CN110204569B - Silane coupling agent with dual stimulus responses and preparation method and application thereof - Google Patents
Silane coupling agent with dual stimulus responses and preparation method and application thereof Download PDFInfo
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- CN110204569B CN110204569B CN201910416776.4A CN201910416776A CN110204569B CN 110204569 B CN110204569 B CN 110204569B CN 201910416776 A CN201910416776 A CN 201910416776A CN 110204569 B CN110204569 B CN 110204569B
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- silane coupling
- azobenzene
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 46
- 230000004044 response Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000009977 dual effect Effects 0.000 title claims description 34
- 239000011521 glass Substances 0.000 claims abstract description 96
- 230000003647 oxidation Effects 0.000 claims abstract description 51
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 3-ferrocenyl Chemical group 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000000638 stimulation Effects 0.000 claims abstract description 26
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940095102 methyl benzoate Drugs 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical group [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 7
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000012974 tin catalyst Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 4
- MMNLHUHQFDVPSQ-UHFFFAOYSA-N N=C=O.CCO[Si](OCC)(OCC)C(C)C Chemical compound N=C=O.CCO[Si](OCC)(OCC)C(C)C MMNLHUHQFDVPSQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- YIQFIIPZBORNOU-UHFFFAOYSA-N cyclopenta-1,3-diene (2-cyclopenta-2,4-dien-1-ylphenyl)-phenyldiazene iron(2+) Chemical compound [CH-]1C=CC=C1.C1=CC=C(C=C1)N=NC2=CC=CC=C2[C-]3C=CC=C3.[Fe+2] YIQFIIPZBORNOU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 229910000077 silane Inorganic materials 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- 239000012043 crude product Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000005457 ice water Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- VULLAHRTKMHXNU-UHFFFAOYSA-N decyl benzenecarboperoxoate Chemical compound CCCCCCCCCCOOC(=O)C1=CC=CC=C1 VULLAHRTKMHXNU-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical group CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical group 0.000 description 1
- 238000010432 pen painting Methods 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a silane coupling agent with double stimulus responses, and a preparation method and application thereof. The preparation method comprises the steps of generating 3-ferrocenyl alkoxy-5-azobenzene alkoxy methyl benzoate from 3-hydroxy-5-ferrocenyl alkoxy methyl benzoate and bromoalkoxy azobenzene under the catalysis of alkali, and reducing the 3-ferrocenyl alkoxy-5-azobenzene alkoxy methyl benzoate into a 3-ferrocenyl alkoxy-5-azobenzene alkoxy benzyl alcohol end capping agent; under the protection of nitrogen, adding 3-ferrocenyl alkoxy-5-azobenzene alkoxy benzyl alcohol, isopropyl triethoxy silane isocyanate and catalyst organotin into toluene, heating to 80-110 ℃ and reacting to obtain the ferrocenyl azobenzene silane coupling agent. The silane coupling agent can be used for modifying the surface of glass, and the modified glass has the characteristic of changing the surface hydrophilicity by double stimulation responses of ultraviolet irradiation and oxidation.
Description
Technical Field
The invention relates to a preparation method of a silane coupling agent with double stimulus responses, in particular to a preparation method of a silane coupling agent modified by ferroceneazobenzene; the silane coupling agent can be used for modifying the surface of glass and preparing the glass with controllable surface wettability.
Background
The silane coupling agent is an organosilicon compound having a specific structure, which has both a reactive group capable of binding to an inorganic material (e.g., glass, cement, metal, etc.) and a reactive group capable of binding to an organic material, and thus the surface properties of the inorganic material can be changed by the silane coupling agent.
The wettability of a solid surface is one of very important surface properties, the control of the wettability of the surface is very important in many practical applications, and the hydrophobic/hydrophilic reversible material with the dynamically controllable surface wettability can make precise and predictable changes and regulation on external stimuli, so that the hydrophobic/hydrophilic reversible material has huge application potential in the aspects of stimulus response devices, self-cleaning surfaces, liquid microsphere manipulators, zoom lenses and the like, attracts more interest, and becomes a challenging research subject in material science. Wetting of a solid surface occurs at the contact angle of a water droplet with the surface.
It is reported that Wan Fei et al use nitroxide free radical polymerization to polymerize PVBIm-PF6Successful grafting of polyionic liquids onto inorganic surfacesPreparation of several wettability-controllable surfaces on copper substrates [ D]Lanzhou: northwest university, 2010: 48-58). The reversible conversion between hydrophilicity and hydrophobicity of the inorganic surface modified by the polyionic liquid can be realized by changing related anions. However, the method is complex in synthesis, complicated in conditions, required for polymerization reaction, and single in control method, and can be realized only by changing related anions. The finding of the controllable wettability surface with simple synthesis is of great significance.
Disclosure of Invention
The invention aims to provide a silane coupling agent with double stimulus response and a preparation method thereof; the silane coupling agent has the characteristic of generating ultraviolet light oxidation dual stimulation reaction.
The invention also aims to provide application of the silane coupling agent with double stimulus responses in preparing the glass with controllable surface wettability, and the surface of the modified glass can be quickly changed in surface wettability by dropping an oxidant and irradiating ultraviolet light to obtain surfaces with wettability of different degrees; the modified glass has the characteristics of stimulating reaction under ultraviolet illumination and oxidation to regulate the hydrophilicity of the glass surface without complex operation and expensive instruments.
Ferrocene is an active group capable of undergoing a reversible redox reaction, and can be oxidized into ferrocene ions by oxidants such as ferric sulfate, hydrogen peroxide and the like, ferrocene ions have positive charges, the hydrophilicity of the ferrocene ions can be greatly enhanced, and the ferrocene ions can be reduced into ferrocene by reducing agents such as vitamin C and the like. Azobenzene is an active group capable of photoisomerization, and is irradiated by ultraviolet light to be converted into a cis-structure, and irradiated by visible light to be converted into a trans-structure, the dipole moment of the cis-structure is 3D, the dipole moment of the trans-structure is 0.5D, and the hydrophilicity of the cis-structure is greater than that of the reaction structure.
The purpose of the invention is realized by the following technical scheme:
a silane coupling agent with dual stimulus response has a molecular structural formula as follows:
n is an integer of 3 to 7.
The preparation method of the silane coupling agent with dual stimulus response comprises the following steps:
1) synthesis of alkyl alcohol with double stimulation response of ultraviolet light oxidation: under the protection of nitrogen, 3-hydroxy-5-ferrocene alkoxy methyl benzoate and bromoalkoxy azobenzene are mixed according to the molar ratio of 1: 1-1: 1.5 adding into N, N-Dimethylformamide (DMF) solution, adding carbonate catalyst, heating to 60-80 deg.C, reacting for 5-10 hr; cooling, filtering to remove solid, and performing reduced pressure rotary evaporation to remove N, N-dimethylformamide; dissolving the product in a recrystallization solvent, and recrystallizing at low temperature to obtain a solid product, namely 3-ferrocenyl alkoxy-5-azobenzene alkoxy methyl benzoate; reducing the solid product with lithium aluminum hydride to generate 3-ferrocene alkoxy-5-azobenzene alkoxy benzyl alcohol;
2) preparation of silane coupling agent with ultraviolet light oxidation dual stimulus response: under the protection of nitrogen, 3-ferrocene alkoxy-5-azobenzene alkoxy benzyl alcohol and isocyanatopropyl triethoxysilane are mixed according to a molar ratio of 1:1, adding the organic tin catalyst into anhydrous toluene solution, heating to 70-100 ℃, and reacting for 5-10 hours; the silane coupling agent with ultraviolet light oxidation dual stimulus response is obtained.
To further achieve the object of the present invention, preferably, the carbonate catalyst is at least one of potassium carbonate, sodium carbonate and cesium carbonate.
Preferably, the molar ratio of the carbonate catalyst to the 3-hydroxy-5-ferrocene alkoxy methyl benzoate is 1: 1-2: 1.
preferably, the organic tin catalyst is at least one of dibutyltin dilaurate and stannous octoate.
Preferably, the molar ratio of the organotin catalyst to the isopropyltriethoxysilane isocyanate is 1: 500-1: 1000.
Preferably, the recrystallization solvent is at least one of butanone, acetone, ethanol, diethyl ether and n-hexane.
Preferably, the low-temperature recrystallization is performed for 2 to 6 times.
The silane coupling agent with double stimulus response is applied to the preparation of the glass with controllable surface wettability: uniformly coating a toluene solution containing a silane coupling agent with ultraviolet irradiation and oxidation dual stimulus response on the surface of glass, standing in the air for 2-4 hours, heating to 80-110 ℃, and reacting for 6-12 hours to obtain the glass with ultraviolet irradiation and oxidation dual stimulus response and controllable surface wettability, wherein the glass generates stimulus reaction under ultraviolet irradiation and oxidation, and the surface hydrophilicity of the glass is changed.
The glass generates stimulation reaction under ultraviolet illumination and oxidation, and the change of the surface hydrophilicity of the glass is shown as follows:
1) ultraviolet irradiation: irradiating the glass for 15-30min under ultraviolet light, gradually converting azobenzene groups from a trans-structure to a cis-structure, and increasing the dipole moment from 0.5D to 3D, so that the hydrophilicity of the glass surface is improved;
2) and (3) oxidation: dropwise adding a ferric sulfate aqueous solution with the concentration of 30-50g/L onto the surface of the glass, standing for 1-2 hours, absorbing the aqueous solution, oxidizing ferrocene groups into ferrocene ions, wherein the ferrocene ions have positive charges, and the hydrophilicity of the surface of the glass is greatly improved;
3) co-processing of ultraviolet irradiation and oxidation: dripping 30-50g/L ferric sulfate solution on glass, standing for 1-2 hours, absorbing and removing the water solution, irradiating for 15-30min by using ultraviolet light, converting azobenzene groups into cis-structures, oxidizing ferrocene into ferrocene ions, and improving the hydrophilicity of the glass surface to the maximum extent.
The temperature rise to 80-110 ℃ is carried out in a muffle furnace.
The method is characterized in that the toluene solution containing the ultraviolet light oxidation dual stimulus response silane coupling agent is uniformly coated on the surface of the glass, and 10-20 mu L of water is dripped to be used as a reaction catalyst.
The temperature is raised to 80-100 ℃ when the price glass is immersed in the Paranda solution.
The method for modifying the surface of the glass by using the silane coupling agent is simple, complex operation and expensive instruments are not needed, and the modified glass not only has hydrophobicity, but also has the characteristic of being capable of generating stimulation reaction under ultraviolet illumination and oxidation so as to regulate and control the hydrophilicity of the surface of the glass.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) the silane coupling agent has the characteristic of generating ultraviolet illumination oxidation dual-stimulation reaction, and the surface wettability of the modified glass surface can be rapidly changed by dripping an oxidant and irradiating ultraviolet light to obtain surfaces with different degrees of wettability.
2) The silane coupling agent can be used for improving the hydrophobicity of the glass surface, the modification method is simple, and complex operation and expensive instruments are not needed.
Drawings
FIG. 1A structural diagram and NMR chart of 3-ferrocenehexyloxy, 5-azophenylhexyloxy benzyl alcohol prepared in example 1.
Fig. 2 contact angle test chart of uv light oxidation dual stimulus responsive surface hydrophilicity controllable glass prepared in example 1 under non-stimulation condition.
Fig. 3 is a contact angle test chart of the ultraviolet light irradiation oxidation dual stimulus responsive surface wettability controllable glass prepared in example 1 after the ultraviolet light irradiation.
Fig. 4 is a contact angle test graph of the ultraviolet light oxidation dual stimulus response surface hydrophilicity controllable glass prepared in the example 1 after oxidation.
Fig. 5 is a contact angle test chart of the ultraviolet irradiation and oxidation dual stimulus response surface hydrophilicity controllable glass prepared in the example 1 after the ultraviolet irradiation and oxidation.
Fig. 6 the ultraviolet light oxidation dual stimulus responsive surface hydrophilicity controllable glass prepared in example 1 has an effect of applying an oily pen without stimulus.
Fig. 7 oil pen painting effect of the ultraviolet light oxidation dual stimulus responsive surface wettability controllable glass prepared in example 1 after ultraviolet light irradiation.
Fig. 8 the oil pen smearing effect of the ultraviolet light oxidation dual stimulus responsive surface hydrophilicity controllable glass prepared in example 1 after oxidation.
Fig. 9 the ultraviolet light oxidation dual stimulus responsive surface hydrophilicity controllable glass prepared in example 1 has the smearing effect of the oil pen after ultraviolet light and oxidation.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following embodiments and drawings, but the present invention is not limited thereto.
Example 1
Under the protection of nitrogen, 1g (2.8mmol) of 3-hydroxy, 5-ferrocenehexyloxybenzoic acid methyl ester, 1.52g (4.2mmol) of hexabromohexyloxyazobenzene, 1.37g (4.2mmol) of cesium carbonate and 50mLN, N-Dimethylformamide (DMF) are added into a 150mL three-neck flask, the temperature is increased to 85 ℃ for reaction, the reaction process is determined by thin layer chromatography, after 12 hours, the reaction is finished, the heating is stopped, the cesium carbonate is removed by suction filtration after being cooled to room temperature, the cesium salt is washed by dichloromethane until the cesium salt is colorless, and the solvent is removed by reduced pressure rotary evaporation to obtain a crude product which is orange yellow. And dissolving the crude product in butanone, placing the crude product into a refrigerator for cooling and crystallizing, and repeating the cooling and crystallizing for 3 times to obtain 3-ferrocene hexyloxy-5-azobenzene hexyloxy methyl benzoate.
Adding 10mL of anhydrous tetrahydrofuran into a 150mL three-neck flask under the protection of nitrogen, adding 0.3g (4.7mmol) of lithium aluminum hydride into the tetrahydrofuran under the cooling of an ice water bath, and stirring; dissolving 1g (1.46mmol) of 3-ferrocene hexyloxy-5-azobenzene hexyloxy methyl benzoate in 20mL of anhydrous tetrahydrofuran, slowly dripping the tetrahydrofuran solution in which the 3-ferrocene hexyloxy-5-azobenzene hexyloxy methyl benzoate is dissolved into a three-neck flask through a constant pressure funnel under the cooling of an ice water bath, removing the ice water bath after dripping is finished, and reacting for 7 hours at normal temperature. After the reaction is finished, 0.3g of deionized water with the same weight as that of lithium aluminum hydride is added for quenching reaction, 1.5g/L of sodium hydroxide solution with the same weight is added for stirring reaction for 30min, the reaction is stopped, solid impurities are removed by suction filtration, and the solid is washed by tetrahydrofuran until the color is colorless. And (3) performing rotary evaporation on the product to remove tetrahydrofuran, adding dichloromethane for extraction, and performing rotary evaporation on the extract to remove dichloromethane to obtain an orange-yellow crude product. Dissolving in butanone, and cooling in refrigeratorAnd crystallizing for three times to obtain the 3-ferrocene hexyloxy-5-azobenzene hexyloxy benzoic acid methanol. By passing1H nuclear magnetic hydrogen spectrum is characterized, the characterization result is shown in figure 1,1HNMR(CDCl3,TMS)δ(ppm):7.83(d,4H,H(Azo)),7.41(t,2H,H(Azo)),7.32(t,1H,H(Azo)),6.91(s,2H,H(Ar)),6.42(d,2H,H(Azo)),6.21(s,1H,H(Ar)),4.52(s,2H,HO-CH2-Ar),4.22(s,9H,H(Cp)),3.91(t,2H,-CH2-O-Azo),3.84(t,4H,-O-CH2-Ar),2.13(t,2H,-CH2-Cp),1.74(m,4H,-O-CH2-CH2-),1.51-1.24(m,12H,-(CH2)3-). δ (ppm) ═ 7.83,7.41,7.32,6.42 are proton absorption peaks on azobenzene, and δ (ppm) ═ 4.22 are proton absorption peaks of ferrocene. The results show that the obtained target product is 3-ferrocene hexyloxy, 5-azobenzene hexyloxy benzyl alcohol.
Under the protection of nitrogen, 1g (1.52mmol) of 3-ferrocenylhexyloxy-5-azophenylhexyloxyphenylmethanol, 0.39g (1.52mmol) of isopropyltriethoxysilane isocyanate, 2mg (0.003mmol) of dibutyltin dilaurate as a catalyst and 50mL of anhydrous toluene were added to a 250mL three-necked flask, the temperature was raised to 80 ℃ and the reaction was carried out for 7 hours, thereby obtaining a ferrocenylazosilane coupling agent.
One end of the silane coupling agent is an ethyl silane coupling which can react with hydroxyl on the surface of the glass to generate a chemical bond to be connected with the surface of the glass, and the other end of the silane coupling agent is a hydrophobic chain which can enhance the hydrophobicity of the surface of the glass when the silane coupling agent is connected with the surface of the glass. The structural formula of the silane coupling agent is as follows:
60mL of 98 wt% concentrated sulfuric acid is weighed by a measuring cylinder and poured into a beaker, 20mL of 30% wt% hydrogen peroxide is weighed and slowly added into the concentrated sulfuric acid while stirring to prepare Paranha washing liquid, after the Paranha washing liquid is cooled, a commercially available glass sheet is immersed in the concentrated sulfuric acid, the temperature is increased to 80 ℃, the temperature is kept constant for 1 hour, the glass sheet is taken out, washed by deionized water, washed by absolute ethyl alcohol and dried.
Uniformly coating a toluene solution containing the ferrocenyl azobenzene silane coupling agent on the treated glass sheet, standing for half an hour, putting the glass sheet into a muffle furnace for heat treatment at the heating rate of 5 ℃/min, heating to 110 ℃, and preserving heat for 2 hours to obtain the glass with the surface subjected to hydrophobic modification.
The ultraviolet light oxidation dual stimulus response surface wettability controllable glass obtained in the example is used for contact angle test, and the wettability of the glass surface is characterized by the contact angle. The contact angle was measured by using a surface tension surface contact angle tester model OCA40Micro (temperature 25 ℃ C.) manufactured by Aapthysics. FIG. 2 is a graph of the contact angle of the glass surface measured without stimulus, which is 89, indicating that the glass surface has good hydrophobicity; FIG. 3 is a result of a contact angle test of a glass surface after ultraviolet irradiation stimulation, in which the ultraviolet irradiation stimulation operation is to irradiate the glass with ultraviolet light for 15min and then perform a contact angle test, and the measured contact angle is 75 degrees, which shows that the hydrophobicity of the glass surface is reduced compared with that in a non-stimulation state; FIG. 4 shows the contact angle test result of the glass surface after the oxidation stimulation, the oxidation operation is to drop the ferric sulfate solution with the concentration of 30g/L on the glass, stand for 30min, use filter paper to absorb the water solution, and perform the contact angle test after drying, and the measured contact angle is 58 degrees, which indicates that the hydrophobicity of the glass surface is greatly reduced after the oxidation stimulation. FIG. 5 shows the contact angle test result of the glass surface after the double stimulation of ultraviolet light oxidation, the operation steps of the double stimulation of ultraviolet light oxidation include that firstly, ferric sulfate solution with the concentration of 30g/L is dripped on the glass, the glass is kept still for 30min, filter paper is used for absorbing the water solution, and after the glass is dried, ultraviolet light is used for irradiating for 15 min. The contact angle test was then carried out and the contact angle was found to be 43 deg., which indicates that the hydrophobicity of the glass surface was reduced by more than one time.
The glass before and after the stimulus response has different antifouling abilities, fig. 6 shows that the oily pen on the surface of the modified glass has a better anti-graffiti ability under the non-stimulation state, the oily pen is difficult to attach to the oily pen, fig. 7 shows that the oily pen on the surface of the modified glass under the ultraviolet illumination state has a slightly weaker anti-graffiti ability than that of fig. 6, the oily pen is difficult to attach to the oily pen, fig. 8 shows that the oily pen can be continuously attached to the oxidized glass, the anti-graffiti ability of the oily pen is far smaller than that of the non-stimulation state, fig. 9 shows that the oily pen can be continuously attached to the oxidized glass under the ultraviolet illumination state, and the oily pen can be well and continuously attached to the oily pen, and the anti-graffiti ability of the oily pen is the weakest.
From the above results, it can be proved that the glass with the surface wettability controllable by ultraviolet light oxidation dual stimulation can obtain glass surfaces with different wettability by ultraviolet light stimulation, oxidation stimulation and ultraviolet light oxidation dual stimulation, wherein the surface hydrophobicity is maximum under the non-stimulation state, the surface hydrophobicity is reduced after ultraviolet light irradiation, the surface hydrophobicity is greatly reduced after oxidation stimulation, the surface hydrophobicity is reduced maximum after ultraviolet light oxidation dual stimulation, and is reduced by more than one time compared with the non-stimulation state, the glass surfaces under different states have different dustproof effects, and different purposes can be realized.
Example 2
Under the protection of nitrogen, 1g (2.6mmol) of 3-hydroxy, 5-ferrocene octyloxybenzoic acid methyl ester, 0.8g (2.6mmol) of hexabromooctyloxybenzone, 0.54g (3.9mmol) of potassium carbonate and 50mLN, N-Dimethylformamide (DMF) are added into a 150mL three-neck flask, the temperature is raised to 85 ℃ for reaction, the reaction process is determined by thin layer chromatography, the reaction is finished after 12 hours, the heating is stopped, the potassium carbonate is removed by suction filtration after the temperature is cooled to room temperature, the potassium salt is washed to be colorless by dichloromethane, and the solvent is removed by reduced pressure rotary evaporation to obtain an orange-yellow crude product. Dissolving the crude product with butanone, placing the crude product into a refrigerator for cooling and crystallizing, and repeating the steps for 3 times to obtain 3-ferrocene octyloxy, 5-azobenzene octyloxy methyl benzoate.
Under the protection of nitrogen, 10mL of anhydrous tetrahydrofuran is added into a 150mL three-neck flask, 0.3g (4.7mmol) of lithium aluminum hydride is added into the tetrahydrofuran under the cooling of an ice-water bath, 1g (1.37mmol) of 3-ferrocene octyloxy and 5-azobenzene octyloxy methyl benzoate is dissolved into 20mL of anhydrous tetrahydrofuran, stirring is carried out, a solution in which the 3-ferrocene octyloxy and 5-azobenzene octyloxy methyl benzoate are dissolved is slowly dripped into the three-neck flask through a constant pressure funnel under the cooling of the ice-water bath, the ice-water bath is removed after the dripping is finished, and the reaction is carried out for 7 hours at normal temperature. After the reaction is finished, 0.3g of deionized water with the same weight as that of lithium aluminum hydride is added for quenching reaction, 1.5g/L of sodium hydroxide solution with the same weight is added for stirring reaction for 30min, the reaction is stopped, and the product is filtered by suction to remove solid impurities and is washed by tetrahydrofuran for many times until the product is colorless. And (3) performing rotary evaporation on the product solution to remove tetrahydrofuran, adding dichloromethane for extraction, and performing rotary evaporation on the extract to remove dichloromethane to obtain an orange-yellow crude product. Adding butanone for dissolution, and placing the mixture into a refrigerator for cooling and crystallizing for three times to obtain the 3-ferrocene octyloxy-5-azobenzene octyloxy benzyl alcohol.
Under the protection of nitrogen, 1g (1.42mmol) of 3-ferrocene octyloxy-5-azobenzene octyloxy benzyl alcohol, 0.2 wt% of catalyst dibutyltin dilaurate, 0.35g (1.42mmol) of isocyanatopropyl triethoxysilane and 50mL of anhydrous toluene are added into a 250mL three-neck flask, the temperature is raised to 80 ℃, and the reaction is carried out for 7 hours, thus obtaining the ferrocene azobenzene silane coupling agent.
60mL of 98 wt% concentrated sulfuric acid is weighed by a measuring cylinder and poured into a beaker, 20mL of 30% wt% hydrogen peroxide is weighed and slowly added into the concentrated sulfuric acid while stirring to prepare Paranha washing liquid, after the Paranha washing liquid is cooled, a commercially available glass sheet is immersed in the concentrated sulfuric acid, the commercially available glass sheet is heated to 80 ℃ and is kept at the constant temperature for 1 hour, the glass sheet is taken out, washed by deionized water, washed by absolute ethyl alcohol and dried.
And uniformly coating a toluene solution containing the ferrocenyl azobenzene silane coupling agent on the treated glass sheet, standing for half an hour, putting the glass sheet into a muffle furnace for heat treatment at the heating rate of 5 ℃/min, heating to 110 ℃, and preserving heat for 2 hours to obtain the glass with controllable surface wettability.
The self-assembled monolayer film obtained in example 2 has a longer hydrophobic chain, and the surface hydrophobicity is stronger than that in example 1 in four cases of no stimulus response, ultraviolet irradiation stimulus response, oxidation stimulus response and ultraviolet irradiation oxidation stimulus response.
Example 3
Under the protection of nitrogen, 1g (2.5mmol) of methyl 3-hydroxy-5-ferrocenium decyloxybenzoate, 1.54g (3.75mmol) of hexabromodecyloxyiazobenzene, 1.22g (3.75mmol) of cesium carbonate and 50mLN, N-Dimethylformamide (DMF) are added into a 150mL three-neck flask, the temperature is raised to 85 ℃ for reaction, the reaction process is determined by thin layer chromatography, after 12 hours, the reaction is finished, the heating is stopped, the cesium carbonate is removed by suction filtration after being cooled to room temperature, the cesium salt is washed by dichloromethane until the cesium salt is colorless, and the solvent is removed by reduced pressure rotary evaporation to obtain a crude product which is orange yellow. Dissolving the crude product with butanone, placing the crude product into a refrigerator for cooling and crystallizing, and repeating for 3 times to obtain 3-ferrocene decyloxy-5-azobenzene decyloxy methyl benzoate.
Under the protection of nitrogen, 10mL of anhydrous tetrahydrofuran is added into a 150mL three-neck flask, 0.3g (4.7mmol) of lithium aluminum hydride is added into the tetrahydrofuran under the cooling of an ice-water bath, 1g (1.28mmol) of methyl 3-ferrocene decyloxy-5-azobenzene decyloxy benzoate is dissolved into 20mL of anhydrous tetrahydrofuran, the mixture is stirred, the solution in which the methyl 3-ferrocene decyloxy-5-azobenzene decyloxy benzoate is dissolved is slowly dripped into the three-neck flask through a constant pressure funnel under the cooling of the ice-water bath, the ice-water bath is removed after the dripping is finished, and the reaction is carried out for 7 hours at normal temperature. After the reaction is finished, 0.3g of deionized water with the same weight as that of lithium aluminum hydride is added for quenching reaction, 1.5g/L of sodium hydroxide solution with the same weight is added for stirring reaction for 30min, the reaction is stopped, and the product is filtered by suction to remove solid impurities and is washed by tetrahydrofuran for many times until the product is colorless. And (3) performing rotary evaporation on the product solution to remove tetrahydrofuran, adding dichloromethane for extraction, and performing rotary evaporation on the extract to obtain an orange-yellow crude product. Adding butanone for dissolution, and placing the mixture into a refrigerator for cooling and crystallizing for three times to obtain the 3-ferrocene decyloxy-5-azobenzene decyloxy benzyl alcohol.
Under the protection of nitrogen, 1g (1.33mmol) of 3-ferrocene decyloxy-5-azobenzene decyloxy benzyl alcohol, 0.2 wt% of catalyst dibutyltin dilaurate, 0.33g (1.33mmol) of isocyanatopropyl triethoxysilane and 50mL of anhydrous toluene are added into a 250mL three-neck flask, the temperature is raised to 80 ℃, and the reaction is carried out for 7 hours, thus obtaining the ferrocene azobenzene silane coupling agent.
60mL of 98 wt% concentrated sulfuric acid is weighed by a measuring cylinder and poured into a beaker, 20mL of 30% wt% hydrogen peroxide is weighed and slowly added into the concentrated sulfuric acid while stirring to prepare Paranha washing liquid, after the Paranha washing liquid is cooled, a commercially available glass sheet is immersed in the concentrated sulfuric acid, the commercially available glass sheet is heated to 80 ℃ and is kept at the constant temperature for 1 hour, the glass sheet is taken out, washed by deionized water, washed by absolute ethyl alcohol and dried.
And uniformly coating a toluene solution containing the ferrocenyl azobenzene silane coupling agent on the treated glass sheet, standing for half an hour, putting the glass sheet into a muffle furnace for heat treatment at the heating rate of 5 ℃/min, heating to 110 ℃, and preserving heat for 2 hours to obtain the glass with controllable surface wettability.
The modified glass obtained in example 3 has a longer hydrophobic chain, and the surface hydrophobicity is stronger than that in example 2 in four cases of no stimulus response, ultraviolet irradiation stimulus response, oxidation stimulus response and ultraviolet irradiation oxidation stimulus response.
The above-mentioned embodiments are merely illustrative, but the embodiments of the present invention are not limited to the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (10)
1. A silane coupling agent with dual stimulus response is characterized in that the molecular structural formula of the silane coupling agent is as follows:
n is an integer of 3 to 7.
2. The method for producing a silane coupling agent having a dual stimulus response according to claim 1, characterized by comprising the steps of:
1) synthesis of alkyl alcohol with double stimulation response of ultraviolet light oxidation: under the protection of nitrogen, 3-hydroxy-5-ferrocene alkoxy methyl benzoate and bromoalkoxy azobenzene are mixed according to the molar ratio of 1: 1-1: 1.5 adding the mixture into N, N-dimethylformamide solution, adding carbonate catalyst, heating to 60-80 ℃, and reacting for 5-10 hours; cooling, filtering to remove solid, and performing reduced pressure rotary evaporation to remove N, N-dimethylformamide; dissolving the product in a recrystallization solvent, and recrystallizing at low temperature to obtain a solid product, namely 3-ferrocenyl alkoxy-5-azobenzene alkoxy methyl benzoate; reducing the solid product with lithium aluminum hydride to generate 3-ferrocene alkoxy-5-azobenzene alkoxy benzyl alcohol;
2) preparation of silane coupling agent with ultraviolet light oxidation dual stimulus response: under the protection of nitrogen, 3-ferrocene alkoxy-5-azobenzene alkoxy benzyl alcohol and isocyanatopropyl triethoxysilane are mixed according to a molar ratio of 1:1, adding the organic tin catalyst into anhydrous toluene solution, heating to 70-100 ℃, and reacting for 5-10 hours; the silane coupling agent with ultraviolet light oxidation dual stimulus response is obtained.
3. The method for producing a silane coupling agent having a dual stimulus response according to claim 2, characterized in that: the carbonate catalyst is at least one of potassium carbonate, sodium carbonate and cesium carbonate.
4. The method for producing a silane coupling agent having a dual stimulus response according to claim 2, characterized in that: the mol ratio of the carbonate catalyst to the 3-hydroxy-5-ferrocene alkoxy methyl benzoate is 1: 1-2: 1.
5. the method for producing a silane coupling agent having a dual stimulus response according to claim 2, characterized in that: the organic tin catalyst is at least one of dibutyltin dilaurate and stannous octoate.
6. The method for producing a silane coupling agent having a dual stimulus response according to claim 2, characterized in that: the mol ratio of the organic tin catalyst to the isopropyltriethoxysilane isocyanate is 1: 500-1: 1000.
7. The method for producing a silane coupling agent having a dual stimulus response according to claim 2, characterized in that: the recrystallization solvent is at least one of butanone, acetone, ethanol, diethyl ether and n-hexane.
8. The method for producing a silane coupling agent having a dual stimulus response according to claim 2, characterized in that: the low-temperature recrystallization time is 2-6.
9. Use of the silane coupling agent with dual stimulus response of claim 1 for the preparation of surface wettability-controlled glass, characterized in that: uniformly coating a toluene solution containing a silane coupling agent with ultraviolet light oxidation double stimulus response on the surface of glass, standing in the air for 2-4 hours, heating to 80-110 ℃, and reacting for 6-12 hours to obtain the glass with ultraviolet light oxidation double stimulus response and controllable surface wettability; the glass generates stimulation reaction under ultraviolet irradiation and oxidation, and the hydrophilicity of the surface of the glass is changed.
10. Use of a silane coupling agent with dual stimulus response according to claim 9 for the preparation of a surface wettability-controlled glass, characterized in that: the glass generates stimulation reaction under ultraviolet illumination and oxidation, and the change of the surface hydrophilicity of the glass is shown as follows:
1) ultraviolet irradiation: irradiating the glass for 15-30min under ultraviolet light, gradually converting azobenzene groups from a trans-structure to a cis-structure, and increasing the dipole moment from 0.5D to 3D, so that the hydrophilicity of the glass surface is improved;
2) and (3) oxidation: dropwise adding a ferric sulfate aqueous solution with the concentration of 30-50g/L onto the surface of the glass, standing for 1-2 hours, absorbing the aqueous solution, oxidizing ferrocene groups into ferrocene ions, wherein the ferrocene ions have positive charges, and the hydrophilicity of the surface of the glass is greatly improved;
3) co-processing of ultraviolet irradiation and oxidation: dripping 30-50g/L ferric sulfate solution on glass, standing for 1-2 hours, absorbing and removing the water solution, irradiating for 15-30min by using ultraviolet light, converting azobenzene groups into cis-structures, oxidizing ferrocene into ferrocene ions, and improving the hydrophilicity of the glass surface to the maximum extent.
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