CN117186744A - Giant POSS (polyhedral oligomeric silsesquioxane) molecular doped super-hydrophobic epoxy resin coating and preparation method and application thereof - Google Patents
Giant POSS (polyhedral oligomeric silsesquioxane) molecular doped super-hydrophobic epoxy resin coating and preparation method and application thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 70
- 239000011248 coating agent Substances 0.000 title claims abstract description 69
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 39
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 36
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004744 fabric Substances 0.000 claims abstract description 44
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 29
- 229920000742 Cotton Polymers 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- FYQFWFHDPNXORA-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C FYQFWFHDPNXORA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005260 corrosion Methods 0.000 claims abstract description 15
- 230000007797 corrosion Effects 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000007259 addition reaction Methods 0.000 claims abstract description 5
- 238000000016 photochemical curing Methods 0.000 claims abstract description 5
- 238000007865 diluting Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229920000178 Acrylic resin Polymers 0.000 claims abstract 4
- 239000004593 Epoxy Substances 0.000 claims abstract 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 10
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 4
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- VLGNTAHJZQOHJE-UHFFFAOYSA-N (6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)-phenylmethanone Chemical compound OC1(C(C(=O)C2=CC=CC=C2)C=CC=C1)C VLGNTAHJZQOHJE-UHFFFAOYSA-N 0.000 claims description 3
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 claims 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 7
- 239000011247 coating layer Substances 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 150000001879 copper Chemical class 0.000 description 7
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005536 corrosion prevention Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000003396 thiol group Chemical class [H]S* 0.000 description 4
- -1 mercapto compound Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
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- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Abstract
The invention provides a giant POSS (polyhedral oligomeric silsesquioxane) molecular doped super-hydrophobic epoxy resin coating, and a preparation method and application thereof. The preparation method of the coating comprises the following steps: seven-trifluoropropyl vinyl POSS, octamercaptopropyl POSS, perfluorohexyl ethylene and a photoinitiator I are dissolved in a solvent A, and a mercapto-alkene addition reaction is carried out under ultraviolet light to obtain a giant POSS molecular solution; dissolving epoxy acrylate resin into the solvent B, and adding the photoinitiator II to obtain an epoxy acrylate resin solution; uniformly mixing a giant POSS molecular solution and an epoxy acrylic resin solution, and diluting to obtain a mixed solution; the obtained mixed solution is coated on a substrate and is obtained after photo-curing. The resin can form a coating layer on different substrates and has excellent hydrophobicity. The coating can be loaded on the surface of cotton fabric to endow the cotton fabric with super-hydrophobic property, and has self-cleaning performance; the coating can also be applied to the surface of metallic copper to slow down the corrosion of copper.
Description
Technical Field
The invention relates to a giant POSS (polyhedral oligomeric silsesquioxane) molecular doped super-hydrophobic epoxy resin coating, and a preparation method and application thereof, and belongs to the technical field of organosilicon surface modification.
Background
In recent years, silsesquioxane-based materials have received widespread attention. Polyhedral oligomeric cage silsesquioxanes (POSS) are a class of cubic, multifunctional compounds of the formula [ RSiO ] 1.5 ] n (R is an organofunctional group, n=6, 8, 10, 12, n=8 being most common). The inside of the POSS molecule is an inorganic core formed by silicon-oxygen-silicon bonds, so that the POSS molecule has the characteristics of good heat stability, rigidity and radiation resistance, and meanwhile, the silicon-oxygen-silicon bonds have low specific surface energy and are easy to self-assemble, so that a rough micro-nano structure is constructed; the periphery of the POSS is different types of organic groups, the change of the substituent groups can be changed according to the expected change of a designer, the POSS is endowed with more functions, in addition, the periphery of the POSS can be modified by the organic groups, different types of POSS can be further modified to form giant molecules, the size of the giant molecules is improved, and new properties are expected to be obtained. POSS is a good hydrophobic additive that can effectively increase the water repellency of the material surface. However, POSS itself has a low surface energy and poor adhesion, and is prone to phase separation when used as an additive, which tends to reduce service life. To solve the phase separation problem, it is desirable to introduce the modifier to the coating in a chemical bond connection. While substances containing a large number of hydrogen bonds may be selected to promote adhesion between the coating and the substrate. The adherent substrate may be selected from commercially available, inexpensive Epoxy Acrylate (EA), which is the most recently used, fastest polymerizing, photocurable oligomer containing a large number of hydroxyl groups, which provides high adhesion. The epoxy acrylate resin can also be used as a protective layer for metals to prevent metal corrosion, and the application range of the epoxy acrylate resin is further expanded when the epoxy acrylate resin is doped with a low-surface-energy substance. The POSS and EA chemical doping has good hydrophobic property, and can be used for self-cleaning, corrosion prevention and other aspects.
Modification with POSS has been attracting attention so far, but the POSS species are relatively single and cannot be fully utilized, so that research on giant branched POSS is rare, and research on using giant POSS as a hydrophobic modifier has not been reported yet. For this purpose, the present invention is proposed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a giant POSS molecular doped super-hydrophobic epoxy resin coating, and a preparation method and application thereof. The invention prepares a novel giant POSS molecule by using heptatrifluoropropyl vinyl POSS, octamercaptopropyl POSS and perfluorohexyl ethylene, and dopes the novel giant POSS molecule into EA to obtain a photo-curable hydrophobic epoxy resin which can form a coating on different substrates and has excellent hydrophobicity. The coating can be loaded on the surface of cotton fabric to endow the cotton fabric with super-hydrophobic property, and has self-cleaning performance; the coating can be coated on the surface of metallic copper to slow down the corrosion of copper, and has great potential in practical application.
The technical scheme of the invention is as follows:
a preparation method of a giant POSS molecular doped super-hydrophobic epoxy resin coating comprises the following steps:
(1) Heptatrifluoropropyl vinyl POSS (CF) 3 -POSS), octamercaptopropyl POSS (SH-POSS), perfluorohexyl ethylene and a photoinitiator I are dissolved in a solvent A, and are mixed and stirred uniformly, and a mercapto-alkene addition reaction is carried out under ultraviolet light to obtain a giant POSS molecular solution;
(2) Dissolving epoxy acrylate resin (EA) into a solvent B, and adding a photoinitiator II to obtain an epoxy acrylate resin solution;
(3) Uniformly mixing a giant POSS molecular solution and an epoxy acrylate resin solution, and diluting to obtain a mixed solution; coating the obtained mixed solution on a substrate, and carrying out photo-curing to obtain the giant POSS molecular doped super-hydrophobic epoxy resin coating.
According to a preferred embodiment of the present invention, the heptatrifluoropropyl vinyl POSS (CF 3 -POSS) and perfluorohexyl ethylene to octamercaptopropyl POSS (SH-POSS) in a ratio of 2-7:1, more preferably 2-4:1; the heptatrifluoropropyl vinyl POSS (CF 3 The molar ratio of POSS) to perfluorohexyl ethylene is 1-6:1-6, more preferably 1:1.
According to the invention, the heptatrifluoropropyl vinyl POSS (CF) of step (1) 3 POSS), octamercaptopropyl POSS (SH-POSS) according to literature Surface, respectively&Coatings Technology 457 (2023) 129285 and Advanced Functional Materials 2011,21,2960-2967, respectively, have the structure described by the following formula:
preferably according to the invention, the photoinitiator I in step (1) is 2, 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, ethyl 4-dimethylaminobenzoate, benzophenone, 4-chlorobenzophenone, 4-methylbenzophenone or methyl o-benzoylbenzoate, more preferably 2, 2-dimethoxy-2-phenylacetophenone; the photoinitiator I has the mass of heptatrifluoropropyl vinyl POSS (CF) 3 -POSS), octamercaptopropyl POSS (SH-POSS) and perfluorohexyl ethylene in total mass 1-2%.
According to a preferred embodiment of the present invention, the solvent A in step (1) is tetrahydrofuran, dichloromethane, toluene, chloroform, methanol, ethanol, isopropanol or 1, 2-dichloroethane, more preferably tetrahydrofuran.
According to the invention, the light source of the ultraviolet light in the step (1) is a 100W ultraviolet lamp with the wavelength of 200-400nm.
According to the present invention, the time for the addition reaction of the mercapto compound in the step (1) is preferably 10 to 180 minutes, more preferably 50 to 70 minutes.
According to the invention, the concentration of the giant POSS molecules in the giant POSS molecule solution in the step (1) is preferably 10-150mg/mL, more preferably 45-50mg/mL; the molecular mass of the giant POSS is that of heptatrifluoropropyl vinyl POSS (CF 3 -POSS), octamercaptopropyl POSS (SH-POSS), perfluorohexyl ethylene.
According to a preferred embodiment of the invention, the solvent B in step (2) is the same as the solvent A in step (1).
Preferably according to the invention, the photoinitiator II in step (2) is 2, 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, ethyl 4-dimethylaminobenzoate, benzophenone, 4-chlorobenzophenone, 4-methylbenzophenone or methyl o-benzoylbenzoate, more preferably 2, 2-dimethoxy-2-phenylacetophenone; the mass of the photoinitiator II is 1-2% of that of the epoxy acrylate resin.
According to the present invention, the concentration of the epoxy acrylate resin in the epoxy acrylate resin solution in the step (2) is preferably 100 to 400mg/mL, more preferably 200 to 300mg/mL; the epoxy acrylate resin (EA) is prepared from epoxy resin and acrylic acid or methyl acrylic acid, wherein the epoxy resin is bisphenol A type, bisphenol F type and phenolic aldehyde type epoxy resin, and the epoxy acrylate resin is a common commercial product.
According to the invention, the mass of the giant POSS molecule in the step (3) is preferably 1-40%, more preferably 5-20%, and even more preferably 10% of the mass of the epoxy acrylate resin; the mass of the giant POSS molecule was determined as heptatrifluoropropyl vinyl POSS (CF 3 -POSS), octamercaptopropyl POSS (SH-POSS), perfluorohexyl ethylene.
According to the invention, preferably, in the dilution step (3), a solvent C is added into the system for dilution, wherein the solvent C is the same as the solvent A; the concentration of the epoxy acrylate resin in the resulting mixed solution is diluted to 25 to 100mg/mL, more preferably 50 to 75mg/mL.
According to a preferred embodiment of the present invention, the substrate in step (3) is a cotton fabric or a copper sheet; coating the obtained mixed solution on a substrate by adopting a soaking treatment method; further preferably, when the substrate is cotton fabric, the soaking treatment time is 10-30min, and the ultrasonic treatment is carried out in the soaking process; when the substrate is a copper sheet, the soaking time is 5-20s.
According to a preferred embodiment of the present invention, the conditions for the photo-curing in step (3) are: irradiating with ultraviolet light for 10-40min, preferably 20-30min; the ultraviolet light wavelength is 200-400nm.
The invention also provides the giant POSS molecular doped super-hydrophobic epoxy resin coating prepared by the preparation method.
According to the invention, the giant POSS molecular doped super-hydrophobic epoxy resin coating is applied to cotton fabric modification and copper corrosion prevention.
The invention has the technical characteristics and beneficial effects that:
1. the novel giant POSS molecule is prepared by carrying out a mercapto ene click chemical reaction on heptatrifluoro propyl vinyl POSS, octamercapto propyl POSS and perfluorohexyl ethylene, so that the fluorine-containing giant POSS material for modifying the surface of a substrate is enriched; then coating fluorine-containing giant POSS material and epoxy acrylate resin on the cotton fabric, wherein hydroxyl on the cotton fabric can be strongly combined with the epoxy acrylate resin due to the action of hydrogen bond, so that the epoxy acrylate resin is firmly adhered on the substrate, and the structural stability of the material is ensured; the giant POSS molecules are firmly connected to epoxy acrylate resin through sulfhydryl chemistry, and finally the giant POSS molecule doped super-hydrophobic epoxy resin coating is obtained; meanwhile, the epoxy acrylate resin can be firmly adhered to the copper sheet, and the giant POSS molecules are firmly connected to the epoxy acrylate resin through mercapto chemistry, so that the giant POSS molecule doped super-hydrophobic epoxy resin coating is finally obtained, and the copper surface can be effectively protected. The method has the advantages of mild, simple and efficient reaction conditions, mass preparation and simple and efficient coating preparation process.
2. After the giant POSS molecular doped super-hydrophobic epoxy resin coating is coated on the surface of cotton fabric, a stable super-hydrophobic surface is formed, the hydrophobic effect is obvious, the water contact angle is more than 150 degrees, and meanwhile, the self-cleaning performance is good; after the coating is coated on the surface of the metal copper sheet, a hydrophobic coating is formed, the coating can effectively protect the copper surface, slow down corrosion, and meanwhile, compared with other POSS molecules, the anti-corrosion performance is more excellent.
3. The giant POSS molecule modified epoxy acrylate used in the invention is coated on a substrate, the utilization rate of the POSS molecule is high, meanwhile, the fluorine content of the giant POSS molecule is low, the biodegradation is easy, and the excellent hydrophobic property of cotton fabrics and the corrosion resistance of copper sheets can be realized by adding a small amount of the giant POSS molecule with low fluorine content, so that the cost is lower, the environmental protection advantage is realized, and the corrosion resistance is more excellent.
Drawings
FIG. 1 is a FT-IR spectrum of POSS molecules obtained in example 1 and comparative examples 1-3.
FIG. 2 is a graph showing the change in the Water Contact Angle (WCA) and the rolling angle (SA) of POSS-2-Fabric obtained in comparative example 1, POSS-4-Fabric obtained in comparative example 2, POSS-6-Fabric obtained in comparative example 3, and POSS-2F-Fabric obtained in example 1.
FIG. 3 is a photograph of different water droplets on the surface of POSS-2F-Fabric obtained in example 1 of test example 1, which was colored with cola, tea, coffee, methylene blue, in this order from left to right.
FIG. 4 is a photograph showing the immersion of POSS-2F-Fabric obtained in example 1 of test example 2 in methylene blue solution.
FIG. 5 is a photograph of POSS-2F-Fabric surface coffee powder obtained in test example 2 using methylene blue solution to rinse example 1.
FIG. 6 is a Tafel polarization graph of POSS-2-Coating obtained in comparative example 1, POSS-4-Coating obtained in comparative example 2, POSS-6-Coating obtained in comparative example 3, and POSS-2F-Coating obtained in example 1 in test example 3.
FIG. 7 is a Nyquist plot of the POSS-2-Coating obtained in comparative example 1, POSS-4-Coating obtained in comparative example 2, POSS-6-Coating obtained in comparative example 3, and POSS-2F-Coating obtained in example 1 in test example 3.
Detailed Description
The invention will be further described with reference to specific experimental examples in conjunction with the accompanying drawings, but the scope of the invention is not limited thereto.
In the examples the ultraviolet light is provided by a 100W ultraviolet lamp.
The epoxy acrylate resin used in the examples was obtained by reacting bisphenol A type epoxy resin with acrylic acid, and was sold by Hengli New Material Co., ltd., model HL-G100.
Example 1
A preparation method of a giant POSS molecular doped super-hydrophobic epoxy resin coating comprises the following steps:
(1) Heptatrifluoropropyl vinyl POSS (751mg, 0.640 mmol), octamercaptopropyl POSS (3411 mg,0.335 mmol), perfluorohexyl ethylene (232 mg, 0.640 mmol), 2-dimethoxy-2-phenyl acetophenone (18 mg) and THF (26.5 mL) are added into a eggplant-shaped bottle in sequence, and after stirring uniformly, reacted for 60min under 365nm ultraviolet light irradiation, a uniform transparent giant POSS molecule (designated as POSS-2F) solution is obtained with a concentration of 50mg/mL.
(2) 1g of epoxy acrylate resin (EA) is weighed and dissolved in 5mL of THF, and a photoinitiator 2, 2-dimethoxy-2-phenylacetophenone accounting for 1% of the mass of the epoxy acrylate resin is added to obtain an epoxy acrylate resin solution with the concentration of 200 mg/mL; different volumes of the giant POSS molecule (POSS-2F) solution with the concentration of 50mg/mL obtained in the step (1) are respectively added into EA solution with the concentration of 200mg/mL, so that the mass of the POSS-2F is respectively 1%, 3%, 5%, 7%, 10%, 20%, 30% and 40% of the mass of EA, and then THF is added for dilution based on EA to obtain a mixed solution with the concentration of 50mg/mL (the POSS-2F is synchronously diluted). Soaking cotton Fabric in the mixed solution, carrying out ultrasonic treatment for 20 minutes, taking out, curing for 20 minutes under 365nm ultraviolet light, and obtaining a giant POSS (polyhedral oligomeric silsesquioxane) molecular doped super-hydrophobic epoxy resin coating on the surface of the cotton Fabric, wherein the obtained modified super-hydrophobic cotton Fabric is designated as POSS-2F-Fabric.
The giant POSS molecules obtained in this example have the structure shown below, and their infrared characterization is shown in fig. 1.
Example 2
The preparation method of the giant POSS molecular doped super-hydrophobic epoxy resin coating is as described in example 1, except that: in the step (2), the cotton fabric is replaced by a copper sheet, the copper sheet is soaked in the solution for 10 seconds, taken out and cured for 20 minutes under 365nm ultraviolet light, a giant POSS molecular doped super-hydrophobic epoxy resin Coating is obtained on the surface of the copper sheet, and the obtained modified copper sheet is marked as POSS-2F-Coating.
Comparative example 1
A preparation method of a POSS molecular doped super-hydrophobic epoxy resin coating comprises the following steps:
(1) Heptatrifluoropropyl vinyl POSS (751mg, 0.640 mmol), octamercaptopropyl POSS (3411 mg,0.335 mmol), 2-dimethoxy-2-phenylacetophenone (14.8 mg) and THF (22 mL) were added sequentially to a eggplant-shaped bottle, and reacted under 365nm ultraviolet irradiation for 60min after stirring uniformly to give a homogeneous transparent POSS (designated POSS-2) solution at a concentration of 50mg/mL.
(2) The preparation of the modified super-hydrophobic cotton Fabric is as described in the step (2) of the example 1, and the obtained modified super-hydrophobic cotton Fabric is marked as POSS-2-Fabric; the modified copper flakes were prepared as described in example 2, step (2), and the resulting modified copper flakes were designated POSS-2-Coating.
The POSS-2 obtained in this example has the structure shown below, and its infrared characterization is shown in FIG. 1.
Comparative example 2
The preparation method of the POSS molecular doped super-hydrophobic epoxy resin coating is as described in comparative example 1, except that: in the step (1), heptatrifluoropropyl vinyl POSS (1505 mg,1.34 mmol), octamercaptopropyl POSS (3411 mg,0.335 mmol), 2-dimethoxy-2-phenyl acetophenone (25.1 mg) and THF (37 mL) were sequentially added into a eggplant-shaped bottle, and reacted under 365nm ultraviolet irradiation for 60min after stirring uniformly to obtain a uniform and transparent POSS (designated as POSS-4) solution.
The obtained modified super-hydrophobic cotton Fabric is marked as POSS-4-Fabric; the resulting modified copper sheet was designated POSS-4-Coating.
The POSS-4 obtained in this example has the structure shown below, and its infrared characterization is shown in FIG. 1.
Comparative example 3
The preparation method of the POSS molecular doped super-hydrophobic epoxy resin coating is as described in comparative example 1, except that: in the step (1), heptatrifluoropropyl vinyl POSS (2257 mg,2.01 mmol), octamercaptopropyl POSS (3411 mg,0.335 mmol), 2-dimethoxy-2-phenyl acetophenone (35.3 mg) and THF (52 mL) were sequentially added into a eggplant-shaped bottle, and reacted under 365nm ultraviolet irradiation for 60min after stirring uniformly to obtain a uniform and transparent POSS (designated as POSS-6) solution.
The obtained modified super-hydrophobic cotton Fabric is marked as POSS-6-Fabric; the resulting modified copper sheet was designated POSS-6-Coating.
The POSS-6 obtained in this example has the structure shown below, and its infrared characterization is shown in FIG. 1.
Comparative example 4
The preparation method of the POSS molecular doped super-hydrophobic epoxy resin coating is described in example 1, except that: in step (1), octamercaptopropyl POSS (114 mg,0.112 mmol), DMPA (1.6 mg) and THF (12.5 mL) were sequentially added to a eggplant-shaped bottle, and reacted under 365nm ultraviolet irradiation for 60min after uniform stirring to obtain a uniform transparent POSS solution, however, a coating (POSS mass 10% of EA mass) was prepared using this POSS solution, and the obtained coating had hydrophilicity.
Test example 1
The samples obtained in example 1 and comparative examples 1 to 3 were evaluated for the change in water contact angle as to the liquid repellency, and the results are shown in FIG. 2. In all samples of different POSS content (referring to the mass percent of POSS to EA), the water repellency was hardly increased when the POSS content was about 10%, indicating that the POSS molecules on the surface were almost saturated and therefore optimal when the POSS content was 10%. The contact angle values of POSS-2F-Fabric obtained in example 1 are all higher than those of the samples in the comparative example, because perfluorohexyl ethylene is added in a specific amount in example 1 and is more hydrophobic. The reason for the lower contact angle values of POSS-4-Fabric and POSS-6-Fabric is that the blocking effect on reactive sulfhydryl groups is generated due to too many cage-type molecules connected, so that the cross-linking with EA is difficult, and the hydrophobicity is lost. POSS-2F-Fabric is therefore the best performing sample. POSS-2F-Fabric was able to impart water repellency to different water samples (cola, tea, coffee, methylene blue stained water) (figure 3).
Test example 2
Self-cleaning application discovery:
the modified cotton fabric has good liquid repellent capability, so the modified cotton fabric has potential application value in the aspects of dirt resistance and self-cleaning. As shown in fig. 4, the modified cotton fabric (POSS content is 10%) obtained in example 1 is soaked in sewage dyed by methylene blue dye, and after the cotton fabric is taken out, the surface of the cotton fabric is not polluted and has anti-fouling capability; as shown in FIG. 5, when coffee powder is sprinkled on the surface of the cotton fabric, the pollution can be removed by using water dyed by methylene blue, and the self-cleaning capability of double pollution prevention is achieved.
Test example 3
Copper sheet corrosion prevention application exploration:
when the coating (POSS content is 10%) is covered on the copper sheet, the corrosion resistance effect of the modified copper sheet is greatly improved compared with that of a pure copper sheet. The Tafel polarization curve and electrochemical impedance spectroscopy of a three-electrode electrochemical workstation were used to analyze corrosion resistance. The structure of the three electrode system is as follows: copper sheets and modified copper sheets are used as working electrodes, ag/AgCl is used as a reference electrode, a platinum sheet is used as a counter electrode, a 3.5wt% NaCl solution is used as electrolyte, and the soaking area of the working electrodes is kept at 1cm 2 . The Tafel polarization curve was scanned at a speed of 10mV/s. Impedance frequency test range is between 1000000Hz and 0.01 Hz. Tafel polarization curves are shown in FIG. 6. When the pure copper sheet is covered by the Coating, the corrosion current density of the pure copper sheet is reduced, and the corrosion potential moves forward, wherein the corrosion potential of POSS-2F-Coating moves forward maximally, and moves forward from-299 mV to-170 mV respectively, which indicates the effectiveness of the POSS functionalized silane Coating in corrosion prevention. Further analysis of corrosion resistance using the Nyquist plot, as shown in FIG. 7, the semi-circular diameter of the POSS-2F-Coating curve was maximized, further demonstrating that POSS-2F-Coating has good corrosion resistance.
The above-described embodiments are merely preferred embodiments of the present invention, and are not intended to limit the present invention.
Claims (10)
1. A preparation method of a giant POSS molecular doped super-hydrophobic epoxy resin coating comprises the following steps:
(1) Seven-trifluoropropyl vinyl POSS, octamercaptopropyl POSS, perfluorohexyl ethylene and a photoinitiator I are dissolved in a solvent A, and are mixed and stirred uniformly, and a mercapto-alkene addition reaction is carried out under ultraviolet light to obtain a giant POSS molecular solution;
(2) Dissolving epoxy acrylate resin into the solvent B, and adding the photoinitiator II to obtain an epoxy acrylate resin solution;
(3) Uniformly mixing a giant POSS molecular solution and an epoxy acrylic resin solution, and diluting to obtain a mixed solution; coating the obtained mixed solution on a substrate, and carrying out photo-curing to obtain the giant POSS molecular doped super-hydrophobic epoxy resin coating.
2. The method for preparing a giant POSS molecular doped superhydrophobic epoxy resin coating according to claim 1, wherein the ratio of the total mole number of heptatrifluoropropyl vinyl POSS and perfluorohexyl ethylene to the mole number of octamercaptopropyl POSS in step (1) is 2-7:1, preferably 2-4:1; the molar ratio of the heptatrifluoropropyl vinyl POSS to the perfluorohexyl ethylene is 1-6:1-6, preferably 1:1.
3. The method for preparing a giant POSS molecule doped super hydrophobic epoxy resin coating according to claim 1, wherein the photoinitiator I in step (1) is 2, 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, 4-dimethylaminoethyl benzoate, benzophenone, 4-chlorobenzophenone, 4-methylbenzophenone or methyl o-benzoate, preferably 2, 2-dimethoxy-2-phenylacetophenone; the mass of the photoinitiator I is 1-2% of the total mass of the heptatrifluoropropyl vinyl POSS, the octamercaptopropyl POSS and the perfluorohexyl ethylene.
4. The method for preparing the giant POSS molecular doped super hydrophobic epoxy resin coating according to claim 1, wherein in the step (1), the solvent a is tetrahydrofuran, dichloromethane, toluene, chloroform, methanol, ethanol, isopropanol or 1, 2-dichloroethane, preferably tetrahydrofuran;
the light source of the ultraviolet light is a 100W ultraviolet lamp with the wavelength of 200-400nm;
the time of the thiol-ene addition reaction is 10-180min, preferably 50-70min.
5. The method for preparing the giant POSS molecule-doped superhydrophobic epoxy resin coating according to claim 1, wherein the concentration of the giant POSS molecules in the giant POSS molecule solution in the step (1) is 10-150mg/mL, preferably 45-50mg/mL.
6. The method for preparing the giant POSS molecular doped superhydrophobic epoxy resin coating according to claim 1, wherein the solvent B in the step (2) is the same as the solvent a in the step (1);
the photoinitiator II is 2, 2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl propiophenone, 1-hydroxy cyclohexyl phenyl ketone, 4-dimethylamino ethyl benzoate, diphenyl ketone, 4-chlorobenzophenone, 4-methyl benzophenone or methyl o-benzoyl benzoate, preferably 2, 2-dimethoxy-2-phenyl acetophenone; the mass of the photoinitiator II is 1-2% of that of the epoxy acrylic resin;
the concentration of the epoxy acrylate resin in the epoxy acrylate resin solution is 100-400mg/mL, preferably 200-300mg/mL.
7. The method for preparing the giant POSS molecule-doped superhydrophobic epoxy resin coating according to claim 1, wherein the mass of the giant POSS molecule in the step (3) is 1-40%, preferably 5-20%, further preferably 10% of the mass of the epoxy acrylic resin;
in the dilution step (3), a solvent C is added into the system for dilution, wherein the solvent C is the same as the solvent A; the concentration of the epoxy acrylate resin in the diluted mixed solution is 25-100mg/mL, preferably 50-75mg/mL.
8. The method for preparing the giant POSS molecular doped superhydrophobic epoxy resin coating according to claim 1, wherein the substrate in the step (3) is cotton fabric or copper sheet; coating the obtained mixed solution on a substrate by adopting a soaking treatment method; preferably, when the substrate is cotton fabric, the soaking treatment time is 10-30min, and ultrasonic treatment is carried out in the soaking process; when the substrate is a copper sheet, the soaking time is 5-20s;
the conditions of the photo-curing are as follows: irradiating with ultraviolet light for 10-40min, preferably 20-30min; the ultraviolet light wavelength is 365nm.
9. A giant POSS molecular doped super-hydrophobic epoxy resin coating is characterized in that the coating is prepared by the preparation method of claim 1.
10. The use of the giant POSS molecule-doped superhydrophobic epoxy resin coating of claim 9 in cotton fabric modification and copper corrosion protection.
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| CN117683412A (en) * | 2024-02-04 | 2024-03-12 | 湖南旗滨光能科技有限公司 | Fluorine-free self-cleaning coating and preparation method and application thereof |
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| CN117683412A (en) * | 2024-02-04 | 2024-03-12 | 湖南旗滨光能科技有限公司 | Fluorine-free self-cleaning coating and preparation method and application thereof |
| CN117683412B (en) * | 2024-02-04 | 2024-04-19 | 湖南旗滨光能科技有限公司 | Fluorine-free self-cleaning coating and preparation method and application thereof |
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