CN110204569A - A kind of silane coupling agent and the preparation method and application thereof with double stimuli responsive - Google Patents
A kind of silane coupling agent and the preparation method and application thereof with double stimuli responsive Download PDFInfo
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- CN110204569A CN110204569A CN201910416776.4A CN201910416776A CN110204569A CN 110204569 A CN110204569 A CN 110204569A CN 201910416776 A CN201910416776 A CN 201910416776A CN 110204569 A CN110204569 A CN 110204569A
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- Prior art keywords
- coupling agent
- silane coupling
- ferrocene
- glass
- stimuli responsive
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- 239000006087 Silane Coupling Agent Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 84
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 alkoxybenzyl alcohol Chemical compound 0.000 claims abstract description 18
- 238000010792 warming Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 43
- 238000007254 oxidation reaction Methods 0.000 claims description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 18
- 230000010148 water-pollination Effects 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- 230000004044 response Effects 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000007787 solid Substances 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
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000000047 product Substances 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 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 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
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000007788 liquid 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
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 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 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 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 2
- 239000012975 dibutyltin dilaurate Substances 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
- 238000005815 base catalysis Methods 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 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 15
- 238000012360 testing method Methods 0.000 description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 239000005457 ice water Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 7
- 230000000638 stimulation Effects 0.000 description 7
- 235000019445 benzyl alcohol Nutrition 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000005357 flat glass Substances 0.000 description 6
- 239000006210 lotion Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229940095102 methyl benzoate Drugs 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000002441 reversible 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-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
- 150000001450 anions Chemical class 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 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
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- OTVPWGHMBHYUAX-UHFFFAOYSA-N [Fe].[CH]1C=CC=C1 Chemical compound [Fe].[CH]1C=CC=C1 OTVPWGHMBHYUAX-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- QECQLMGRLZYSEW-UHFFFAOYSA-N decoxybenzene Chemical compound CCCCCCCCCCOC1=CC=CC=C1 QECQLMGRLZYSEW-UHFFFAOYSA-N 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 1
- KNRQFACTBMDELK-UHFFFAOYSA-N hexoxybenzene Chemical compound CCCCCCOC1=CC=CC=C1 KNRQFACTBMDELK-UHFFFAOYSA-N 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 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
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
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
Landscapes
- 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 kind of silane coupling agent and the preparation method and application thereof with double stimuli responsive.The preparation method is by 3- hydroxyl, 5- ferrocene alkoxybenzoic acid methyl esters and bromine alkoxy azobenzene generate 3- ferrocene alkoxy under base catalysis, 5- azobenzene alkoxybenzoic acid methyl esters, then it is reduced into 3- ferrocene alkoxy, 5- azobenzene alkoxybenzyl alcohol end-capping reagent；Under nitrogen protection, by 3- ferrocene alkoxy, 5- azobenzene alkoxybenzyl alcohol, isocyanatopropyl triethoxysilane, catalyst organotin are added in toluene, are warming up to 80-110 DEG C of reaction and obtain ferrocene azobenzene silane coupling agent.Silane coupling agent of the invention can be used for modified glass surface, and modified glass has the characteristics that can aoxidize double stimuli responsive by ultraviolet lighting changes surface hydrophilicity.
Description
Technical field
The present invention relates to a kind of preparation methods of silane coupling agent with double stimuli responsive, especially relate to two
The preparation method of the modified silane coupling agent of cyclopentadienyl iron azobenzene；The silane coupling agent can be used for Glass Surface Modification, prepare surface
The controllable glass of wettability.
Background technique
Silane coupling agent is a kind of organo-silicon compound with special construction, and having simultaneously can be with inorganic material (such as
Glass, cement, metal etc.) reactive group that combines and the reactive group in conjunction with organic material, therefore silicon can be passed through
Alkane coupling agent changes the surface naturies of inorganic substances.
The wettability of the surface of solids is very important one of surface nature, and the wet of surface is controlled in many practical applications
Lubricant nature is most important, and the controllable hydrophobic/hydrophilic character reversible material of surface wettability dynamic is due to that can make essence to outside stimulus
True and predictable change and regulation, in stimuli responsive device, self-cleaning surface, liquid microballoon executor, the first-class side of varifocal mirror
Face has huge applications potential, has attracted the interest that people are bigger, has become challenging research topic in material science.Gu
The wettability in body surface face is embodied in the contact angle of water droplet Yu the surface.
It is reported that ten thousand phenanthrene et al. utilize NO free radical polymerization reaction by PVBIm-PF6Poly ion liquid is successfully grafted to
Inorganic surfaces (Lanzhou preparation [D] of Wan Fei several wettability controlled surfaces on copper-based bottom: Northwest Normal University, 2010:
48-58).The inorganic surfaces of this poly ion liquid modification, the reversible transformation between hydrophilic and hydrophobic can pass through transformation related anion
To realize.But this method synthesis is complicated, and condition is cumbersome, needs to carry out polymerization reaction, and control method is single, can only be by changing
Become related anion to realize.The simple controllable wettability surface of synthesis is found to have great importance.
Summary of the invention
Primary and foremost purpose of the invention is to provide a kind of silane coupling agent and preparation method thereof with double stimuli responsive；This
The silane coupling agent of invention has the characteristics that ultraviolet lighting oxidation double stimuli reaction occurs.
Another object of the present invention be to provide the silane coupling agent with double stimuli responsive prepare surface moist can
The application in glass is controlled, modified glass surface can be by quickly changing surface wettability in dropwise addition oxidant and ultraviolet lighting
Property, obtain the surface of different degrees of wettability；Without complex operations and expensive instrument, modified glass has can be in ultraviolet light
According to, the lower stimulate the reaction that occurs of oxidation to regulate and control the hydrophilic feature of glass surface.
Ferrocene is a kind of active group that Reversible redox reaction can occur, it can be oxidized agent such as ferric sulfate,
Hydrogen peroxide etc. is oxidized to ferrocene Weng ion, and ferrocene Weng ion has positive charge, and hydrophily can greatly enhance, ferrocene
Weng ion can be reduced agent vitamin C etc. and be reduced into ferrocene.Azobenzene is a kind of active group that photoisomerization can occur,
It is transformed into cis-structure after ultraviolet light, is transformed into transconfiguration after radiation of visible light, and cis-structure dipole moment is
3D, transconfiguration dipole moment are 0.5D, and the hydrophily of cis-structure is greater than the hydrophily of reaction structure.
The purpose of the present invention is achieved through the following technical solutions:
A kind of silane coupling agent with double stimuli responsive, molecular structural formula are as follows:
N is the integer of 3-7.
The preparation method of the silane coupling agent with double stimuli responsive, includes the following steps:
1) synthesis with ultraviolet lighting oxidation double stimuli responsive alkylol: under nitrogen protection, by 3- hydroxyl, bis- cyclopentadienyl of 5-
Iron alkoxybenzoic acid methyl esters is added to N,N-dimethylformamide with molar ratio with bromine alkoxy azobenzene for 1:1~1:1.5
(DMF) in solution, carbonate catalyst is added, is warming up to 60-80 DEG C, reacts 5-10 hours；It is cooling, it filters and removes solid, subtract
Pressure revolving removes N,N-dimethylformamide；Product is dissolved in recrystallization solvent, low temperature recrystallization obtains solid product 3- bis-
Luxuriant iron alkoxy, 5- azobenzene alkoxybenzoic acid methyl esters；Solid product lithium aluminium hydride reduction is generated into 3- ferrocene alcoxyl
Base, 5- azobenzene alkoxybenzyl alcohol；
2) preparation with ultraviolet lighting oxidation double stimuli responsive silane coupling agent: under nitrogen protection, by bis- cyclopentadienyl of 3-
Iron alkoxy, 5- azobenzene alkoxybenzyl alcohol are added to isocyanatopropyl triethoxysilane with molar ratio for 1:1 anhydrous
In toluene solution, organotin catalysts are added, are warming up to 70-100 DEG C, reaction time 5-10 hour；It obtains with ultraviolet lighting
Aoxidize double stimuli responsive silane coupling agent.
To further realize the object of the invention, it is preferable that the carbonate catalyst is potassium carbonate, sodium carbonate and carbonic acid
At least one of caesium.
Preferably, the carbonate catalyst and 3- hydroxyl, the molar ratio of 5- ferrocene alkoxybenzoic acid methyl esters are
1:1~2:1.
Preferably, the organotin catalysts are at least one of dibutyl tin dilaurate and stannous octoate.
Preferably, the organotin catalysts and isocyanatopropyl triethoxysilane molar ratio are 1:500~1:
1000。
Preferably, the recrystallization solvent is at least one of butanone, acetone, ethyl alcohol, ether and n-hexane.
Preferably, the number of low temperature recrystallization is 2-6 times.
The silane coupling agent with double stimuli responsive is preparing the application in the controllable glass of surface moist: will
It is uniformly applied to glass surface containing the toluene solution with ultraviolet lighting oxidation double stimuli responsive silane coupling agent, in air
2-4 hours are stood, is warming up to 80-110 DEG C, reaction time 6-12 hour obtains aoxidizing double stimuli responsive with ultraviolet lighting
Stimulate the reaction, the change of glass surface hydrophily occur under ultraviolet lighting, oxidation for the controllable glass of surface moist, glass.
Stimulate the reaction occurs under ultraviolet lighting, oxidation for the glass, and the change of glass surface hydrophily shows themselves in that
1) ultraviolet lighting: glass is irradiated into 15-30min under ultraviolet light, azobenzene group gradually changes from transconfiguration
For cis-structure, dipole moment is promoted from 0.5D to 3D, the raising of glass surface hydrophily；
2) it aoxidizes: the ferric sulfate aqueous solution that concentration is 30-50g/L being added drop-wise to glass surface, 1-2 hours is stood, absorbs
Aqueous solution, ferrocene group can be oxidized to ferrocene Weng ion, and ferrocene Weng ion has positive charge, glass surface hydrophily
It is substantially improved；
3) ultraviolet lighting is jointly processed by with oxidation: the ferrum sulfuricum oxydatum solutum that concentration is 30-50g/L is added drop-wise on glass, it is quiet
It sets 1-2 hours, absorbs aqueous solution, then with ultraviolet light 15-30min, azobenzene group is changed into cis-structure, ferrocene oxygen
It is melted into ferrocene Weng ion, glass surface hydrophily obtains amplitude peak promotion.
It is described that be warming up to 80-110 DEG C carried out in Muffle furnace.
Described will uniformly be applied to containing the toluene solution with ultraviolet lighting oxidation double stimuli responsive silane coupling agent
Glass surface further includes that 10-20 μ L water is added dropwise as catalysts.
It is described that be warming up to 80-110 DEG C be that price glass heats to 80-100 DEG C when being immersed in Paranda solution.
The present invention is simple with the silane coupling agent modified glass surface method, modified without complex operations and expensive instrument
Glass afterwards not only has hydrophobicity, and stimulate the reaction can be occurred under ultraviolet lighting, oxidation to regulate and control glass surface by also having
Hydrophilic feature.
The present invention have the following advantages compared with the existing technology and the utility model has the advantages that
1) silane coupling agent of the invention has the characteristics that ultraviolet lighting oxidation double stimuli reaction occurs, modified
Glass surface can obtain the table of different degrees of wettability by quickly changing surface moist in dropwise addition oxidant and ultraviolet lighting
Face.
2) silane coupling agent of the invention can be used for improving glass surface hydrophobicity, and method of modifying is simple, not need complexity
Operation and expensive instrument.
Detailed description of the invention
The 3- ferrocene hexyloxy prepared in Fig. 1 embodiment 1, the structure chart and nuclear-magnetism of 5- azobenzene hexyloxy benzyl alcohol are total
Shake hydrogen spectrogram.
The ultraviolet lighting oxidation controllable glass of double stimuli response surface hydrophily prepared in Fig. 2 embodiment 1 is non-stimulated
Under the conditions of contact angle test figure.
The ultraviolet lighting oxidation controllable glass of double stimuli response surface wettability prepared in Fig. 3 embodiment 1 is in ultraviolet light
Contact angle test figure after irradiation.
The ultraviolet lighting oxidation controllable glass of double stimuli response surface hydrophily prepared in Fig. 4 embodiment 1 is after oxidation
Contact angle test figure.
The ultraviolet lighting oxidation controllable glass of double stimuli response surface hydrophily prepared in Fig. 5 embodiment 1 is in ultraviolet light
According to and oxidation after contact angle test figure.
The ultraviolet lighting oxidation controllable glass of double stimuli response surface hydrophily prepared in Fig. 6 embodiment 1 is non-stimulated
Condition oil pen's scribble effect.
The ultraviolet lighting oxidation controllable glass of double stimuli response surface wettability prepared in Fig. 7 embodiment 1 is in ultraviolet light
Oil pen's scribble effect after irradiation.
The ultraviolet lighting oxidation controllable glass of double stimuli response surface hydrophily prepared in Fig. 8 embodiment 1 is after oxidation
Oil pen's scribble effect.
The ultraviolet lighting oxidation controllable glass of double stimuli response surface hydrophily prepared in Fig. 9 embodiment 1 is in ultraviolet light
According to and oxidation after oil pen's scribble effect.
Specific embodiment
For a better understanding of the present invention, below with reference to case study on implementation and attached drawing, the invention will be further described, but this
The embodiment of invention is without being limited thereto.
Embodiment 1
Under nitrogen protection, 1g (2.8mmol) 3- hydroxyl, 5- ferrocene hexyloxy benzene are added in the three-necked flask of 150mL
Methyl formate, 1.52g (4.2mmol) hexabromo hexaoxyazobenzene, 1.37g (4.2mmol) cesium carbonate, 50mLN, N- dimethyl methyl
Amide (DMF), is warming up to 85 DEG C of reactions, determines reaction process with thin-layer chromatography chromatography in reaction process, reacts after 12 hours
It completes, stops heating, filtered after being cooled to room temperature and remove cesium carbonate, rinse cesium salt to colourless with methylene chloride, vacuum rotary steam removes
Solvent is removed, orange-yellow crude product is obtained.Crude product is dissolved in butanone, crystallisation by cooling in refrigerator is put into, is repeated 3 times, obtain
3- ferrocene hexyloxy, 5- azobenzene hexyloxybenzoate methyl esters.
Under nitrogen protection, 10mL anhydrous tetrahydro furan is added in the three-necked flask of 150mL, by 0.3g under ice-water bath is cooling
(4.7mmol) lithium aluminium hydride reduction is added in tetrahydrofuran, stirring；By 1g (1.46mmol) 3- ferrocene hexyloxy, 5- azobenzene oneself
P-methoxybenzoic acid methyl esters is dissolved in 20mL anhydrous tetrahydro furan, will be dissolved with 3- ferrocene by constant pressure funnel under ice-water bath is cooling
The tetrahydrofuran solution of hexyloxy, 5- azobenzene hexyloxybenzoate methyl esters is slowly dropped into three-necked flask, and recession is added dropwise
Ice-water bath is removed, is reacted 7 hours under room temperature.The deionized water 0.3g quenching reaction with weights such as lithium aluminium hydride reductions is added after completion of the reaction,
The sodium hydroxide solution for the 1.5g/L of weight such as adding is stirred to react 30min, stops reaction, filters and removes solid impurity and be used in combination
Tetrahydrofuran rinses solid to colourless.Product is rotated and removes tetrahydrofuran, methylene chloride extraction is added, extract liquor revolving is removed
Methylene chloride is removed, orange-yellow crude product is obtained.Be added butanone dissolution, be put into refrigerator crystallisation by cooling three times, obtain 3- ferrocene oneself
Oxygroup, 5- azobenzene hexyloxybenzoate methanol.Pass through1H nucleus magnetic hydrogen spectrum is characterized, characterization result as 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 is azo
Proton uptake peak on benzene, δ (ppm)=4.22 are the proton uptake peak of ferrocene.The above result shows that obtained target product
For 3- ferrocene hexyloxy, 5- azobenzene hexyloxy benzyl alcohol.
Under nitrogen protection, by 1g (1.52mmol) 3- ferrocene hexyloxy, 5- azobenzene hexyloxy benzyl alcohol, 0.39g
Catalyst dibutyltin dilaurylate, the 50mL of (1.52mmol) isocyanatopropyl triethoxysilane, 2mg (0.003mmol)
Dry toluene is added in 250mL three-necked flask, is warming up to 80 DEG C, reacts 7 hours, it is coupled to obtain ferrocene azo phenylsilane
Agent.
The silane coupling agent one end is that ethylsilane is even, can react with the hydroxyl of glass surface and generate chemical key connection
In glass surface, the other end is hydrophobic chain, can reinforcing glass surface hydrophobic when silane coupling agent is connected to glass surface.
The silane coupling agent structural formula is as follows:
It is poured into beaker with the concentrated sulfuric acid that graduated cylinder weighs 60mL98wt%, then measures the dioxygen waterside of 20mL30%wt% and stir
It mixes side to be slowly added in the concentrated sulfuric acid, Paranha washing lotion is made, after Paranha washing lotion is cooling, available glass piece is immersed it
In, after being heated to 80 DEG C, constant temperature 1 hour, sheet glass is taken out, is rinsed with deionized water, then is rinsed with dehydrated alcohol, dried.
By on the sheet glass that is uniformly applied to that treated of the toluene solution containing ferrocene azobenzene silane coupling agent, stand
Half an hour is put into Muffle furnace and is heat-treated, and the rate of heat addition is 5 DEG C/min, is warming up to 110 DEG C, keeps the temperature 2 hours, obtains surface
By the glass of hydrophobically modified.
It is contacted using the oxidation controllable glass of double stimuli response surface wettability of ultraviolet lighting obtained in this example
Angle test, the wettability of glass surface is characterized by contact angle.The OCA40Micro type table produced with Aataphysics company
Face tensile surface contact angle tester (25 DEG C of temperature) tests contact angle.Glass surface contact angle test when Fig. 2 is non-stimulated
As a result, the contact angle is 89 °, this shows that glass surface has good hydrophobicity；Fig. 3 is the post-stimulatory glass table of ultraviolet lighting
Face contact angle test result, ultraviolet lighting stimulation applications are first to use ultraviolet light glass 15min, then carry out contact angle test,
Measuring contact angle is 75 °, this shows glass surface hydrophobicity relative to being reduced under non-stimulated state；Fig. 4 is oxidation stimulation
Rear glass surface contact angle test as a result, oxidation operation is that first the ferrum sulfuricum oxydatum solutum that concentration is 30g/L is added dropwise on glass,
30min is stood, aqueous solution is absorbed with filter paper, carries out contact angle test after to be dried, measuring contact angle is 58 °, this shows to aoxidize
Glass surface hydrophobicity substantially reduces after stimulation.Fig. 5 is that ultraviolet lighting aoxidizes the glass surface contact angle test after double stimuli
As a result, ultraviolet lighting oxidation double stimuli operating procedure is that first the ferrum sulfuricum oxydatum solutum that concentration is 30g/L is added dropwise on glass, it is quiet
30min is set, aqueous solution is absorbed with filter paper, uses ultraviolet light 15min after to be dried.Contact angle test is carried out again, measures contact
Angle is 43 °, this shows that the hydrophobicity of glass surface reduces one times or more.
Glass before and after stimuli responsive has different antifouling capacities, and Fig. 6 is modified glass surface under non-stimulated state
Oil pen's scribble effect, it can be seen that it has a preferable anti-graffiti ability, and oil pen is difficult to attached above, and Fig. 7 is ultraviolet
Oil pen's scribble effect on modified glass surface under illumination conditions, it can be seen that its anti-graffiti ability is slightly weaker than Fig. 6, and oil pen exists
Also more difficult attached above, Fig. 8 is oil pen's scribble effect of the glass after oxidation, it can be seen that oil pen can be continuous above
It smears, anti-graffiti ability is far smaller than non-stimulated state, and Fig. 9 is that the oil pen of the glass after ultraviolet lighting oxidation smears effect
Fruit, it can be seen that oil pen can continuously smear very well above, and anti-graffiti ability is most weak.
From the above it can be proved that the controllable glass of ultraviolet lighting of the invention oxidation double stimuli surface moist can
It aoxidizes double stimuli by ultraviolet lighting stimulation, oxidation stimulation, ultraviolet lighting and respectively obtains the different glass surface of wettability,
In surface hydrophobic under non-stimulated state it is maximum, ultraviolet lighting rear surface hydrophobicity reduces, oxidation stimulation rear surface hydrophobicity
Substantially reduce, ultraviolet lighting aoxidize double stimuli rear surface hydrophobicity reduce it is maximum, compared to non-stimulated state reduce one times with
On, the glass surface under different conditions has different dust-proof effects, and can realize different purposes.
Embodiment 2
Under nitrogen protection, 1g (2.6mmol) 3- hydroxyl, 5- ferrocene octyloxy benzene are added in the three-necked flask of 150mL
Methyl formate, 0.8g (2.6mmol) hexabromo octyloxy azobenzene, 0.54g (3.9mmol) potassium carbonate, 50mLN, N- dimethyl methyl
Amide (DMF), is warming up to 85 DEG C of reactions, determines reaction process with thin-layer chromatography chromatography in reaction process, reacts after 12 hours
It completes, stops heating, filtered after being cooled to room temperature and remove potassium carbonate, rinse sylvite to colourless with methylene chloride, vacuum rotary steam removes
Solvent is removed, orange-yellow crude product is obtained.Crude product is dissolved with butanone, refrigerator crystallisation by cooling is put into, is repeated 3 times, obtains 3- bis-
Luxuriant iron octyloxy, 5- azobenzene octyloxy methyl benzoate.
Under nitrogen protection, 10mL anhydrous tetrahydro furan is added in the three-necked flask of 150mL, by 0.3g under ice-water bath is cooling
(4.7mmol) lithium aluminium hydride reduction is added in tetrahydrofuran, by 1g (1.37mmol) 3- ferrocene octyloxy, 5- azobenzene octyloxy benzene
Methyl formate is dissolved in 20mL anhydrous tetrahydro furan, stirring, will be dissolved with 3- ferrocene by constant pressure funnel under ice-water bath is cooling
The solution of octyloxy, 5- azobenzene octyloxy methyl benzoate is slowly dropped into three-necked flask, and recession is added dropwise and removes ice-water bath,
It is reacted 7 hours under room temperature.The deionized water 0.3g quenching reaction with the weight such as lithium aluminium hydride reduction is added after completion of the reaction, the weight such as adds
1.5g/L sodium hydroxide solution, be stirred to react 30min, stop reaction, product is filtered and removes solid impurity and repeatedly uses
Tetrahydrofuran rinses until colourless.Reaction mixture is rotated and removes tetrahydrofuran, methylene chloride extraction is added, extract liquor is rotated
Methylene chloride is removed, orange-yellow crude product is obtained.Butanone dissolution is added, is put into refrigerator crystallisation by cooling three times, obtains 3- ferrocene
Octyloxy, 5- azobenzene octyloxy benzyl alcohol.
Under nitrogen protection, by 1g (1.42mmol) 3- ferrocene octyloxy, 5- azobenzene octyloxy benzyl alcohol, 0.2wt%
Catalyst dibutyltin dilaurylate, 0.35g (1.42mmol) isocyanatopropyl triethoxysilane, 50mL dry toluene add
Enter into 250mL three-necked flask, be warming up to 80 DEG C, reacts 7 hours, obtain ferrocene azobenzene silane coupling agent.
It is poured into beaker with the concentrated sulfuric acid that graduated cylinder weighs 60mL98wt%, then measures the dioxygen waterside of 20mL30%wt% and stir
It mixes side to be slowly added in the concentrated sulfuric acid, Paranha washing lotion is made, after Paranha washing lotion is cooling, available glass piece is immersed it
In, 80 DEG C of constant temperature are heated to after 1 hour, sheet glass is taken out, is rinsed with deionized water, then is rinsed with dehydrated alcohol, are dried.
By on the sheet glass that is uniformly applied to that treated of the toluene solution containing ferrocene azobenzene silane coupling agent, stand
Half an hour is put into Muffle furnace and is heat-treated, and the rate of heat addition is 5 DEG C/min, is warming up to 110 DEG C, keeps the temperature 2 hours, obtains surface
The controllable glass of wettability.
The self-assembled monolayer obtained by embodiment 2 is since hydrophobic chain is longer, and surface hydrophobic is in non-stimulated response, purple
The response of outer light stimulation, oxidation stimuli responsive, ultraviolet lighting aoxidize four kinds of stimuli responsive in the case of will than in embodiment 1 more
By force.
Embodiment 3
Under nitrogen protection, 1g (2.5mmol) 3- hydroxyl, 5- ferrocene decyloxy benzene are added in the three-necked flask of 150mL
Methyl formate, 1.54g (3.75mmol) hexabromo decyloxy azobenzene, 1.22g (3.75mmol) cesium carbonate, 50mLN, N- dimethyl
Formamide (DMF), is warming up to 85 DEG C of reactions, determines reaction process with thin-layer chromatography chromatography in reaction process, anti-after 12 hours
It should complete, stop heating, be filtered after being cooled to room temperature and remove cesium carbonate, rinse cesium salt to colourless, vacuum rotary steam with methylene chloride
Solvent is removed, orange-yellow crude product is obtained.Crude product is dissolved with butanone, refrigerator crystallisation by cooling is put into, is repeated 3 times, obtain 3-
Ferrocene decyloxy, 5- azobenzene decyloxy methyl benzoate.
Under nitrogen protection, 10mL anhydrous tetrahydro furan is added in the three-necked flask of 150mL, by 0.3g under ice-water bath is cooling
(4.7mmol) lithium aluminium hydride reduction is added in tetrahydrofuran, by 1g (1.28mmol) 3- ferrocene decyloxy, 5- azobenzene decyloxy benzene
Methyl formate is dissolved in 20mL anhydrous tetrahydro furan, stirring, will be dissolved with 3- ferrocene by constant pressure funnel under ice-water bath is cooling
Decyloxy, 5- azobenzene decyloxy methyl benzoate solution are slowly dropped into three-necked flask, recession are added dropwise and removes ice-water bath, often
Temperature lower reaction 7 hours.The deionized water 0.3g quenching reaction with the weight such as lithium aluminium hydride reduction is added after completion of the reaction, the weight such as adds
The sodium hydroxide solution of 1.5g/L is stirred to react 30min, stops reaction, and product is filtered and removes solid impurity and repeatedly with four
Hydrogen furans rinses until colourless.Reaction mixture is rotated and removes tetrahydrofuran, methylene chloride extraction is added, extract liquor is rotated
It is dry, obtain orange-yellow crude product.Butanone dissolution is added, is put into refrigerator crystallisation by cooling three times, obtains 3- ferrocene decyloxy, 5- is even
Pyridine decyloxy benzyl alcohol.
Under nitrogen protection, by 1g (1.33mmol) 3- ferrocene decyloxy, 5- azobenzene decyloxy benzyl alcohol, 0.2wt%
Catalyst dibutyltin dilaurylate, 0.33g (1.33mmol) isocyanatopropyl triethoxysilane, 50mL dry toluene add
Enter into 250mL three-necked flask, be warming up to 80 DEG C, reacts 7 hours, obtain ferrocene azobenzene silane coupling agent.
It is poured into beaker with the concentrated sulfuric acid that graduated cylinder weighs 60mL98wt%, then measures the dioxygen waterside of 20mL30%wt% and stir
It mixes side to be slowly added in the concentrated sulfuric acid, Paranha washing lotion is made, after Paranha washing lotion is cooling, available glass piece is immersed it
In, 80 DEG C of constant temperature are heated to after 1 hour, sheet glass is taken out, is rinsed with deionized water, then is rinsed with dehydrated alcohol, are dried.
By on the sheet glass that is uniformly applied to that treated of the toluene solution containing ferrocene azobenzene silane coupling agent, stand
Half an hour is put into Muffle furnace and is heat-treated, and the rate of heat addition is 5 DEG C/min, is warming up to 110 DEG C, keeps the temperature 2 hours, obtains surface
The controllable glass of wettability.
The modified glass obtained by embodiment 3 is since hydrophobic chain is longer, and surface hydrophobic is in non-stimulated response, ultraviolet light
It will be more stronger than in embodiment 2 in the case of aoxidizing four kinds of stimuli responsive according to stimuli responsive, oxidation stimuli responsive, ultraviolet lighting.
Above-described embodiment is explanation of the invention, but embodiments of the present invention are not by the limit of the embodiment
System, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of silane coupling agent with double stimuli responsive, which is characterized in that the silane coupling agent molecular structural formula are as follows:
N is the integer of 3-7.
2. the preparation method of the silane coupling agent described in claim 1 with double stimuli responsive, it is characterised in that including such as
Lower step:
1) synthesis with ultraviolet lighting oxidation double stimuli responsive alkylol: under nitrogen protection, by 3- hydroxyl, 5- ferrocene alkane
P-methoxybenzoic acid methyl esters is added to N,N-dimethylformamide solution with molar ratio with bromine alkoxy azobenzene for 1:1~1:1.5
In, carbonate catalyst is added, is warming up to 60-80 DEG C, reacts 5-10 hours；It is cooling, it filters and removes solid, vacuum rotary steam removes
N,N-dimethylformamide；Product is dissolved in recrystallization solvent, low temperature recrystallization obtains solid product 3- ferrocene alcoxyl
Base, 5- azobenzene alkoxybenzoic acid methyl esters；Solid product lithium aluminium hydride reduction is generated into 3- ferrocene alkoxy, 5- azo
Benzene alkoxybenzyl alcohol；
2) preparation with ultraviolet lighting oxidation double stimuli responsive silane coupling agent: under nitrogen protection, by 3- ferrocene alkane
Oxygroup, 5- azobenzene alkoxybenzyl alcohol and isocyanatopropyl triethoxysilane are that 1:1 is added to dry toluene with molar ratio
In solution, organotin catalysts are added, are warming up to 70-100 DEG C, reaction time 5-10 hour；It obtains with ultraviolet lighting oxidation
Double stimuli responsive silane coupling agent.
3. the preparation method of the silane coupling agent according to claim 2 with double stimuli responsive, it is characterised in that: institute
The carbonate catalyst stated is at least one of potassium carbonate, sodium carbonate and cesium carbonate.
4. the preparation method of the silane coupling agent according to claim 2 with double stimuli responsive, it is characterised in that: institute
The carbonate catalyst and 3- hydroxyl stated, the molar ratio of 5- ferrocene alkoxybenzoic acid methyl esters are 1:1~2:1.
5. the preparation method of the silane coupling agent according to claim 2 with double stimuli responsive, it is characterised in that: institute
The organotin catalysts stated are at least one of dibutyl tin dilaurate and stannous octoate.
6. the preparation method of the silane coupling agent according to claim 2 with double stimuli responsive, it is characterised in that: institute
The organotin catalysts and isocyanatopropyl triethoxysilane molar ratio stated are 1:500~1:1000.
7. the preparation method of the silane coupling agent according to claim 2 with double stimuli responsive, it is characterised in that: institute
The recrystallization solvent stated is at least one of butanone, acetone, ethyl alcohol, ether and n-hexane.
8. the preparation method of the silane coupling agent according to claim 2 with double stimuli responsive, it is characterised in that: institute
The number for the low temperature recrystallization stated is 2-6 times.
9. the silane coupling agent described in claim 1 with double stimuli responsive is in preparing the controllable glass of surface moist
Using, it is characterised in that: it will uniformly be smeared containing the toluene solution with ultraviolet lighting oxidation double stimuli responsive silane coupling agent
In glass surface, 2-4 hours are stood in air, 80-110 DEG C is warming up to, in reaction time 6-12 hour, obtains with ultraviolet light
According to the controllable glass of oxidation double stimuli response surface wettability；Stimulate the reaction, glass occur under ultraviolet lighting, oxidation for glass
The surface hydrophilicity change.
10. the silane coupling agent according to claim 9 with double stimuli responsive is preparing the controllable glass of surface moist
Application in glass, it is characterised in that: stimulate the reaction, glass surface hydrophily occur under ultraviolet lighting, oxidation for the glass
The change shows themselves in that
1) ultraviolet lighting: glass is irradiated into 15-30min under ultraviolet light, azobenzene group is gradually changed into from transconfiguration suitable
Formula structure, dipole moment are promoted from 0.5D to 3D, the raising of glass surface hydrophily；
2) it aoxidizes: the ferric sulfate aqueous solution that concentration is 30-50g/L being added drop-wise to glass surface, 1-2 hours is stood, absorbs water-soluble
Liquid, ferrocene group can be oxidized to ferrocene Weng ion, and ferrocene Weng ion has positive charge, and glass surface hydrophily is substantially
It is promoted；
3) ultraviolet lighting is jointly processed by with oxidation: the ferrum sulfuricum oxydatum solutum that concentration is 30-50g/L being added drop-wise on glass, 1-2 is stood
Hour, absorb aqueous solution, then with ultraviolet light 15-30min, azobenzene group is changed into cis-structure, Oxidation of Ferrocene at
Ferrocene Weng ion, glass surface hydrophily obtain amplitude peak promotion.
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