CN105885564B - Super-hydrophobic composite coating of the multiple fluorinated epoxy of full stress-strain and preparation method thereof and application method - Google Patents
Super-hydrophobic composite coating of the multiple fluorinated epoxy of full stress-strain and preparation method thereof and application method Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 109
- 239000011248 coating agent Substances 0.000 title claims abstract description 105
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000004593 Epoxy Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 29
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 29
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 25
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 24
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 claims abstract description 23
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011859 microparticle Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003682 fluorination reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000010147 laser engraving Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011185 multilayer composite material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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Abstract
本发明公开了一种全有机多重氟化环氧超疏水复合涂料及其制备方法和使用方法，该涂料包括涂料体系和固化剂，其中涂料体系的组分包括环氧树脂、聚四氟乙烯微粒、聚全氟甲基异丙基醚和有机溶剂，固化剂是由二乙烯三胺和全氟丁酸经反应制成。其制备方法包括涂料体系的制备和固化剂的制备。其使用方法是将固化剂溶于稀释剂中，将所得固化剂溶液加入到涂料体系中，混合均匀，涂覆于所需表面固化即可。本发明的全有机多重氟化环氧超疏水复合涂料具有良好超疏水性能、较好耐磨性能、耐水流冲击、耐腐蚀性、粘附力强、适用范围广等优点，且制备方法简单易实施，适合大面积使用。
The invention discloses an all-organic multi-fluorinated epoxy superhydrophobic composite coating and its preparation method and application method. The coating includes a coating system and a curing agent, wherein the components of the coating system include epoxy resin and polytetrafluoroethylene particles , polyperfluoromethyl isopropyl ether and organic solvent, and the curing agent is made by reacting diethylenetriamine and perfluorobutyric acid. The preparation method includes the preparation of the coating system and the preparation of the curing agent. The method of use is to dissolve the curing agent in the diluent, add the obtained curing agent solution into the coating system, mix evenly, and apply it on the desired surface for curing. The all-organic multiple fluorinated epoxy superhydrophobic composite coating of the present invention has the advantages of good superhydrophobic performance, good wear resistance, water impact resistance, corrosion resistance, strong adhesion, wide application range, etc., and the preparation method is simple and easy implementation, suitable for large area use.
Description
技术领域technical field
本发明属于涂料的制备领域，涉及一种超疏水涂料及其制备和使用方法，具体涉及一种全有机多重氟化环氧超疏水复合涂料及其制备方法和使用方法。The invention belongs to the field of coating preparation, and relates to a super-hydrophobic coating and its preparation and application method, in particular to an all-organic multiple fluorinated epoxy super-hydrophobic composite coating and its preparation method and application method.
背景技术Background technique
因在自清洁、防冰、油水分离等领域的可应用性，接触角大于150°、滚动角小于10°的超疏水现象在近些年引起了广泛关注。且研究表明，制备超疏水表面通常需要满足两个条件：使用低表面能物质以及在材料表面构筑微纳二级结构。Due to its applicability in self-cleaning, anti-icing, oil-water separation and other fields, the superhydrophobic phenomenon with a contact angle greater than 150° and a rolling angle less than 10° has attracted widespread attention in recent years. And studies have shown that the preparation of superhydrophobic surfaces usually needs to meet two conditions: the use of low surface energy substances and the construction of micro-nano secondary structures on the surface of the material.
目前制备超疏水表面的方法有溶胶-凝胶法、化学气相沉积、相分离、电沉积以及激光雕刻等，这些方法常常存在着制备麻烦，条件苛刻等缺点。使用微米或纳米粒径的粒子来提高疏水表面的粗糙度是一个行之有效的方法，常用的粒子有SiO2、Fe3O4、ZnO、PTFE等。At present, methods for preparing superhydrophobic surfaces include sol-gel method, chemical vapor deposition, phase separation, electrodeposition, and laser engraving, etc. These methods often have disadvantages such as troublesome preparation and harsh conditions. It is an effective method to increase the roughness of the hydrophobic surface by using micron or nanometer particle size particles. Commonly used particles include SiO 2 , Fe 3 O 4 , ZnO, PTFE, etc.
在已知的大量方法中，所制备的超疏水表面由于受到耐水压冲击、耐磨性和耐腐蚀性等性能不佳的制约而难以大规模应用。因此，发展一种具有良好疏水性、耐磨性、耐水流冲击和耐腐蚀性的超疏水涂料具有重要的意义。In a large number of known methods, the prepared superhydrophobic surface is difficult to be applied on a large scale due to the constraints of poor performance such as hydraulic shock resistance, wear resistance and corrosion resistance. Therefore, it is of great significance to develop a superhydrophobic coating with good hydrophobicity, abrasion resistance, water impact resistance and corrosion resistance.
发明内容Contents of the invention
本发明所要解决的技术问题是克服现有技术的不足，提供一种具有良好超疏水性能、较好耐磨性能、耐水流冲击、耐腐蚀性、粘附力强、适用范围广的全有机多重氟化环氧超疏水复合涂料及其制备方法和使用方法。The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide an all-organic multi-layer composite material with good superhydrophobic properties, good wear resistance, water impact resistance, corrosion resistance, strong adhesion and wide application range. Fluorinated epoxy superhydrophobic composite coating and its preparation method and application method.
为解决上述技术问题，本发明采用的技术方案是：In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
一种全有机多重氟化环氧超疏水复合涂料，所述全有机多重氟化环氧超疏水复合涂料包括涂料体系和固化剂；An all-organic multiple fluorinated epoxy superhydrophobic composite coating, the all-organic multiple fluorinated epoxy superhydrophobic composite coating includes a coating system and a curing agent;
所述涂料体系包括环氧树脂、聚四氟乙烯微粒、聚全氟甲基异丙基醚和有机溶剂；所述环氧树脂、聚四氟乙烯微粒、聚全氟甲基异丙基醚的质量比为1∶0.4～3.5∶0.1～0.3；所述有机溶剂的质量与所述环氧树脂、聚四氟乙烯微粒、聚全氟甲基异丙基醚的总质量之比为1.5～10∶1；The coating system includes epoxy resin, polytetrafluoroethylene microparticles, polyperfluoromethyl isopropyl ether and organic solvent; the epoxy resin, polytetrafluoroethylene microparticles, polyperfluoromethyl isopropyl ether The mass ratio is 1:0.4～3.5:0.1～0.3; the ratio of the mass of the organic solvent to the total mass of the epoxy resin, polytetrafluoroethylene particles and polyperfluoromethyl isopropyl ether is 1.5～10 : 1;
所述固化剂是由二乙烯三胺和全氟丁酸经反应制备得到。The curing agent is prepared by reacting diethylenetriamine and perfluorobutyric acid.
上述的全有机多重氟化环氧超疏水复合涂料中，优选的，所述环氧树脂、聚四氟乙烯微粒、聚全氟甲基异丙基醚的质量比为1∶1～3∶0.2～0.3。In the above-mentioned all-organic multiple fluorinated epoxy superhydrophobic composite coating, preferably, the mass ratio of the epoxy resin, polytetrafluoroethylene particles, and polyperfluoromethyl isopropyl ether is 1:1 to 3:0.2 ~0.3.
上述的全有机多重氟化环氧超疏水复合涂料中，更优选的，所述环氧树脂、聚四氟乙烯微粒、聚全氟甲基异丙基醚的质量配比为1∶1.5～3∶0.2。In the above-mentioned all-organic multiple fluorinated epoxy superhydrophobic composite coating, more preferably, the mass ratio of the epoxy resin, polytetrafluoroethylene particles, and polyperfluoromethyl isopropyl ether is 1: 1.5 to 3 : 0.2.
上述的全有机多重氟化环氧超疏水复合涂料中，优选的，所述环氧树脂为E-51环氧树脂、E-44环氧树脂、E-42环氧树脂中的一种；In the above-mentioned all-organic multiple fluorinated epoxy superhydrophobic composite coating, preferably, the epoxy resin is one of E-51 epoxy resin, E-44 epoxy resin, and E-42 epoxy resin;
和/或，所述有机溶剂为丙酮、乙醇或乙酸乙酯；And/or, the organic solvent is acetone, ethanol or ethyl acetate;
和/或，所述二乙烯三胺的纯度为99%以上，所述全氟丁酸的纯度为99.5%以上。And/or, the purity of the diethylenetriamine is above 99%, and the purity of the perfluorobutyric acid is above 99.5%.
上述的全有机多重氟化环氧超疏水复合涂料中，更优选的，所述二乙烯三胺与全氟丁酸的摩尔比为1∶1～2。In the above-mentioned all-organic multi-fluorinated epoxy superhydrophobic composite coating, more preferably, the molar ratio of diethylenetriamine to perfluorobutyric acid is 1:1-2.
上述的全有机多重氟化环氧超疏水复合涂料中，进一步优选的，所述二乙烯三胺与全氟丁酸的摩尔比为1∶1，所述环氧树脂为E-51环氧树脂，所述环氧树脂与所述固化剂的质量比为10∶4。In the above-mentioned all-organic multiple fluorinated epoxy superhydrophobic composite coating, it is further preferred that the molar ratio of the diethylenetriamine to perfluorobutyric acid is 1:1, and the epoxy resin is E-51 epoxy resin , the mass ratio of the epoxy resin to the curing agent is 10:4.
上述的全有机多重氟化环氧超疏水复合涂料中，优选的，所述聚四氟乙烯微粒的平均粒径为100nm～1μm。In the above-mentioned all-organic multi-fluorinated epoxy superhydrophobic composite coating, preferably, the average particle diameter of the polytetrafluoroethylene particles is 100 nm-1 μm.
上述的全有机多重氟化环氧超疏水复合涂料中，更优选的，所述聚四氟乙烯微粒的平均粒径为100nm～200nm。In the above-mentioned all-organic multiple fluorinated epoxy superhydrophobic composite coating, more preferably, the average particle diameter of the polytetrafluoroethylene particles is 100nm-200nm.
作为一个总的技术构思，本发明还提供一种上述的全有机多重氟化环氧超疏水复合涂料的制备方法，所述制备方法包括涂料体系的制备和固化剂的制备：As a general technical conception, the present invention also provides a kind of preparation method of above-mentioned all-organic multiple fluorinated epoxy superhydrophobic composite coating, and described preparation method comprises the preparation of coating system and the preparation of curing agent:
所述涂料体系的制备过程如下：将环氧树脂溶于部分有机溶剂中，得到环氧树脂溶液；将聚四氟乙烯微粒分散于另一部分有机溶剂中，得到聚四氟乙烯悬浊液；将聚四氟乙烯悬浊液与环氧树脂溶液混合，经搅拌后，加入聚全氟甲基异丙基醚，继续搅拌，得到涂料体系；The preparation process of the coating system is as follows: dissolve the epoxy resin in part of the organic solvent to obtain an epoxy resin solution; disperse the polytetrafluoroethylene particles in another part of the organic solvent to obtain a polytetrafluoroethylene suspension; The polytetrafluoroethylene suspension is mixed with the epoxy resin solution, and after stirring, polyperfluoromethyl isopropyl ether is added, and the stirring is continued to obtain a coating system;
所述固化剂的制备过程如下：先将二乙烯三胺与全氟丁酸分别溶解于溶剂中，然后将所得全氟丁酸溶液加入到所得二乙烯三胺溶液中，经氟化反应后，除去溶剂，得到固化剂。The preparation process of the curing agent is as follows: firstly dissolve diethylenetriamine and perfluorobutyric acid in a solvent respectively, then add the obtained perfluorobutyric acid solution into the obtained diethylenetriamine solution, and after the fluorination reaction, The solvent is removed to obtain a curing agent.
作为一个总的技术构思，本发明还提供一种上述的全有机多重氟化环氧超疏水复合涂料或者上述的制备方法制得的全有机多重氟化环氧超疏水复合涂料的使用方法，包括以下步骤：将固化剂溶于稀释剂中，将所得固化剂溶液加入到所述涂料体系中，混合均匀后，涂覆于所需表面固化即可。As a general technical concept, the present invention also provides a method for using the above-mentioned all-organic multiple fluorinated epoxy superhydrophobic composite coating or the all-organic multiple fluorinated epoxy superhydrophobic composite coating obtained by the above-mentioned preparation method, including The following steps: dissolve the curing agent in the diluent, add the obtained curing agent solution into the coating system, mix evenly, and apply it on the desired surface for curing.
本发明的全有机多重氟化环氧超疏水复合涂料中，固化剂与100g环氧树脂的质量比是根据固化剂的胺用量=固化剂的胺当量×环氧树脂的环氧值的计算公式来获得，具体计算过程为本领域的公知常识，即二乙烯三胺与全氟丁酸的摩尔比、环氧树脂的具体型号确定后，固化剂与环氧树脂的质量比也确定了。其中，固化剂的胺当量由二乙烯三胺和全氟丁酸的摩尔比1∶a（a≤2）确定，胺当量为（103+214a-18a）/（5-a），其中103为二乙烯三胺的分子质量，214为全氟丁酸的分子质量，18为所生成水的分子质量，（103+214a-18a）为新生产固化剂的分子质量，（5-a）为所含活泼氢个数。In the all-organic multiple fluorinated epoxy superhydrophobic composite coating of the present invention, the mass ratio of curing agent to 100g epoxy resin is based on the calculation formula of the amine amount of curing agent=amine equivalent of curing agent×epoxy value of epoxy resin The specific calculation process is common knowledge in the art, that is, after the molar ratio of diethylenetriamine to perfluorobutyric acid and the specific type of epoxy resin are determined, the mass ratio of curing agent to epoxy resin is also determined. Among them, the amine equivalent of the curing agent is determined by the molar ratio of diethylenetriamine and perfluorobutyric acid 1:a (a≤2), and the amine equivalent is (103+214a-18a)/(5-a), where 103 is The molecular mass of diethylenetriamine, 214 is the molecular mass of perfluorobutyric acid, 18 is the molecular mass of the produced water, (103+214a-18a) is the molecular mass of the newly produced curing agent, (5-a) is the molecular mass of the obtained Contains the number of active hydrogen.
本发明的制备方法中，所述固化剂的制备中所用溶剂优选为水或乙醇。In the preparation method of the present invention, the solvent used in the preparation of the curing agent is preferably water or ethanol.
本发明的使用方法中，所述固化是在常温下固化12h或在100℃下固化1h，但不限于此。In the use method of the present invention, the curing is at room temperature for 12 hours or at 100° C. for 1 hour, but not limited thereto.
本发明的使用方法中，所述稀释剂为丙酮、乙醇或乙酸乙酯，优选与涂料体系的有机溶剂保持一致。In the use method of the present invention, the diluent is acetone, ethanol or ethyl acetate, preferably consistent with the organic solvent of the coating system.
与现有技术相比，本发明的优点在于：Compared with the prior art, the present invention has the advantages of:
1、本发明提供了一种全有机多重氟化环氧超疏水复合涂料，包括涂料体系和固化剂，其中涂料体系包括环氧树脂、聚四氟乙烯微粒和聚全氟甲基异丙基醚，固化剂是由二乙烯三胺和全氟丁酸经反应制成。本发明中全有机涂料在耐腐蚀方面有着独特的优势，多重氟化则有利于表面疏水性能以及在耐腐蚀性能上的提高，环氧树脂拥有优良的力学性能、耐化学腐蚀性能和与基底的粘接性能，这三个重要的技术特征在本发明的复合涂料中起到了协同增效的作用，使本发明的全有机多重氟化环氧超疏水复合涂料具有优异的超疏水性能、较好耐磨性能、耐水流冲击、耐腐蚀性、粘附力强、适用范围广等性能。1. The present invention provides an all-organic multiple fluorinated epoxy superhydrophobic composite coating, including a coating system and a curing agent, wherein the coating system includes epoxy resin, polytetrafluoroethylene particles and polyperfluoromethyl isopropyl ether , The curing agent is made by reacting diethylenetriamine and perfluorobutyric acid. In the present invention, the all-organic coating has unique advantages in terms of corrosion resistance. Multiple fluorination is beneficial to the improvement of surface hydrophobicity and corrosion resistance. Epoxy resin has excellent mechanical properties, chemical corrosion resistance and adhesion with the substrate. Adhesive performance, these three important technical characteristics have played the synergistic effect in the composite coating of the present invention, make the all-organic multiple fluorinated epoxy superhydrophobic composite coating of the present invention have excellent superhydrophobic performance, better Wear resistance, water impact resistance, corrosion resistance, strong adhesion, wide application range and other properties.
2、本发明的超疏水复合涂料所制备的超疏水表面在抗水流冲击方面具有良好的性能，最高能承受流速高达34m/s（韦伯数43000）的水流冲击，在一定程度上能满足室内外的大规模应用。2. The superhydrophobic surface prepared by the superhydrophobic composite coating of the present invention has good performance in resisting water flow impact, and can withstand the water flow impact with a flow rate as high as 34m/s (Weber number 43000), and can meet indoor and outdoor conditions to a certain extent. large-scale application.
3、本发明超疏水复合涂料所制备的超疏水表面具有良好的耐腐蚀性，在王水中浸泡1h和1mol/L的NaOH溶液中浸泡24h，都仍然能保持超疏水状态。3. The superhydrophobic surface prepared by the superhydrophobic composite coating of the present invention has good corrosion resistance, and can still maintain a superhydrophobic state after soaking in aqua regia for 1 hour and immersing in 1mol/L NaOH solution for 24 hours.
4、本发明的超疏水复合涂料所制备的超疏水表面具有优良的耐磨性能，循环100次后，5cm处的样品表面的接触角仍然能保持在145°以上。4. The superhydrophobic surface prepared by the superhydrophobic composite coating of the present invention has excellent wear resistance, and after 100 cycles, the contact angle of the sample surface at 5 cm can still be kept above 145°.
5、本发明的超疏水复合涂料所制备的超疏水表面具有与基底粘附力强的特点，经粘附力测试，在循环30次后，表面仍保持超疏水性能。5. The superhydrophobic surface prepared by the superhydrophobic composite coating of the present invention has the characteristics of strong adhesion to the substrate. After the adhesion test, the surface still maintains superhydrophobic performance after 30 cycles.
6、本发明的全有机多重氟化环氧超疏水复合涂料的制备方法简单易行，成本低廉，使用方法方便快捷、简单易操作，适用于不同材质基板的大面积使用。6. The preparation method of the all-organic multiple fluorinated epoxy superhydrophobic composite coating of the present invention is simple and easy, the cost is low, the use method is convenient, fast, simple and easy to operate, and it is suitable for large-area use of different material substrates.
附图说明Description of drawings
图1为本发明实施例1中全有机多重氟化环氧超疏水复合涂料所制备涂层试样的SEM图（放大倍数为10000倍）。Figure 1 is the SEM image of the coating sample prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in Example 1 of the present invention (magnification is 10000 times).
图2为本发明实施例1中全有机多重氟化环氧超疏水复合涂料所制备涂层试样的粘附性能测试方法示意图。Fig. 2 is a schematic diagram of the adhesion performance test method of the coating sample prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in Example 1 of the present invention.
图3为本发明实施例1中全有机多重氟化环氧超疏水复合涂料所制备涂层试样的粘附性能测试结果图。Fig. 3 is a graph showing the adhesion performance test results of the coating samples prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in Example 1 of the present invention.
图4为本发明实施例1中全有机多重氟化环氧超疏水复合涂料所制备涂层试样的耐磨性能测试方法示意图。Fig. 4 is a schematic diagram of the test method for the wear resistance of the coating sample prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in Example 1 of the present invention.
图5为本发明实施例1中全有机多重氟化环氧超疏水复合涂料所制备涂层试样的耐磨性能测试结果图。Fig. 5 is a graph showing the wear resistance test results of the coating samples prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in Example 1 of the present invention.
图6为本发明实施例1中全有机多重氟化环氧超疏水复合涂料所制备涂层试样的耐水流冲击试验方法示意图。Fig. 6 is a schematic diagram of the water flow impact test method of the coating sample prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in Example 1 of the present invention.
图7为本发明实施例1中全有机多重氟化环氧超疏水复合涂料所制备涂层试样在34m/s的水流冲击下不同时间的实景高速摄像拍摄图。Fig. 7 is a real-scene high-speed camera shot of the coating sample prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in Example 1 of the present invention under the impact of 34m/s water flow at different times.
具体实施方式Detailed ways
以下结合说明书附图和具体优选的实施例对本发明作进一步描述，但并不因此而限制本发明的保护范围。The present invention will be further described below in conjunction with the accompanying drawings and specific preferred embodiments, but the protection scope of the present invention is not limited thereby.
以下实施例中所采用的材料和仪器均为市售，其中二乙烯三胺的纯度为99%以上，全氟丁酸的纯度为99.5%以上。The materials and instruments used in the following examples are all commercially available, wherein the purity of diethylenetriamine is above 99%, and the purity of perfluorobutyric acid is above 99.5%.
实施例1：Example 1:
一种本发明的全有机多重氟化环氧超疏水复合涂料，该超疏水复合涂料包括涂料体系和固化剂。An all-organic multi-fluorinated epoxy super-hydrophobic composite coating of the present invention, the super-hydrophobic composite coating includes a coating system and a curing agent.
涂料体系包括3g E-51环氧树脂、10.5g 聚四氟乙烯微粒、0.3g聚全氟甲基异丙基醚和35ml丙酮；聚四氟乙烯微粒的平均粒径为100nm。The coating system includes 3g of E-51 epoxy resin, 10.5g of polytetrafluoroethylene microparticles, 0.3g of polyperfluoromethyl isopropyl ether and 35ml of acetone; the average particle size of polytetrafluoroethylene microparticles is 100nm.
固化剂是由二乙烯三胺和全氟丁酸经氟化反应制备得到，二乙烯三胺与全氟丁酸的摩尔比为1∶1。The curing agent is prepared by fluorinating diethylenetriamine and perfluorobutyric acid, and the molar ratio of diethylenetriamine to perfluorobutyric acid is 1:1.
E-51环氧树脂与固化剂的质量比为10∶4。The mass ratio of E-51 epoxy resin to curing agent is 10:4.
一种上述本实施例的全有机多重氟化环氧超疏水复合涂料的制备方法，包括涂料体系的制备和固化剂的制备。A preparation method of the above-mentioned all-organic multiple fluorinated epoxy superhydrophobic composite coating of the present embodiment, including the preparation of the coating system and the preparation of the curing agent.
涂料体系的制备过程如下：首先，将3g E-51环氧树脂溶解于5ml丙酮中，得到环氧树脂的丙酮溶液；将10.5g平均粒径为100nm的聚四氟乙烯微粒分散于30ml丙酮中，并使用电磁搅拌机在1000r/min的转速下分散10min，得到均匀分散的聚四氟乙烯微粒悬浊液。然后，将聚四氟乙烯微粒悬浊液加入环氧树脂的丙酮溶液中，并用电磁搅拌机搅拌15min，保证充分混合。最后，加入0.3g聚全氟甲基异丙基醚，并在1000 r/min的转速下分散20min，得到涂料体系。The preparation process of the coating system is as follows: First, dissolve 3g of E-51 epoxy resin in 5ml of acetone to obtain an acetone solution of epoxy resin; disperse 10.5g of polytetrafluoroethylene particles with an average particle size of 100nm in 30ml of acetone , and use an electromagnetic stirrer to disperse for 10 min at a speed of 1000 r/min to obtain a uniformly dispersed suspension of polytetrafluoroethylene particles. Then, add the suspension of polytetrafluoroethylene particles into the acetone solution of epoxy resin, and stir with an electromagnetic stirrer for 15 minutes to ensure thorough mixing. Finally, 0.3 g of polyperfluoromethyl isopropyl ether was added and dispersed for 20 min at a speed of 1000 r/min to obtain a coating system.
固化剂的制备过程如下：首先，将0.01mol二乙烯三胺溶解于10ml去离子水中，得到二乙烯三胺溶液；将0.01mol全氟丁酸溶解于10ml去离子水中，得到全氟丁酸溶液。然后将全氟丁酸溶液逐滴滴加到二乙烯三胺溶液中进行氟化反应，反应完成后，将产物溶液加热至100℃，使去离子水蒸发，得到固化剂。为方便实验操作和反应的进行，本实施例制备了过量的固化剂，制备完成后取其中的1.2g固化剂作为上述本实施例超疏水复合涂料的固化剂组分。The preparation process of the curing agent is as follows: First, dissolve 0.01mol of diethylenetriamine in 10ml of deionized water to obtain a solution of diethylenetriamine; dissolve 0.01mol of perfluorobutyric acid in 10ml of deionized water to obtain a solution of perfluorobutyric acid . Then, the perfluorobutyric acid solution is added dropwise to the diethylenetriamine solution to carry out the fluorination reaction. After the reaction is completed, the product solution is heated to 100° C. to evaporate the deionized water to obtain a curing agent. In order to facilitate the experimental operation and reaction, an excess amount of curing agent was prepared in this embodiment, and 1.2 g of the curing agent was used as the curing agent component of the superhydrophobic composite coating in this embodiment above after the preparation was completed.
一种上述本实施例的全有机多重氟化环氧超疏水复合涂料的使用方法，包括以下步骤：首先，将1.2g所制备的固化剂溶解于10ml丙酮中，然后将固化剂的丙酮溶液加入到41.4g涂料体系中，在1000r/min的转速下分散20min，然后使用超声分散15min，再在1000r/min的转速下分散5min。最后，使用喷涂或滚涂、刷涂的方式将均匀混合的涂料涂覆至铝板基底上，在室温下固化12h或在100℃条件下固化1h小时，得到全有机多重氟化环氧超疏水复合涂料的涂层试样，该试样具有耐水流冲击、耐腐蚀、耐磨、粘附力强等性能的超疏水表面，接触角为160°～165°，滚动角小于2°。A method for using the all-organic multiple fluorinated epoxy superhydrophobic composite coating of the above-mentioned present embodiment, comprising the following steps: first, 1.2g of the prepared curing agent is dissolved in 10ml of acetone, and then the acetone solution of the curing agent is added Into 41.4g of the coating system, disperse at a speed of 1000r/min for 20 minutes, then use ultrasonic dispersion for 15 minutes, and then disperse at a speed of 1000r/min for 5 minutes. Finally, apply the uniformly mixed paint on the aluminum substrate by spraying, rolling, or brushing, and cure it at room temperature for 12 hours or at 100°C for 1 hour to obtain an all-organic multi-fluorinated epoxy superhydrophobic composite. A coating sample of paint, which has a super-hydrophobic surface with properties such as water impact resistance, corrosion resistance, wear resistance, and strong adhesion, with a contact angle of 160°-165° and a rolling angle of less than 2°.
图1为本实施例中全有机多重氟化环氧超疏水复合涂料所制备涂层试样的SEM图（放大倍数为10000倍）。从图1中可以明显观察到涂层表面的微纳二级结构，这对超疏水性能至关重要。Figure 1 is the SEM image of the coating sample prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in this example (magnification is 10000 times). From Figure 1, the micro-nano secondary structure on the coating surface can be clearly observed, which is crucial to the superhydrophobic performance.
图2为本实施例中全有机多重氟化环氧超疏水复合涂料所制备涂层试样的粘附性能测试方法示意图，使用强粘附力的胶布（与钢铁表面的粘附力值达到3900N/m）对表面进行重复的粘附与撕开过程。使用图2的方法对涂层试样的粘附力进行测试的结果如图3所示，由图3可知，本发明所制备的超疏水表面具有与基底粘附力强的特点，在循环30次后，表面仍保持超疏水性能。Fig. 2 is the schematic diagram of the adhesion performance test method of the coating sample prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in the present embodiment, using adhesive tape with strong adhesion (the adhesion value with the steel surface reaches 3900N /m) Repeated sticking and peeling process on the surface. Use the method of Fig. 2 to test the result of the adhesion of the coating sample as shown in Fig. 3, as can be seen from Fig. 3, the superhydrophobic surface prepared by the present invention has the characteristics of strong adhesion with the substrate, after cycle 30 After several times, the surface still maintains superhydrophobic properties.
图4为本实施例中全有机多重氟化环氧超疏水复合涂料所制备涂层试样的耐磨性能测试方法示意图，将涂覆有超疏水涂层的样品在装有砂砾的烧杯中重复插拔，并测定不同深度条件下在不同摩擦次数下的接触角值。使用图4的耐磨性测试方法对样品性能进行测试的结果如图5所示，由图5可知，本发明所制备的超疏水表面具有优良的耐磨性能，循环100次后，h=5cm处的样品表面的接触角仍然能保持在145°以上。Figure 4 is a schematic diagram of the wear resistance test method of the coating sample prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in this embodiment, and the sample coated with the superhydrophobic coating is repeated in a beaker equipped with gravel Insert and pull out, and measure the contact angle value under different friction times under different depth conditions. Use the abrasion resistance testing method of Fig. 4 to test the result of sample performance as shown in Fig. 5, as can be seen from Fig. 5, the superhydrophobic surface prepared by the present invention has excellent abrasion resistance, and after 100 cycles, h=5cm The contact angle of the sample surface can still be kept above 145°.
图6为本实施例中全有机多重氟化环氧超疏水复合涂料所制备涂层试样的耐水流冲击试验方法示意图。在电脑控制下使用高压氮气产生不同流速的水柱来冲击表面，并使用高速摄像机对冲击过程进行记录。使用图6的方法对样品性能进行测试的结果如图7所示，图7为本实施例中全有机多重氟化环氧超疏水复合涂料所制备涂层试样在34m/s（雷诺数43000）的水流冲击下不同时间的实景高速摄像拍摄图。由图7可知，在水流冲击后，表面仍能保持较好的超疏水状态。Fig. 6 is a schematic diagram of the water impact resistance test method of the coating sample prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in this embodiment. Under computer control, high-pressure nitrogen gas is used to generate water columns with different flow rates to impact the surface, and a high-speed camera is used to record the impact process. Use the method of Fig. 6 to test the result of sample performance as shown in Fig. 7, Fig. 7 is that the coating sample prepared by the all-organic multiple fluorinated epoxy superhydrophobic composite coating in this embodiment is at 34m/s (Reynolds number 43000 ) real-scene high-speed camera pictures under the impact of water flow at different times. It can be seen from Figure 7 that the surface can still maintain a good superhydrophobic state after the impact of water flow.
本发明所制备的超疏水表面具有良好的耐腐蚀性，在王水中浸泡1h和1mol/L的NaOH溶液中浸泡24h，都仍然能保持超疏水状态。The super-hydrophobic surface prepared by the present invention has good corrosion resistance, and can still maintain a super-hydrophobic state when soaked in aqua regia for 1 hour and in a 1mol/L NaOH solution for 24 hours.
对比例1：Comparative example 1:
将1份二乙烯三胺、10份E-51环氧树脂以及10份丙酮混合并充分搅拌得到混合体系，然后将混合体系均匀涂至铝板上。固化后所得到表面的接触角为40°～45°。Mix 1 part of diethylenetriamine, 10 parts of E-51 epoxy resin and 10 parts of acetone and stir thoroughly to obtain a mixed system, and then evenly coat the mixed system on an aluminum plate. The contact angle of the obtained surface after curing is 40°-45°.
对比例2：Comparative example 2:
将4份实施例1中所制备的固化剂与10份E-51环氧树脂、10份丙酮混合并充分搅拌得到的混合体系均匀涂覆至铝板上。固化后所得到表面的接触角为77°～82°。4 parts of the curing agent prepared in Example 1 were mixed with 10 parts of E-51 epoxy resin and 10 parts of acetone, and the mixed system obtained by fully stirring was evenly coated on the aluminum plate. The contact angle of the obtained surface after curing is 77°-82°.
对比例3：Comparative example 3:
将4份实施例1中所制备的固化剂与10份E-51环氧树脂、1.5份聚全氟甲基异丙基醚、10份丙酮混合并充分搅拌得到的混合体系均匀涂覆至铝板上。固化后所得到表面的接触角为90°～95°。Mix 4 parts of the curing agent prepared in Example 1 with 10 parts of E-51 epoxy resin, 1.5 parts of polyperfluoromethyl isopropyl ether, and 10 parts of acetone, and fully stir the obtained mixed system to evenly coat the aluminum plate superior. The contact angle of the obtained surface after curing is 90°-95°.
实施例2：Example 2:
一种本发明的全有机多重氟化环氧超疏水复合涂料及其制备方法和使用方法，与实施例1基本相同，区别仅在于：在使用时，所用基底为玻璃或A4纸、环氧树脂板、钢板。所得超疏水复合涂料的涂层表面与水的接触角为160°～165°，滚动角小于2°。A kind of all-organic multiple fluorinated epoxy superhydrophobic composite coating of the present invention and its preparation method and use method are basically the same as Example 1, the only difference is: when in use, the substrate used is glass or A4 paper, epoxy resin Board, steel plate. The coating surface of the obtained superhydrophobic composite paint has a contact angle with water of 160° to 165°, and a rolling angle of less than 2°.
实施例3：Example 3:
一种本发明的全有机多重氟化环氧超疏水复合涂料及其制备方法和使用方法，与实施例1基本相同，区别仅在于：超疏水复合涂料中，所用聚四氟乙烯微粒为4.5g。所得超疏水复合涂料的涂层表面与水的接触角为150°～153°。A kind of all-organic multiple fluorinated epoxy superhydrophobic composite coating of the present invention and its preparation method and using method are basically the same as Example 1, the only difference is that in the superhydrophobic composite coating, the polytetrafluoroethylene particles used are 4.5g . The contact angle between the coating surface of the obtained superhydrophobic composite coating and water is 150°-153°.
以上所述仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例。凡属于本发明思路下的技术方案均属于本发明的保护范围。应该指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下的改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above descriptions are only preferred implementations of the present invention, and the scope of protection of the present invention is not limited to the above examples. All technical solutions under the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those skilled in the art, improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.
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| CN109777012B (en) * | 2019-01-30 | 2021-08-13 | 中国人民解放军国防科技大学 | A kind of epoxy-based superhydrophobic fiber-reinforced composite material and preparation method thereof |
| CN110066573A (en) * | 2019-05-07 | 2019-07-30 | 深圳德诚达光电材料有限公司 | A kind of anti-high velocity fluid strikes hydrophobic coating and preparation method thereof |
| CN110272668A (en) * | 2019-06-19 | 2019-09-24 | 东南大学 | A kind of super-hydrophobic coat and preparation method thereof |
| CN111117384A (en) * | 2020-01-06 | 2020-05-08 | 哈尔滨工业大学 | A kind of preparation method of high mechanical strength wear-resistant and corrosion-resistant superhydrophobic coating material |
| CN111607308A (en) * | 2020-06-09 | 2020-09-01 | 向怀珍 | Super-hydrophobic modified epoxy resin electromagnetic shielding paint and preparation method thereof |
| CN113105777A (en) * | 2021-05-31 | 2021-07-13 | 齐鲁工业大学 | Wear-resistant and stable flame-retardant super-hydrophobic/super-oleophobic coating and preparation and application thereof |
| CN113502114B (en) * | 2021-07-07 | 2022-03-22 | 上海库曜新材料有限公司 | Two-component ultra-fast-drying weather-resistant hydrophobic and oleophobic polyurea finish paint |
| CN113637370A (en) * | 2021-08-03 | 2021-11-12 | 广州先进技术研究所 | Super-lyophobic surface material based on all-polymer and preparation method thereof |
| CN116875122A (en) * | 2023-07-26 | 2023-10-13 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Super-hydrophobic alkali-resistant fiber reinforced composite material and preparation method thereof |
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| CN105646848A (en) * | 2016-03-18 | 2016-06-08 | 咸阳伟华绝缘材料有限公司 | Fluorine-containing catalyst capable of improving water resistance of epoxy resin/amine curing system and preparation method thereof |
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