CN116285675B - Novel POSS functionalized hydrophobic silane coating and preparation method and application thereof - Google Patents
Novel POSS functionalized hydrophobic silane coating and preparation method and application thereof Download PDFInfo
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- CN116285675B CN116285675B CN202310023739.3A CN202310023739A CN116285675B CN 116285675 B CN116285675 B CN 116285675B CN 202310023739 A CN202310023739 A CN 202310023739A CN 116285675 B CN116285675 B CN 116285675B
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- 229910000077 silane Inorganic materials 0.000 title claims abstract description 63
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000576 coating method Methods 0.000 title claims abstract description 47
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000742 Cotton Polymers 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- -1 salt compound Chemical class 0.000 claims abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005050 vinyl trichlorosilane Substances 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims abstract description 5
- 238000003618 dip coating Methods 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- DWUCCPNOMFYDOL-UHFFFAOYSA-N propyl(sulfanyl)silicon Chemical compound CCC[Si]S DWUCCPNOMFYDOL-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical group CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000013032 photocatalytic reaction Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical group C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 238000005286 illumination Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- 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
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical group C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 41
- 238000000926 separation method Methods 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 8
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000005536 corrosion prevention Methods 0.000 abstract description 4
- 238000012650 click reaction Methods 0.000 abstract description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- 150000001879 copper Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical class O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
Abstract
The invention provides a novel POSS functionalized hydrophobic silane coating, and a preparation method and application thereof. The preparation method of the hydrophobic silane coating comprises the following steps: firstly, preparing POSS metal salt compound of unfilled corner by taking trialkoxysilane as raw material, further reacting with vinyl trichlorosilane to introduce vinyl, finally connecting active alkoxy silane through mercapto click reaction, preparing novel POSS functionalized silane solution, and dispersing the solution on the surfaces of cotton fabric and metallic copper in a dip-coating and spray-coating mode to obtain the hydrophobic silane coating. The preparation method disclosed by the invention is simple in steps, mild in conditions and has potential application value in the aspects of oil-water separation and corrosion prevention. The coating can be applied to the surface of cotton fabric to endow the cotton fabric with super-hydrophobic property and is used for separating oil from water; the coating can be coated on the surface of metal copper to slow down the corrosion of copper, and has great application potential in the aspects of oil-water separation, corrosion prevention and the like.
Description
Technical Field
The invention relates to a novel POSS functionalized hydrophobic silane coating, and a preparation method and application thereof, and belongs to the technical field of organosilicon surface modification.
Background
Inspired by the water repellency and self-cleaning property of animals and plants in the nature, the research of manually preparing the super-hydrophobic system is started. The super-hydrophobic material has potential application value in the fields of antifouling, corrosion prevention, flame retardance, ice resistance, antibiosis, oil-water separation and the like, so that great interest is brought to academia and industry. Silane materials are one of the important substances for constructing superhydrophobic materials. The silane-based material can be effectively bonded to the base material by hydrolysis of the alkoxy group, functioning as a binder. The silane material also has low surface energy, and can effectively improve water repellency. The functional groups of the silane coupling agents in the current market are mostly flexible chain structures or benzene rings with smaller volumes, and the effect of constructing surface roughness is poor. This limits the application effect of silanes directly for superhydrophobic coatings.
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 an organic group of different types, and the change of the substituent groups can be changed according to the expected change of a designer, so that the POSS is endowed with more functions, and therefore, the POSS is a good additive of the super-hydrophobic material. However, POSS itself has poor adhesion and is prone to phase separation when used as an additive.
At present, the preparation and application research of POSS functionalized silane is less, and the preparation of novel POSS functionalized silane and the exploration of related application are very significant. For this purpose, the present invention is proposed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel POSS functionalized hydrophobic silane coating, and a preparation method and application thereof. The invention uses trifluoro propyl and phenyl functional POSS to modify silane to obtain novel POSS functional silane, and exerts cohesiveness of alkoxy part and hydrophobicity of POSS part to obtain novel hydrophobic coating of POSS silane. The coating can be applied to the surface of cotton fabric to endow the cotton fabric with super-hydrophobic property and is used for separating oil from water; the coating can be coated on the surface of metallic copper to slow down the corrosion of copper. Therefore, the coating has great application potential in the aspects of oil-water separation, corrosion prevention and the like.
Description of the terminology:
room temperature: has the meaning known in the art, meaning 25.+ -. 5 ℃.
The technical scheme of the invention is as follows:
a preparation method of a novel POSS functionalized hydrophobic silane coating comprises the following steps:
(1) Uniformly mixing trialkoxysilane, water, alkali and a solvent A, heating and refluxing, and stirring at room temperature for reaction; after the reaction is finished, removing the solvent to obtain POSS metal salt compounds of unfilled corners;
(2) Adding the POSS metal salt compound and the acid absorbent of the unfilled corner obtained in the step (1) into a solvent B, dropwise adding vinyl trichlorosilane under the protection of protective gas at the temperature of 0-5 ℃, and converting the reaction into room temperature reaction after the reaction at the temperature of 0-5 ℃; after the reaction is finished, obtaining vinylsilane end-capped POSS through filtration, concentration and precipitation;
(3) Dispersing the vinyl-terminated POSS obtained in the step (2) into a solvent C, adding mercaptopropyl silane and a photoinitiator, and carrying out photocatalytic reaction to obtain a POSS functionalized silane solution;
(4) And (3) dispersing the POSS functionalized silane solution in the step (3) on a substrate to prepare the hydrophobic silane coating.
Preferably according to the present invention, the trialkoxysilane in step (1) is trimethoxy (3, 3-trifluoropropyl) silane, triethoxy (3, 3-trifluoropropyl) silane, trimethoxyphenyl silane or triethoxyphenyl silane; further preferred is trimethoxy (3, 3-trifluoropropyl) silane or trimethoxyphenyl silane.
According to the invention, the molar ratio of water to trialkoxysilane in step (1) is preferably from 1.1 to 1.5:1.
Preferably according to the invention, the base in step (1) is sodium hydroxide, potassium hydroxide or lithium hydroxide, more preferably sodium hydroxide; the molar ratio of the alkali to the trialkoxysilane is 0.43-0.45:1; if the proportion of the base is too high or too low, the POSS metal salt compound of the unfilled corner of the present invention is not obtained.
According to a preferred embodiment of the present invention, the solvent A in step (1) is tetrahydrofuran, toluene, chloroform, 1, 2-dichloroethane, N-dimethylformamide or dimethyl sulfoxide, more preferably tetrahydrofuran; the ratio of the volume of the solvent A to the mole number of the trialkoxysilane is 0.5-1.5 mL/1 mmol.
According to a preferred embodiment of the present invention, the temperature of the heated reflux in step (1) is 65-75 ℃; the heating reflux time is 3 to 6 hours, more preferably 4 to 5 hours.
According to the present invention, the stirring reaction at room temperature in the step (1) is preferably carried out for a period of 10 to 20 hours, more preferably 15 to 18 hours.
According to a preferred embodiment of the present invention, the solvent B in step (2) is diethyl ether, tetrahydrofuran, chloroform, 1, 2-dichloroethane or toluene, more preferably tetrahydrofuran; the ratio of the volume of the solvent B to the mole number of the POSS metal salt compound of the unfilled corner is 15-25 mL/1 mmol.
Preferably according to the present invention, the acid absorbent in step (2) is triethylamine; the molar ratio of the acid absorbent to the unfilled corner POSS metal salt compound is 2-4:1.
According to a preferred embodiment of the present invention, the protective gas in step (2) is nitrogen or argon.
According to the invention, the molar ratio of the vinyl trichlorosilane to the unfilled POSS metal salt compound in the step (2) is preferably 1-1.3:1; the dropping speed of the vinyl trichlorosilane is 1-2 drops/second.
According to the invention, in step (2), the reaction time is preferably 1 to 6 hours, more preferably 3 to 4 hours, at 0 to 5 ℃; the reaction time at room temperature is 15 to 24 hours, more preferably 18 to 20 hours.
According to a preferred embodiment of the present invention, the concentration in step (2) is such that the filtrate obtained by filtration is concentrated until a solid is precipitated.
According to a preferred embodiment of the present invention, the precipitation step in step (2) is: adding the concentrated solution obtained by concentration into methanol, precipitating, filtering, and drying at 40-60 ℃ for 2-5h to obtain vinylsilane terminated POSS; the volume ratio of the methanol to the concentrated solution is 15-20:1; the time of the precipitation is 5-10min.
According to the present invention, the solvent C in the step (3) is preferably tetrahydrofuran, chloroform, 1, 2-dichloroethane, benzene, toluene, N-dimethylformamide or dimethylsulfoxide, and more preferably tetrahydrofuran.
According to a preferred embodiment of the present invention, the mercaptopropyl silane in step (3) is gamma-mercaptopropyl trimethoxysilane or gamma-mercaptopropyl triethoxysilane; the molar ratio of the mercaptopropyl silane to the vinyl-terminated POSS is 1:1.
Preferably according to the invention, the photoinitiator in step (3) 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 is 0.5-1.5% of the total mass of the vinyl end-capped POSS and the mercaptopropyl silane.
According to the present invention, the time of the photocatalytic reaction in the step (3) is preferably 10 to 70 minutes, more preferably 30 to 60 minutes; the light source of the illumination of the photocatalysis reaction is a 100W ultraviolet lamp, and the wavelength is 10-400nm.
Preferably according to the invention, the mass concentration of POSS functionalized silane in the POSS functionalized silane solution in step (3) is 10-80mg/mL; the mass of the POSS functionalized silane is the sum of the masses of vinyl terminated POSS and mercaptopropyl silane.
According to the invention, the substrate in the step (4) is cotton fabric, copper and other substrates commonly used in the field; the preparation method of the hydrophobic silane coating is a dip-coating or spray-coating method, which is the prior method in the field;
preferably, the preparation method of the hydrophobic silane coating on the surface of the cotton fabric comprises the following steps: and (3) soaking the cotton fabric in the solution obtained in the step (3) for 3-5 hours, and drying at 130-140 ℃ for 20-40min.
Preferably, the preparation method of the copper surface coating comprises the following steps: spraying the solution obtained in the step (3) on the copper surface by using an atomization spray gun device.
The raw materials in the invention are all common commercial products.
The synthesis process of the novel POSS functionalized hydrophobic silane is as follows:
wherein R is 1 Methyl or ethyl; r is R 2 is-CH 2 CH 2 CF 3 or-Ph; r is R 3 Is methyl or ethyl.
The invention has the technical characteristics and beneficial effects that:
1. the required raw materials are cheap and easy to obtain, expensive catalysts are not required to be used, and the reaction conditions are mild; POSS is synthesized by simple hydrolysis condensation reaction, and further, the mercapto-alkene click reaction is adopted to prepare POSS functionalized silane, the POSS silane is dispersed to different substrates and then is used for preparing a coating, and the coating preparation method is simple and efficient.
2. After the POSS functionalized silane is coated on the surface of cotton fabric, alkoxy is partially hydrolyzed and condensed with hydroxyl on the surface of the fabric in a chemical bonding mode, the POSS has low surface energy, is easy to assemble and construct a rough surface, can form a stable superhydrophobic surface, has obvious hydrophobic effect, and has a water contact angle of more than 150 degrees. However, the surface of the obtained coating is lipophilic, and the oil-water mixture can be effectively separated by utilizing the oleophilic hydrophobicity of the modified cotton fabric.
3. After the POSS silane coating is coated on the surface of the metal copper sheet, a hydrophobic coating is formed, and the coating can effectively isolate water and ions in the water so as to protect the copper surface and slow down corrosion.
Drawings
FIG. 1 is a CF prepared in example 1 3 Fourier infrared spectra of-MPOSS and Ph-MPOSS prepared in example 2.
FIG. 2 shows the original cotton (a, b), CF obtained in example 1 3 SEM images of different magnifications of the MPOSS modified cotton fabric (c, d) and of the Ph-MPOSS modified cotton fabric (e, f) obtained in example 2.
FIG. 3 is a view of Cu, CF obtained in example 1 3 SEM pictures of MPOSS-Cu and Ph-MPOSS-Cu obtained in example 2.
Fig. 4 shows an oil-water separator, wherein the left figures a 1), a 2) and a 3) respectively represent the heavy oil and the water before, during and after separation, and the right figures b 1), b 2) and b 3) respectively represent the light oil and the water before, during and after separation.
FIG. 5 is CF 3 -separation efficiency and flux of the MPOSS modified cotton fabric (a) and the Ph-MPOSS modified cotton fabric (b) on petroleum ether, n-hexane, dichloromethane, chloroform.
FIG. 6 is Cu, CF 3 Tafel polarization curves of MPOSS-Cu and Ph-MPOSS-Cu.
FIG. 7 is Cu, CF 3 Bode plot of MPOSS-Cu and Ph-MPOSS-Cu.
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.
The raw materials used in the examples are all conventional raw materials and are commercially available; the methods are prior art unless specified otherwise.
Example 1
A preparation method of a novel POSS functionalized hydrophobic silane coating comprises the following steps:
(1) Trimethoxy (3, 3-trifluoropropyl) silane (10 g,46 mmol), tetrahydrofuran (50 mL), water (1.04 g,58 mmol) and NaOH (0.8 g,20 mmol) were charged into a flask equipped with a reflux condenser, and the resulting mixture was refluxed at 70℃for 5 hours under magnetic stirring, then naturally cooled to room temperature, and stirred at room temperature for 15 hours; after the reaction is completed, the solvent is removed by rotary evaporation, and white precipitate is obtained, which is the sodium salt of POSS metal salt compound trifluoropropyl POSS triol with a yield of 100 percent.
(2) At N 2 Under protection, trifluoropropyl POSS triol sodium salt (2 g,1.76 mmol), triethylamine (0.284 g,5.28 mmol) and anhydrous tetrahydrofuran (40 mL) were charged into a three-necked flask, and vinyltrichlorosilane (0.3 g,1.86 mmol) was added dropwise to the system at a rate of 1 drop/sec at 0deg.C; after the dripping is finished, the obtained mixture is magnetically stirred at 0 ℃ for reaction for 4 hours, then the temperature is raised to room temperature, and the mixture is stirred at the room temperature for 20 hours; after the reaction is completed, filtering to remove precipitate, concentrating the obtained filtrate until solid is separated out, dispersing the concentrated solution into methanol with the volume of 20 times of that of the concentrated solution for precipitation for 10min, filtering, and drying at 50 ℃ for 4h to obtain white solid vinylsilane end-cappedPOSS, heptatrifluoropropyl vinyl POSS, was produced in 63% yield.
(3) Heptatrifluoropropyl vinyl POSS (2.245 g,2 mmol), gamma-mercaptopropyl trimethoxysilane (0.4 g,2 mmol), 2-dimethoxy-2-phenylacetophenone (0.026 g) and THF (44 mL) were reacted under 365nm ultraviolet light (100W) for 45 min to give a clear CF with a concentration of 60mg/mL 3 MPOSS solution (CF) 3 The mass of MPOSS is based on the total mass of heptatrifluoropropyl vinyl POSS and gamma-mercaptopropyl trimethoxysilane).
(4) CF obtained in the step (3) 3 -forming a hydrophobic silane coating on the surface of the cotton fabric by dip-coating the MPOSS solution, wherein the method comprises the following specific steps: cutting 4cm by 4cm cotton fabric, soaking in CF with the concentration of 60mg/mL obtained in the step (3) 3 After 4 hours in MPOSS solution, the cotton fabric is taken out and heated in an oven at 135 ℃ for 30 minutes, and a novel POSS functionalized hydrophobic silane coating is obtained on the surface of the cotton fabric, thus obtaining CF 3 -an MPOSS modified cotton fabric.
Forming a hydrophobic silane coating on the surface of copper in a spraying mode, wherein the specific steps are as follows: CF using an atomizing spray gun apparatus 3 The MPOSS solution was sprayed onto the copper surface with a gun head distance of 20cm from the copper sheet for about 3 seconds. Drying the modified copper sheet at 135 ℃ for 0.5h to obtain a novel POSS functionalized hydrophobic silane coating on the surface of the copper sheet, thus obtaining the modified copper sheet CF 3 -MPOSS-Cu。
Example 2
A novel POSS functionalized hydrophobic silane coating was prepared as described in example 1, except that:
replacing trimethoxy (3, 3-trifluoropropyl) silane in the step (1) with trimethoxyphenyl silane with an equal molar amount to obtain phenyl POSS triol sodium salt;
in the step (2), the sodium salt of the trifluoropropyl POSS triol is replaced by sodium salt of phenyl POSS triol with equal molar weight to obtain heptaphenyl vinyl POSS;
reacting heptaphenylvinyl POSS (1.97 g,2 mmol), gamma-mercaptopropyl trimethoxysilane (0.4 g,2 mmol), 2-dimethoxy-2-phenylacetophenone (0.024 g) and THF (39.5 mL) in step (3) under 365nm ultraviolet light (100W) for 45 minutes to obtain a Ph-MPOSS solution with a concentration of 60 mg/mL;
and (3) obtaining the Ph-MPOSS modified cotton fabric and the modified copper sheet Ph-MPOSS-Cu in the step (4).
Comparative example 1
A novel POSS functionalized hydrophobic silane coating was prepared as described in example 1, except that: the room temperature reaction time in the step (2) is set to 8 hours, a powdery white solid cannot be obtained, and the obtained product is a viscous oligomer and cannot be put into the next step for use.
Comparative example 2
A novel POSS functionalized hydrophobic silane coating was prepared as described in example 1, except that: the photoreaction time in the step (3) is changed to 90 minutes, and flocculent precipitation occurs in the obtained solution, so that the next step of use is affected.
Test example 1
Example 1CF prepared 3 Fourier infrared spectra of the-MPOSS solution and the Ph-MPOSS solution prepared in example 2 are shown in FIG. 1, CF 3 MPOSS at 1225cm -1 Has a significant C-F bond absorption peak, and Ph-MPOSS is 3065cm -1 The special unsaturated C-H stretching vibration absorption peak is arranged at the position of 1116cm -1 Has a strong absorption peak belonging to Si-O-Si bonds.
Raw cotton fabric used in examples (FIGS. 2a, b), CF obtained in example 1 3 SEM images of the-MPOSS modified cotton fabric (fig. 2c, d) and the Ph-MPOSS modified cotton fabric (fig. 2e, f) obtained in example 2 are shown in fig. 2, and it is evident from fig. 2 that the fabric surface is covered with a roughened film, which is also the reason for the water repellency of the modified fabric. While CF 3 The water contact angles of the MPOSS modified cotton fabric and the Ph-MPOSS modified cotton fabric are 160 DEG and 154 DEG respectively, and the water repellent performance is excellent.
Copper flakes used in the examples, modified copper flakes CF obtained in example 1 3 SEM images of the-MPOSS-Cu and the modified copper sheet Ph-MPOSS-Cu obtained in example 2 are shown in fig. 3, and it can be seen from fig. 3 that the surface of the modified copper sheet has a certain hole due to the volatilization of the solvent. The existence of the holes can improve the surface roughness and further improve the modified copperWater repellency of the sheet.
Test example 2
Oil-water separation application test:
CF 3 the MPOSS modified cotton fabric and the Ph-MPOSS modified cotton fabric have good water repellency, and meanwhile, the modified cotton fabric has lipophilicity and is easy to be soaked by petroleum ether, normal hexane, methylene dichloride, chloroform and other oils. Light oil and heavy oil are separated by using a simple oil-water separation device (figure 4), and the device consists of two sections of spliced glass tubes and a modified cotton fabric in the middle. Since the dense liquid always contacts the modified cotton fabric first during the re-separation process, the device is placed obliquely when separating light oil and water. Oil is easily collected under the cotton fabric when the oil phase contacts the modified cotton fabric, and oil and water are separated by not passing through the hydrophobic cotton fabric when the water phase contacts the cotton fabric. The separation efficiency and separation flux are shown in fig. 5, and the data are listed in table 1. Because of the change of the device, the flux of heavy oil is larger than that of light oil, and the separation efficiency is over 99 percent, which indicates CF 3 The MPOSS modified cotton fabric and the Ph-MPOSS modified cotton fabric have feasibility and practicality in oil-water separation.
TABLE 1CF 3 -specific data of oil-water separation of the MPOSS modified cotton fabric and the Ph-MPOSS modified cotton fabric.
Test example 3
Copper sheet anticorrosion application test:
modified copper sheet CF 3 Compared with pure copper sheets, the anti-corrosion effects of MPOSS-Cu and Ph-MPOSS-Cu are greatly improved. 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. CF compared to pure copper flakes 3 The corrosion current densities of MPOSS-Cu and Ph-MPOSS-Cu were reduced by about 3 orders of magnitude, and the corrosion potential was shifted forward from-299 mV to-213 mV and-217 mV, respectively, demonstrating the effectiveness of POSS functionalized silane coatings in corrosion protection. Further analysis of corrosion resistance using the impedance Bode graph, as shown in FIG. 7, cu, CF are known from FIG. 7 3 The impedance values of the-MPOSS-Cu and the Ph-MPOSS-Cu are 8.9, 63.6 and 102.9kΩ cm, respectively -2 The impedance value is greatly improved, which indicates that the coating has good anti-corrosion effect.
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 novel POSS functionalized hydrophobic silane coating comprises the following steps:
(1) Uniformly mixing trialkoxysilane, water, alkali and a solvent A, heating and refluxing, and stirring at room temperature for reaction; after the reaction is finished, removing the solvent to obtain POSS metal salt compounds of unfilled corners; the molar ratio of the water to the trialkoxysilane is 1.1-1.5:1; the molar ratio of the alkali to the trialkoxysilane is 0.4-0.5:1; the ratio of the volume of the solvent A to the mole number of the trialkoxysilane is 0.5-1.5 mL/1 mmol; the temperature of the heating reflux is 65-75 ℃; the heating reflux time is 3-6 hours; the stirring reaction time at room temperature is 10-20 hours;
(2) Adding the POSS metal salt compound and the acid absorbent of the unfilled corner obtained in the step (1) into a solvent B, dropwise adding vinyl trichlorosilane under the protection of protective gas at the temperature of 0-5 ℃, and converting the reaction into room temperature reaction after the reaction at the temperature of 0-5 ℃; after the reaction is finished, obtaining vinylsilane end-capped POSS through filtration, concentration and precipitation; the ratio of the volume of the solvent B to the mole number of the POSS metal salt compound of the unfilled corner is 15-25 mL/1 mmol; the acid absorbent is triethylamine; the molar ratio of the acid absorbent to the unfilled corner POSS metal salt compound is 2-4:1; the mol ratio of the vinyl trichlorosilane to the POSS metal salt compound with unfilled corners is 1-1.3:1; the reaction time is 1 to 6 hours at the temperature of 0 to 5 ℃; the reaction time at room temperature is 15-24 hours;
(3) Dispersing the vinyl-terminated POSS obtained in the step (2) into a solvent C, adding mercaptopropyl silane and a photoinitiator, and carrying out photocatalytic reaction to obtain a POSS functionalized silane solution; the mercaptopropyl silane is gamma-mercaptopropyl trimethoxy silane or gamma-mercaptopropyl triethoxy silane; the mol ratio of the mercaptopropyl silane to the vinyl end-capped POSS is 1:1; the mass of the photoinitiator is 0.5-1.5% of the total mass of the vinyl end-capped POSS and the mercaptopropyl silane; the time of the photocatalytic reaction is 10-70 minutes; the light source of illumination of the photocatalysis reaction is a 100W ultraviolet lamp with the wavelength of 10-400nm; the mass concentration of POSS functionalized silane in the POSS functionalized silane solution is 10-80mg/mL, and the mass of the POSS functionalized silane is the sum of the masses of vinyl-terminated POSS and mercaptopropyl silane;
(4) Dispersing the solution in the step (3) on a substrate to prepare the hydrophobic silane coating.
2. The method of preparing a novel POSS functionalized hydrophobic silane coating according to claim 1, wherein the trialkoxysilane in step (1) is trimethoxy (3, 3-trifluoropropyl) silane, triethoxy (3, 3-trifluoropropyl) silane, trimethoxyphenyl silane, or triethoxyphenyl silane.
3. The method of preparing a novel POSS functionalized hydrophobic silane coating according to claim 1, wherein the base in step (1) is sodium hydroxide, potassium hydroxide or lithium hydroxide; the solvent A is tetrahydrofuran, toluene, chloroform, 1, 2-dichloroethane, N-dimethylformamide or dimethyl sulfoxide.
4. The method of preparing a novel POSS functionalized hydrophobic silane coating according to claim 1, wherein the time of the heat reflow in step (1) is 4-5 hours; the stirring reaction time at room temperature is 12-15 hours.
5. The method of preparing a novel POSS functionalized hydrophobic silane coating according to claim 1, wherein in step (2) the solvent B is diethyl ether, tetrahydrofuran, chloroform, 1, 2-dichloroethane or toluene; the protective gas is nitrogen or argon.
6. The method of preparing a novel POSS functionalized hydrophobic silane coating according to claim 1, wherein the vinyl trichlorosilane in step (2) is added at a rate of 1-2 drops/sec.
7. The process for preparing a novel POSS functionalized hydrophobic silane coating according to claim 1, characterized in that in step (2) the reaction time is 3-4 hours at 0-5 ℃; the reaction time at room temperature is 18-20 hours;
concentrating the filtrate obtained by filtering until solid is separated out;
the precipitation step is as follows: adding the concentrated solution obtained by concentration into methanol, precipitating, filtering, and drying at 40-60 ℃ for 2-5h to obtain vinylsilane terminated POSS; the volume ratio of the methanol to the concentrated solution is 15-20:1; the time of the precipitation is 5-10min.
8. The method of preparing a novel POSS functionalized hydrophobic silane coating according to claim 1, wherein in step (3) the solvent C is tetrahydrofuran, chloroform, 1, 2-dichloroethane, benzene, toluene, N-dimethylformamide or dimethylsulfoxide;
the photoinitiator is 2, 2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, 4-dimethylamino ethyl benzoate, diphenyl ketone, 4-chlorobenzophenone, 4-methyl diphenyl ketone or methyl o-benzoyl benzoate.
9. The method of preparing a novel POSS functionalized hydrophobic silane coating according to claim 1, wherein the photocatalytic reaction in step (3) takes from 30 to 60 minutes.
10. The method of preparing a novel POSS functionalized hydrophobic silane coating according to claim 1, wherein the substrate in step (4) is cotton or copper; the preparation method of the hydrophobic silane coating is a dip coating or spray coating method.
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