of the composite fluorine-containing resin, filler and curing agent is (60-80): (5-15): (5-10).

[0016] Furthermore, the drying process conditions are: temperature 60-70°C, time 1-2h;

[0017] The curing process conditions are: temperature 130-180℃, insulation 2-3h, pressure 0.5-1MPa.

[0018] Furthermore, the curing agent is a mixture of one or more of ethylenediamine, phthalic anhydride, and m-phenylenediamine.

[0019] Furthermore, the composite fluorine-containing resin is prepared by the following process:

[0020] Step 1: xylene, 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, and concentrated sulfuric acid were mixed, heated under nitrogen atmosphere for reaction, and distilled under reduced pressure after the reaction to obtain polyol A;

[0021] Step 2: Mix polyol A, acrylic acid and concentrated sulfuric acid, and heat to react under nitrogen atmosphere to obtain compound B.

[0022] Step 3: Compound B, toluene, and glacial acetic acid are mixed, stirred magnetically at room temperature, heated to 50-60°C, and hydrogen peroxide is added dropwise. The mixture is reacted at this temperature for 4-6 hours, cooled, and washed to obtain a fluorinated esterified epoxy compound C.

[0023] Step 4: Mix the fluorinated esterified epoxy compound C with the epoxy resin and stir them evenly to obtain a composite fluorinated resin.

[0024] Furthermore, in step 1, the molar ratio of xylene, 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, and concentrated sulfuric acid is (8-16):1:(4.5-6.5):(0.01-0.03).

[0025] Furthermore, the heating reaction conditions in step 1 are: temperature 130-180° C., time 3-5 h.

[0026] Furthermore, in step 2, the molar ratio of polyhydroxy compound A, acrylic acid, and concentrated sulfuric acid is (1-3): (4-12): (0.01-0.03).

[0027] Furthermore, the heating reaction conditions in step 2 are: temperature 130-180° C., time 3-5 h.

[0028] Furthermore, in step 3, the mass ratio of compound B, toluene, glacial acetic acid, and hydrogen peroxide is 1:(1-3):(0.1-0.3):(0.7-1.2).

[0029] Furthermore, the rotation speed of the magnetic stirring in step 3 is: 50-70r / min.

[0030] Furthermore, in step 3, the dropping speed is 2-3 drops / s.

[0031] Furthermore, in step 4, the mass ratio of the fluorinated esterified epoxy compound C to the epoxy resin is (1-3):10.

[0032] Furthermore, xylene, CAS No. 1330-20-7, was obtained from Shanghai Xiangheyi Chemical Technology Co., Ltd.;

[0033] 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), CAS No. 3016-76-0, from Gaide Chemical;

[0034] 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, CAS No. 183162-43-8, from Gaide Chemical;

[0035] Acrylic acid, CAS No. 79-10-7, from Langcheng Chemical;

[0036] Concentrated sulfuric acid, CAS number 7664-93-9, from Merck reagent;

[0037] Toluene, CAS No. 108-88-3, was obtained from Merck Reagent;

[0038] Glacial acetic acid, CAS number 64-19-7, was obtained from Jinan Zesheng Chemical Co., Ltd.

[0039] Hydrogen peroxide, CAS No. 7722-84-1, concentration 30%, was obtained from Merck Reagent.

[0040] In the above technical solution, the carboxyl group of 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid) is esterified with the hydroxyl group of 1H,1H,12H,12H-perfluoro-1,12-dodecanediol to generate a polyhydroxy compound A, which is then esterified with acrylic acid to obtain a compound B, and the double bond in the compound B is epoxidized to obtain a fluorinated esterified epoxy compound C, which is then blended with an epoxy resin to obtain a composite fluorinated resin; the low surface energy and cyclic Due to the good adhesion of epoxy resin, during the curing process of the coating, the fluorine chain segments migrate to the surface of the coating, reducing the surface energy of the coating. The epoxy resin undergoes a cross-linking reaction under the action of the curing agent, solving the problem of poor adhesion of the coating; through esterification and epoxidation reactions, a cross-linking structure is formed, which enhances the strength, hardness and heat resistance of the epoxy esterified compound. The epoxy esterified compound is then blended with the epoxy resin. After the coating is cured, a tighter and stronger three-dimensional network structure is formed, thereby improving the cross-linking strength of the coating and comprehensively improving the hydrophobicity and anti-cracking performance of the coating.

[0041] Furthermore, the filler is surface modified, and the specific process is as follows:

[0042] Mix SiO2 and anhydrous ethanol and stir evenly to form a SiO2 ethanol suspension. Heat the suspension in a water bath, add ammonia water, stir and react for 25-45 minutes, then add a coupling agent, continue stirring and react for 18-22 hours, wash the reaction product 2-4 times, and dry to obtain a modified filler.

[0043] Furthermore, the ratio of SiO2, anhydrous ethanol, ammonia water, and coupling agent is (1.5-2.5) g: (30-50) mL: (3-5) mL: (4-6) mL.

[0044] Furthermore, the process conditions of water bath heating are: temperature 50-60°C, time 20-30 minutes.

[0045] Furthermore, the rotation speed of the stirring reaction is: 60-100r / min.

[0046] Furthermore, anhydrous ethanol, CAS number: 64-17-5, was obtained from Merck reagent;

[0047] Ammonia, CAS number: 1336-21-6, was obtained from Nanjing Shengqinghe Chemical Co., Ltd.

[0048] Furthermore, the coupling agent is prepared by the following process:

[0049] Mix γ-glycidyloxypropyltrimethoxysilane and xylene to obtain a mixed solution, heat it to 80-100° C., add cardanol and initiator under nitrogen atmosphere, stir evenly, and keep the mixture warm for 1-2 hours to obtain a coupling agent.

[0050] Furthermore, the mass ratio of γ-glycidyloxypropyltrimethoxysilane to the solvent is 1:(1.5-2.5);

[0051] The mass ratio of the mixed solution, cardanol and initiator is (8-12): (2-4): (0.05-0.1).

[0052] Furthermore, the initiator was azobisisovaleronitrile, CAS number: 13472-08-7, sourced from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd.;

[0053] γ-Glycidyloxypropyltrimethoxysilane, CAS No. 2530-83-8, from Hangzhou Jessica Chemical Co., Ltd.

[0054] Cardanol, CAS number: 501-24-6, is sourced from Shandong Yingsheng Chemical Co., Ltd.

[0055] In the above technical scheme, γ-glycidyloxypropyltrimethoxysilane is modified by cardanol, phenolic hydroxyl groups are introduced to obtain a coupling agent containing phenolic hydroxyl groups, and then SiO2 is modified to obtain a modified filler; the phenolic hydroxyl groups in cardanol undergo a ring-opening reaction with the epoxy groups in γ-glycidyloxypropyltrimethoxysilane to form stable chemical bonds, thereby enhancing the interaction between molecules, promoting the formation of a three-dimensional network structure, and improving the adhesion performance at the interface between the filler and the epoxy resin, giving the coating excellent toughness and strength, making the coating less likely to crack, and enhancing the mechanical properties of the coating.

[0056] Compared with the prior art, the present invention has the following beneficial effects:

[0057] 1. The carboxyl group of 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid) undergoes esterification reaction with the hydroxyl group of 1H,1H,12H,12H-perfluoro-1,12-dodecanediol to generate a polyhydroxy compound A, which is then esterified with acrylic acid to obtain a compound B. The double bond in the compound B is epoxidized to obtain a fluorinated esterified epoxy compound C, which is then blended with an epoxy resin to obtain a composite fluorinated resin; utilizing the low surface energy of the fluorinated esterified epoxy compound C and the good performance of the epoxy resin Good adhesion. During the curing process of the coating, the fluorine chain segments migrate to the surface of the coating, reducing the surface energy of the coating. The epoxy resin undergoes a cross-linking reaction under the action of the curing agent, solving the problem of poor adhesion of the coating. Through esterification and epoxidation reactions, a cross-linking structure is formed, which enhances the strength, hardness and heat resistance of the epoxy esterified compound. The epoxy esterified compound is then blended with the epoxy resin. After the coating is cured, a tighter and stronger three-dimensional network structure is formed, thereby improving the cross-linking strength of the coating and comprehensively improving the hydrophobicity and anti-cracking performance of the coating.

[0058] 2. γ-glycidyloxypropyltrimethoxysilane is modified by cardanol, and phenolic hydroxyl groups are introduced to obtain a coupling agent containing phenolic hydroxyl groups, which is then used to modify SiO2 to obtain a modified filler. The phenolic hydroxyl groups in cardanol react with the epoxy groups in γ-glycidyloxypropyltrimethoxysilane to form a stable chemical bond, thereby enhancing the intermolecular interaction, promoting the formation of a three-dimensional network structure, and improving the adhesion performance at the interface between the filler and the epoxy resin, giving the coating excellent toughness and strength, making the coating less likely to crack, and enhancing the mechanical properties of the coating. DETAILED DESCRIPTION

[0059] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0060] In the following specific embodiments,

[0061] Epoxy resin: brand E44, epoxy equivalent weight 210-230 g / mol, sourced from Jiangyin Wanqian Chemicals Co., Ltd.

[0062] SiO2, product number: 104014, 200-300 nm, from Jiangsu Xianfeng Nanomaterial Technology Co., Ltd.;

[0063] Xylene, CAS No. 1330-20-7, was obtained from Shanghai Xiangheyi Chemical Technology Co., Ltd.

[0064] 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), CAS No. 3016-76-0, from Gaide Chemical;

[0065] 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, CAS No. 183162-43-8, from Gaide Chemical;

[0066] Acrylic acid, CAS No. 79-10-7, from Langcheng Chemical;

[0067] Concentrated sulfuric acid, CAS number 7664-93-9, from Merck reagent;

[0068] Toluene, CAS No. 108-88-3, was obtained from Merck Reagent;

[0069] Glacial acetic acid, CAS number 64-19-7, was obtained from Jinan Zesheng Chemical Co., Ltd.

[0070] Hydrogen peroxide, CAS No. 7722-84-1, concentration 30%, from Merck reagent;

[0071] Anhydrous ethanol, CAS number: 64-17-5, from Merck reagent;

[0072] Ammonia, CAS number: 1336-21-6, was obtained from Nanjing Shengqinghe Chemical Co., Ltd.

[0073] The initiator was azobisisovaleronitrile, CAS number: 13472-08-7, which was obtained from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd.

[0074] γ-Glycidyloxypropyltrimethoxysilane, CAS No. 2530-83-8, from Hangzhou Jessica Chemical Co., Ltd.

[0075] Cardanol, CAS number: 501-24-6, from Shandong Yingsheng Chemical Co., Ltd.

[0076] The curing agent is ethylenediamine, CAS number: 107-15-3, from Merck reagent;

[0077] 1,12-Dodecanediol, CAS number: 5675-51-4, from Nanjing Reagent;

[0078] 3,3'4,4'-Biphenyltetracarboxylic acid, CAS number: 22803-05-0, derived from MacLean's reagent;

[0079] 1,4-bis(2',3'-epoxypropyl)perfluorobutane, CAS No.: from Shanghai Yuanye Biotechnology Co., Ltd.

[0080] Example 1: A process for preparing a fluorine-containing super-hydrophobic coating, comprising the following steps:

[0081] (1) Preparation of composite fluorine-containing resin:

[0082] Step 1: xylene, 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), 1H,1H,12H,12H-perfluoro-1,12-dodecanediol and concentrated sulfuric acid are mixed, heated under a nitrogen atmosphere for reaction, and distilled under reduced pressure after the reaction to obtain a polyol compound A; Step 2: polyol compound A, acrylic acid and concentrated sulfuric acid are mixed, heated under a nitrogen atmosphere for reaction, and compound B is obtained after the reaction; Step 3: compound B, toluene and glacial acetic acid are mixed, magnetically stirred at room temperature, heated to 50°C, hydrogen peroxide is added dropwise, the reaction is carried out at a constant temperature for 4h, cooled, and washed to obtain a fluorine-containing esterified epoxy compound C; Step 4: the fluorine-containing esterified epoxy compound C is mixed with an epoxy resin, stirred evenly, and a composite fluorine-containing resin is obtained; in step 1 The molar ratio of xylene, 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, and concentrated sulfuric acid is 8:1:4.5:0.01; the heating reaction conditions in step 1 are: temperature 130°C, time 3 hours; the molar ratio of polyol A, acrylic acid, and concentrated sulfuric acid in step 2 is 1:4:0.01; the heating reaction conditions in step 2 are: temperature 130°C, time 3 hours; the mass ratio of compound B, toluene, glacial acetic acid, and hydrogen peroxide in step 3 is 1:1:0.1:0.7; the speed of magnetic stirring in step 3 is 50 r / min; the droplet addition rate in step 3 is 2 drops / s; in step 4, the mass ratio of fluorinated esterified epoxy compound C and epoxy resin is 1:10;

[0083] (2) Preparation of modified filler:

[0084] γ-glycidyloxypropyltrimethoxysilane and xylene were mixed to obtain a mixed solution, which was heated to 80°C. Cardanol and an initiator were added under nitrogen atmosphere and stirred evenly. The mixture was kept warm for 1 hour to obtain a coupling agent. The mass ratio of γ-glycidyloxypropyltrimethoxysilane to the solvent was 1:1.5; the mass ratio of the mixed solution, cardanol, hexafluorobutyl methacrylate, and the initiator was 8:2:0.05.

[0085] SiO2 and anhydrous ethanol were mixed and stirred to form a SiO2 ethanol suspension. The suspension was heated in a water bath, and ammonia water was added. The mixture was stirred and reacted for 25 minutes. A coupling agent was then added and the mixture was stirred and reacted for 18 hours. The reaction product was washed twice and dried to obtain a modified filler. The ratio of SiO2, anhydrous ethanol, ammonia water, and coupling agent was 1.5 g:30 mL:3 mL:4 mL. The water bath heating process conditions were: temperature 50°C, time 20 minutes, and stirring reaction speed 60 r / min.

[0086] (3) Preparation of fluorine-containing super-hydrophobic coating:

[0087] The composite fluorine-containing resin, modified filler and curing agent are mixed in a mass ratio of 60:5:5 and stirred for 0.5 hours to obtain a fluorine-containing hydrophobic rubber material. The rubber material is applied to the substrate, dried and cured to obtain a fluorine-containing super-hydrophobic coating; the drying process conditions are: temperature 60°C, time 1 hour; the curing process conditions are: temperature 130°C, insulation 2 hours, pressure 0.5 MPa.

[0088] Example 2: A process for preparing a fluorine-containing super-hydrophobic coating, comprising the following steps:

[0089] (1) Preparation of composite fluorine-containing resin:

[0090] Step 1: xylene, 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), 1H,1H,12H,12H-perfluoro-1,12-dodecanediol and concentrated sulfuric acid are mixed, heated under a nitrogen atmosphere for reaction, and distilled under reduced pressure after the reaction to obtain a polyol compound A; Step 2: polyol compound A, acrylic acid and concentrated sulfuric acid are mixed, heated under a nitrogen atmosphere for reaction, and compound B is obtained after the reaction; Step 3: compound B, toluene and glacial acetic acid are mixed, magnetically stirred at room temperature, heated to 55°C, hydrogen peroxide is added dropwise, the reaction is carried out at a constant temperature for 5h, cooled, and washed to obtain a fluorine-containing esterified epoxy compound C; Step 4: the fluorine-containing esterified epoxy compound C is mixed with an epoxy resin, stirred evenly, and a composite fluorine-containing resin is obtained; the two in step 1 The molar ratio of toluene, 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, and concentrated sulfuric acid is 12:1:5.5:0.02; the heating reaction conditions in step 1 are: temperature 150°C, time 4h; the molar ratio of polyol A, acrylic acid, and concentrated sulfuric acid in step 2 is 2:8:0.02; the heating reaction conditions in step 2 are: temperature 150°C, time 4h; the mass ratio of compound B, toluene, glacial acetic acid, and hydrogen peroxide in step 3 is 1:2:0.2:1.0; the speed of magnetic stirring in step 3 is 60r / min; the droplet addition rate in step 3 is 2 drops / s; in step 4, the mass ratio of fluorinated esterified epoxy compound C and epoxy resin is 2:10;

[0091] (2) Preparation of modified filler:

[0092] γ-glycidyloxypropyltrimethoxysilane and xylene were mixed to obtain a mixed solution, which was heated to 90°C. Cardanol and an initiator were added under nitrogen atmosphere and stirred evenly. The mixture was kept warm for 1.5 hours to obtain a coupling agent. The mass ratio of γ-glycidyloxypropyltrimethoxysilane to the solvent was 1:2; the mass ratio of the mixed solution to cardanol to the initiator was 10:3:0.08.

[0093] SiO2 and anhydrous ethanol were mixed and stirred to form a SiO2 ethanol suspension. The suspension was heated in a water bath, and ammonia water was added. The mixture was stirred and reacted for 30 minutes. A coupling agent was then added and the mixture was stirred and reacted for 20 hours. The reaction product was washed three times and dried to obtain a modified filler. The ratio of SiO2, anhydrous ethanol, ammonia water, and coupling agent was 2g:40mL:4mL:5mL. The water bath heating process conditions were: temperature 70°C, time 25 minutes, and stirring reaction speed 80r / min.

[0094] (3) Preparation of fluorine-containing super-hydrophobic coating:

[0095] The composite fluorine-containing resin, modified filler and curing agent are mixed in a mass ratio of 70:10:8 and stirred for 1.5 hours to obtain a fluorine-containing hydrophobic rubber material. The rubber material is applied to a substrate, dried and cured to obtain a fluorine-containing super-hydrophobic coating; the drying process conditions are: temperature 65°C, time 1.5 hours; the curing process conditions are: temperature 150°C, insulation 2.5 hours, pressure 0.7 MPa.

[0096] Example 3: A process for preparing a fluorine-containing super-hydrophobic coating, comprising the following steps:

[0097] (1) Preparation of composite fluorine-containing resin:

[0098] Step 1: xylene, 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), 1H,1H,12H,12H-perfluoro-1,12-dodecanediol and concentrated sulfuric acid are mixed, heated under a nitrogen atmosphere for reaction, and distilled under reduced pressure after the reaction to obtain a polyol compound A; Step 2: polyol compound A, acrylic acid and concentrated sulfuric acid are mixed, heated under a nitrogen atmosphere for reaction, and compound B is obtained after the reaction; Step 3: compound B, toluene and glacial acetic acid are mixed, magnetically stirred at room temperature, heated to 60°C, hydrogen peroxide is added dropwise, the reaction is carried out at a constant temperature for 6h, cooled, and washed to obtain a fluorine-containing esterified epoxy compound C; Step 4: the fluorine-containing esterified epoxy compound C is mixed with an epoxy resin, stirred evenly, and a composite fluorine-containing resin is obtained; the two in step 1 The molar ratio of toluene, 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, and concentrated sulfuric acid is 16:1:6.5:0.03; the heating reaction conditions in step 1 are: temperature 180°C, time 5h; the molar ratio of polyol A, acrylic acid, and concentrated sulfuric acid in step 2 is 3:12:0.03; the heating reaction conditions in step 2 are: temperature 180°C, time 5h; the mass ratio of compound B, toluene, glacial acetic acid, and hydrogen peroxide in step 3 is 1:3:0.3:1.2; the speed of magnetic stirring in step 3 is 70r / min; the droplet addition rate in step 3 is 3 drops / s; in step 4, the mass ratio of fluorinated esterified epoxy compound C and epoxy resin is 3:10;

[0099] (2) Preparation of modified filler:

[0100] γ-glycidyloxypropyltrimethoxysilane and xylene were mixed to obtain a mixed solution, which was heated to 100°C. Cardanol and an initiator were added under nitrogen atmosphere, stirred evenly, and kept warm for 2 hours to obtain a coupling agent. The mass ratio of γ-glycidyloxypropyltrimethoxysilane to the solvent was 1:2.5; the mass ratio of the mixed solution to cardanol to the initiator was 12:4:0.1.

[0101] SiO2 and anhydrous ethanol were mixed and stirred to form a SiO2 ethanol suspension. The suspension was heated in a water bath, and ammonia water was added. The mixture was stirred and reacted for 45 minutes. A coupling agent was then added and the mixture was stirred and reacted for 22 hours. The reaction product was washed four times and dried to obtain a modified filler. The ratio of SiO2, anhydrous ethanol, ammonia water, and coupling agent was 2.5 g:50 mL:5 mL:6 mL. The water bath heating process conditions were: temperature 60°C, time 30 minutes, and stirring reaction speed 100 r / min.

[0102] (3) Preparation of fluorine-containing super-hydrophobic coating:

[0103] The composite fluorine-containing resin, modified filler and curing agent are mixed in a mass ratio of 80:15:10 and stirred for 2 hours to obtain a fluorine-containing hydrophobic adhesive. The adhesive is applied to a substrate, dried and cured to obtain a fluorine-containing super-hydrophobic coating; the drying process conditions are: temperature 70°C, time 2 hours; the curing process conditions are: temperature 180°C, insulation 3 hours, pressure 1MPa.

[0104] Comparative Example 1: Using Example 1 as a comparison, 1H,1H,12H,12H-perfluoro-1,12-dodecanediol was replaced by 1,12-dodecanediol, and 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid) was replaced by 3,3'4,4'-biphenyltetracarboxylic acid, while the other conditions remained unchanged;

[0105] Comparative Example 2: Using Example 1 as a comparison, the fluorinated esterified epoxy compound C was replaced with 1,4-bis(2',3'-epoxypropyl)perfluorobutane, while the other conditions remained unchanged;

[0106] Comparative Example 3: Using Example 1 as a comparison, the fluorinated esterified epoxy compound C was replaced with 1,4-bis(2',3'-epoxypropyl)perfluorobutane, and the filler was not modified. Other conditions remained unchanged.

[0107] Comparative Example 4: Using Example 1 as a comparison, the filler was not modified, the fluorinated esterified epoxy compound C was not added, and the other conditions remained unchanged. The specific steps were as follows:

[0108] Epoxy resin, filler and curing agent are mixed in a mass ratio of 60:5:5, stirred for 0.5h to obtain a rubber compound, which is applied to a substrate, dried and cured to obtain a coating; the drying process conditions are: temperature 60°C, time 1h; the curing process conditions are: temperature 130°C, insulation 2h, pressure 0.5MPa.

[0109] Experiment: The hydrophobic coatings obtained in Examples 1-3 and Comparative Examples 1-3 were prepared into samples, and their performance was tested and the results were recorded;

[0110] Hydrophobicity test: 6 μL of deionized water was added to the sample surface, and the water droplet profile was fitted using the circular fitting method to perform contact angle analysis.

[0111] Add 8 μL of deionized water to the sample surface and adjust the rotating platform until the deionized water rolls off. The tilt angle of the platform is the rolling angle. Take the average of the three measurements and record it in the table below.

[0112] Adhesion test: Adhesion test was conducted according to GB / T9286-1998. The test results are shown in the following table;

[0113] Tensile performance test: The tensile performance test was carried out using an electronic universal material testing machine at 25°C and a tensile rate of 300 mm / min.

[0114] The following table shows the test results of the hydrophobic coating contact angle, sliding angle, adhesion, and tensile strength;

[0115] Contact angle / ° Roll angle / ° Adhesion Tensile strength / MPa Example 1 148.2 4.2 Level 1 22.3 Example 2 158.8 3.7 Level 0 27.1 Example 3 166.1 3.3 Level 0 32.9 Comparative Example 1 135.5 4.9 Level 1 21.1 Comparative Example 2 140.7 4.7 Level 1 19.8 Comparative Example 3 136.6 5.6 Level 2 16.8 Comparative Example 4 127.8 6.2 Level 3 14.5

[0116] According to the data in the above table, we can clearly draw the following conclusions:

[0117] The coatings obtained in Examples 1-3 were compared with the coatings obtained in Comparative Examples 1-3. The test results show that:

[0118] Compared with Example 1, the hydrophobicity of Comparative Example 1 is reduced because 1,12-dodecanediol does not contain a hydrophobic fluorine segment. Therefore, the synthesized esterified epoxy compound does not contain a fluorine segment and cannot reduce the surface energy of the coating, resulting in a decrease in the hydrophobicity of the coating.

[0119] Compared with Example 1, the tensile strength of Comparative Example 2 is reduced. The fluorinated esterified epoxy compound C is replaced with 1,4-bis(2',3'-epoxypropyl)perfluorobutane. 1,4-bis(2',3'-epoxypropyl)perfluorobutane contains a longer perfluorocarbon chain, which produces a larger steric hindrance effect, resulting in a low degree of crosslinking with the epoxy resin, resulting in a decrease in the tensile strength of the coating;

[0120] Compared with Example 1, the adhesion and tensile strength of Comparative Example 3 decreased significantly. This is because the filler was not modified, the adhesion performance at the interface between the filler and the epoxy resin decreased, the toughness of the coating decreased, and it was easy to crack, resulting in a decrease in the tensile performance of the coating;

[0121] Compared with Example 1, in Comparative Example 4, the filler is not modified and the fluorinated esterified epoxy compound C is not added. All properties are significantly reduced, indicating that the present invention's setting of the coating preparation process and the components used can promote the comprehensive improvement of its hydrophobicity and mechanical properties.

[0122] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

Claims

1. A fluorine-containing super-hydrophobic coating, characterized in that: It includes the following components by mass: 60-80 parts of composite fluorine-containing resin, 5-15 parts of modified filler, and 5-10 parts of curing agent; The composite fluorine-containing resin is obtained by blending epoxy resin and fluorine-containing esterified epoxy compound; The modified filler is obtained by surface-modifying the filler with a coupling agent; The filler is SiO2; The coupling agent is obtained by reacting cardanol with γ-glycidyloxypropyltrimethoxysilane; The composite fluorine-containing resin is prepared by the following process: Step 1: Mix xylene, 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, and concentrated sulfuric acid, heat and react under a nitrogen atmosphere, and distill under reduced pressure after the reaction to obtain polyol A; Step 2: Mix polyol A, acrylic acid and concentrated sulfuric acid, and heat to react under nitrogen atmosphere to obtain compound B. Step 3: Compound B, toluene, and glacial acetic acid are mixed, stirred magnetically at room temperature, heated to 50-60°C, and hydrogen peroxide is added dropwise. The mixture is reacted at this temperature for 4-6 hours, cooled, and washed to obtain a fluorinated esterified epoxy compound C. Step 4: Mix the fluorinated esterified epoxy compound C with the epoxy resin and stir them evenly to obtain a composite fluorinated resin.

2. A process for preparing a fluorine-containing super-hydrophobic coating according to claim 1, characterized in that: The following steps are involved: The composite fluorine-containing resin, filler and curing agent are mixed and stirred for 0.5-2 hours to obtain a fluorine-containing hydrophobic rubber material. The rubber material is applied to a substrate, dried and cured to obtain a fluorine-containing super-hydrophobic coating.

3. A process for preparing a fluorine-containing super-hydrophobic coating according to claim 2, characterized in that: The composite fluorine-containing resin is prepared by the following process: Step 1: Mix xylene, 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, and concentrated sulfuric acid, heat and react under a nitrogen atmosphere, and distill under reduced pressure after the reaction to obtain polyol A; Step 2: Mix polyol A, acrylic acid and concentrated sulfuric acid, and heat to react under nitrogen atmosphere to obtain compound B. Step 3: Compound B, toluene, and glacial acetic acid are mixed, stirred magnetically at room temperature, heated to 50-60°C, and hydrogen peroxide is added dropwise. The mixture is reacted at this temperature for 4-6 hours, cooled, and washed to obtain a fluorinated esterified epoxy compound C. Step 4: Mix the fluorinated esterified epoxy compound C with the epoxy resin and stir them evenly to obtain a composite fluorinated resin.

4. A process for preparing a fluorine-containing super-hydrophobic coating according to claim 3, characterized in that: In step 1, the molar ratio of xylene, 4,4'-(2,2,2-trifluoro-1-trifluoromethyl)ethylenebis(1,2-benzenedicarboxylic acid), 1H,1H,12H,12H-perfluoro-1,12-dodecanediol, and concentrated sulfuric acid is (8-16):1:(4.5-6.5):(0.01-0.03).

5. A process for preparing a fluorine-containing super-hydrophobic coating according to claim 2, characterized in that: The filler is surface modified, and the specific process is as follows: Mix SiO2 and anhydrous ethanol and stir evenly to form a SiO2 ethanol suspension. Heat the suspension in a water bath, add ammonia water, stir and react for 25-45 minutes, then add a coupling agent, continue stirring and react for 18-22 hours, wash the reaction product 2-4 times, and dry to obtain a modified filler.

6. The process for preparing a fluorine-containing super-hydrophobic coating according to claim 5, wherein: The coupling agent is prepared by the following process: Mix γ-glycidyloxypropyltrimethoxysilane and xylene to obtain a mixed solution, heat it to 80-100° C., add cardanol and initiator under nitrogen atmosphere, stir evenly, and keep the mixture warm for 1-2 hours to obtain a coupling agent.

7. The process for preparing a fluorine-containing super-hydrophobic coating according to claim 2, wherein: The drying process conditions are: temperature 60-70℃, time 1-2h; The curing process conditions are: temperature 130-180℃, insulation 2-3h, pressure 0.5-1MPa.

8. The process for preparing a fluorine-containing super-hydrophobic coating according to claim 3, wherein: In step 2, the molar ratio of polyol A, acrylic acid, and concentrated sulfuric acid is (1-3): (4-12): (0.01-0.03).