CN106432319A - Imidazole ionic liquid silane coupling agent based on thiol-ene click chemistry and preparation method thereof - Google Patents
Imidazole ionic liquid silane coupling agent based on thiol-ene click chemistry and preparation method thereof Download PDFInfo
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000006087 Silane Coupling Agent Substances 0.000 title abstract description 9
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 title abstract 2
- 238000001311 chemical methods and process Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000005030 aluminium foil Substances 0.000 claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 229910000077 silane Inorganic materials 0.000 claims description 70
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 69
- 239000007788 liquid Substances 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 16
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 16
- 238000007306 functionalization reaction Methods 0.000 claims description 13
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 244000028419 Styrax benzoin Species 0.000 claims description 8
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 8
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 8
- 229960002130 benzoin Drugs 0.000 claims description 8
- 235000019382 gum benzoic Nutrition 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- XLXCHZCQTCBUOX-UHFFFAOYSA-N 1-prop-2-enylimidazole Chemical class C=CCN1C=CN=C1 XLXCHZCQTCBUOX-UHFFFAOYSA-N 0.000 claims description 4
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical class C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000011344 liquid material Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- 230000003321 amplification Effects 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- -1 glyoxaline ion Chemical class 0.000 description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 230000031709 bromination Effects 0.000 description 6
- 238000005893 bromination reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZORCBYQJTKBKKD-UHFFFAOYSA-N 1-dodecyl-3-ethenyl-2h-imidazole Chemical compound CCCCCCCCCCCCN1CN(C=C)C=C1 ZORCBYQJTKBKKD-UHFFFAOYSA-N 0.000 description 2
- WLWHLUQQCLCFNE-UHFFFAOYSA-N 1-ethenyl-3-methyl-2h-imidazole Chemical compound CN1CN(C=C)C=C1 WLWHLUQQCLCFNE-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012650 click reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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)
Abstract
The invention provides an imidazole ionic liquid silane coupling agent based on thiol-ene click chemistry and a preparation method thereof. The preparation method is characterized by adding alkenyl functionalized imidazole ionic liquids with different alkyl chain length to a flask, then adding equimolar gamma-mercaptopropyltrialkoxysilane, wrapping the flask with an aluminium foil, then adding a photoinitiator, removing the aluminium foil after exhausting oxygen and carrying out irradiation with an ultraviolet lamp with power of 15-50W and wavelength of 365nm under room temperature for 12-24 hours under the condition of stirring, thus obtaining the imidazole ionic liquid silane coupling agent with different alkyl chain length. The imidazole ionic liquid silane coupling agent and the preparation method have the beneficial effects that the product provided by the invention is accessible in preparation raw materials and is low in cost, so the preparation cost is low; the click chemistry synthetic method provided by the invention has the characteristics of simplicity, high efficiency, practicability, low cost, mild reaction conditions, easiness in amplification, and the like and easily achieves industrial production; the imidazole ionic liquid silane coupling agent with yield more than or equal to 50% is obtained through reaction and is suitable for large-scale industrial production and application.
Description
Technical field
The invention belongs to functional material and its synthesis field, it is related to a kind of conjunction of glyoxaline ion liquid silane coupler
Become and in particular to a kind of glyoxaline ion liquid silane coupler based on mercaptan-alkene clicking chemistry reaction and preparation method thereof.
Background technology
Glyoxaline ion liquid silane coupler, due to having the double properties of imidazole ion liquid and silane coupler concurrently, is
The more important functionalized reagent of one class.By the hydrolysis of coupling agent, condensation, ionic liquid is covalently fixed to host material table
Face, thus giving material unique performance, is widely used in the neighborhoods such as analytical chemistry, heterogeneous catalysiss, electrochemistry, biology tool.
But the research report for such glyoxaline ion liquid silane coupler is fewer, mainly reports nitrogen-imidazoles in document
Propyl trimethoxy silicane is reacted with halogenating agent, and γ-r-chloropropyl trimethoxyl silane reacts to prepare with Methylimidazole.
Glyoxaline ion liquid silane coupler, its reaction principle is the same, but reaction needs higher temperature, and the response time is longer；
Additionally, reaction also needs to substantial amounts of solvent after terminating carries out purification process, lead to complex operation step, relatively costly.
" click " chemical concept is the quick of calendar year 2001 Nobel chemistry Prize winner Americanized scholar Sharpless proposition
Synthesize the new method of a large amount of compounds, click chemistry chemical reaction process is vividly described be simple as click,
Efficiently, practicality is so as to progressively fine in the application in the fields such as biological medicine, functional material, surface modification, nanotechnology appear
Angle, becomes the model of modern synthetic method." click " chemistry has following characteristics：(1) raw material sources are wide, applied widely；(2)
Reaction condition is gentle, has toleration to water and oxygen；(3) stereoselectivity is good；(4) yield is high, easy purification of products；
(5) react quick, simple to operate.At present, in the click-reaction of report, most study, the most widely used Cu (I) that surely belongs to urge
1,3- Dipolar Cycloaddition (abbreviation Cue-AAC) between the alkynes changed and nitrine.Mercaptan-alkene clicking chemistry be 2004 by
A kind of new click chemistry type that Hoyle system summary proposes.Alexander K. etc. [J.Am.Chem.Soc.2011,
133,11,026 11029] be prepared for the silane coupler of 15 kinds of functionalization with light-initiated mercaptan-alkene clicking reaction, and by its
It is applied to the hydrophobically modified of ferroso-ferric oxide microsphere surface, greatly change the property of microsphere surface.Xuedong Wu problem
Group [RSC Adv., 2014,4,15776-15781] adopts γ mercaptopropyitrimethoxy silane and vinyl triethoxyl silicon
Alkane reacts 24h at room temperature and obtains polymer gel, is applied to immobilized copper ion.As can be seen here, by mercaptan-alkene clicking chemistry
Realize the surface modification of functional material or the preparation of functional high molecule material, be simple and direct and efficient research meanses.
As known from the above, the special chemical property based on ionic liquid, anti-by efficient, easy mercaptan-alkene clicking
Should be synthesizing the glyoxaline ion liquid silane coupler of different alkyl chain lengths for building ionic liquid in material surface science
In application be significant.
Content of the invention
It is an object of the invention to provide a kind of glyoxaline ion liquid based on mercaptan-alkene clicking chemistry reaction is silane coupled
Agent and preparation method thereof, the method adopts the imidazole-like ionic of efficient, the easy different alkyl chain length of click chemistry method synthesis
Liquid silane coupling agent, by light-initiated mercaptan-alkene clicking reaction so that thiazolinyl functionalization imidazole ion liquid and sulfydryl third
Base silane coupling agent is connected, and reaction obtains high yield, highly purified imidazole-like ionic liquid liquid silane coupling agent, is suitable for extensive
Industrialized production is applied.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of the glyoxaline ion liquid silane coupler based on mercaptan-alkene clicking chemistry reaction, will not
Thiazolinyl functionalization imidazole ion liquid with alkyl chain length is added in flask, is subsequently adding equimolar γ-mercaptopropyi three
Flask is wrapped up by alkoxy silane with aluminium-foil paper, is subsequently adding light trigger, removes aluminium-foil paper after discharging oxygen, under agitation,
At room temperature with power be 15～50W, the ultra violet lamp 12～24h of wavelength 365nm, obtain the imidazoles of different alkyl chain lengths
Ionic liquid silane coupler；Wherein, the amount of the material of light trigger is the thiazolinyl functionalization imidazol ion of different alkyl chain lengths
The 2～3% of the amount of liquid substance.
The present invention is further improved by, if the thiazolinyl functionalization imidazole ion liquid of different alkyl chain length does not dissolve in
In γ-mercaptopropyi trialkoxy silane, then add solvent, and the thiazolinyl functionalization imidazole ion liquid of different alkyl chain length with
Ratio (1～1.25) mmol of solvent：(0.125～0.25) mL.
The present invention is further improved by, if adding solvent in course of reaction, after the completion of ultra violet lamp, true
Empty lower removing solvent, obtains the glyoxaline ion liquid silane coupler of different alkyl chain lengths.
The present invention is further improved by, and the thiazolinyl functionalization imidazole ion liquid of described difference alkyl chain length is ethylene
Any one in base glyoxaline ion liquid, allyl imidazole class ionic liquid.
The present invention is further improved by, and the structural formula of described vinyl imidazole class ionic liquid is：
In formula, n takes any one integer in 0-11；X-Represent Cl-、Br-、PF6- or BF4 -.
The present invention is further improved by, and the structural formula of described allyl imidazole class ionic liquid is：
In formula, n takes any one integer in 0-11；X-Represent Cl-、Br-、PF6- or BF4-.
The present invention is further improved by, and described γ-mercaptopropyi trialkoxy silane is γ-mercaptopropyi trimethoxy
One of base silane, γ-Mercaptopropyltriethoxysilane.
The present invention is further improved by, and described solvent is absolute methanol, chloroform, any one in acetonitrile.
The present invention is further improved by, and described light trigger is benzoin dimethylether, 2,4,6- trimethylbenzoyl
Any one in base-diphenyl phosphine oxide；The rotating speed of stirring is 200～400rpm.
A kind of glyoxaline ion liquid silane coupler based on mercaptan-alkene clicking chemistry reaction, this imidazole-like ionic liquid
The structural formula of body silane coupler is：
In formula, R representative-CH2CH3Or-CH3；M takes 0 or 1；N takes any one integer in 0-11；X-Represent Cl-、Br-、
PF6 -Or BF4 -.
Compared with prior art, the invention has the advantages that：
Light-initiated mercaptan-alkene clicking reaction is incorporated into the conjunction of glyoxaline ion liquid silane coupler by the present invention first
Cheng Zhong, by utilizing mercaptan-alkene clicking chemistry by thiazolinyl functionalization imidazole ion liquid and γ-mercaptopropyi trialkoxy silane
Method synthesizes glyoxaline ion liquid silane coupler under ultraviolet lighting, there is provided a class can achieve functionalizing material surface
Ionic liquid；The product preparing raw material that the present invention provides is easy to get, and price economy, therefore preparation cost are low；The point that the present invention provides
The features such as hit that chemical synthesis process is simple, efficient, practical and with low cost, reaction condition gentle, easily amplify, easily realizes industry
Metaplasia is produced, and efficiently avoid the use of a large amount of solvents and the reaction condition of harshness, loaded down with trivial details purification process.The present invention reacts
Reach more than 50% glyoxaline ion liquid silane coupler, suitable large-scale industrial production application to yield；Due to imidazoles
Class ionic liquid silane coupler has the double properties of ionic liquid and silane coupler concurrently, can enter with the material of surface hydroxylation
Row chemical bonding, thus give material excellent physicochemical properties.Gained ionic liquid coupling agent of the present invention is used for material list
Face is modified, has widened application in Surface Science, functional material for the ionic liquid, especially in heterogeneous catalysiss, electrochemistry, separation
The fields such as technology, biology.
Brief description
Fig. 1 is the reaction expression of the present invention.
Fig. 2 is the nuclear magnetic spectrogram of embodiment 1.
Fig. 3 is the nuclear magnetic spectrogram of embodiment 2.
Fig. 4 is the nuclear magnetic spectrogram of embodiment 3.
Fig. 5 is the nuclear magnetic spectrogram of embodiment 4.
Fig. 6 is the nuclear magnetic spectrogram of embodiment 5.
Fig. 7 is the nuclear magnetic spectrogram of embodiment 6.
Fig. 8 is the nuclear magnetic spectrogram of embodiment 7.
Specific embodiment
In order to be better understood from the present invention, further illustrated by embodiment in conjunction with accompanying drawing.
Referring to Fig. 1, the structural formula of the glyoxaline ion liquid silane coupler of the present invention is：
In formula, R representative-CH2CH3Or-CH3；M takes 0,1；N takes any one integer in 0-11；X-Represent Cl-、Br-、
PF6 -Or BF4 -.The value of n any one integer in addition to the value in following examples, in 0-11.
Below by specific embodiment, the preparation method of the present invention is described in detail.
Embodiment 1
Take 4mmol γ mercaptopropyitrimethoxy silane in the quartziferous round-bottomed flask that 10mL aluminium-foil paper wraps up, then
Add chlorination 1- vinyl -3- Methylimidazole. ionic liquid, benzoin dimethylether and the 0.5mL absolute methanol of 4mmol, its
In, the amount of benzoin dimethylether is the 2% of the amount of chlorination 1- vinyl -3- Methylimidazole. ionic liquid material；With 200rpm's
Under rotating speed stirring, after being passed through argon 5min, remove aluminium-foil paper, being placed in power at room temperature is under 15W uviol lamp (365nm), shines
Penetrate 12h, reaction finishes, then 40 DEG C of removals solvent (methanol) in vacuum drying oven, obtain yellow viscous liquid 0.73g, that is,
For target imidazole ionic liquid silane coupler, yield 53.4%.
Referring to Fig. 2, figure it is seen that institute in the prepared structure such as Fig. 1 of ionic liquid silane coupler of embodiment 1
Show structure.
Embodiment 2
Weigh 4mmol γ mercaptopropyitrimethoxy silane in the quartziferous round-bottomed flask that 10mL aluminium-foil paper wraps up, so
Add bromination 1- vinyl -3- ethyl imidazol(e) ionic liquid, the oxidation of 2,4,6- trimethylbenzoy-dipheny of 4mmol afterwards
Phosphine (TPO) and 0.5mL absolute methanol, the addition of TPO is the amount of bromination 1- vinyl -3- ethyl imidazol(e) ionic liquid material
2%；With the rotating speed stirring of 300rpm, after being passed through argon 5min, remove aluminium-foil paper, being placed in power at room temperature is 50W ultraviolet
Under lamp (365nm), irradiate 24h, then 40 DEG C of removals solvent (methanol) in vacuum drying oven, obtain yellow, viscous liquid
0.95g, as target imidazole ionic liquid silane coupler, yield 66.3%.
Referring to Fig. 3, from figure 3, it can be seen that institute in the prepared structure such as Fig. 1 of ionic liquid silane coupler of embodiment 2
Show structure.
Embodiment 3
Weigh 5mmol γ-Mercaptopropyltriethoxysilane in the quartziferous round-bottomed flask that 10mL aluminium-foil paper wraps up, so
Add 1- vinyl -3- 1-Butyl-1H-imidazole hexafluorophosphoric acid ionic liquid, benzoin dimethylether and the 0.7mL of 5mmol anhydrous afterwards
Acetonitrile, wherein, the addition of benzoin dimethylether is the amount of 1- vinyl -3- 1-Butyl-1H-imidazole hexafluorophosphoric acid ionic liquid material
2%；With the rotating speed stirring of 400rpm, after being passed through argon 5min, remove aluminium-foil paper, being placed in power at room temperature is 30W ultraviolet
Under lamp (365nm), irradiate 18h, then 40 DEG C of removal solvents in vacuum drying oven, obtain yellow, viscous liquid 1.77g, that is,
For target imidazole ionic liquid silane coupler, yield 73.5%.
Referring to Fig. 4, from fig. 4, it can be seen that institute in the prepared structure such as Fig. 1 of ionic liquid silane coupler of embodiment 3
Show structure.
Embodiment 4
Weigh 4mmol γ mercaptopropyitrimethoxy silane in the quartziferous round-bottomed flask that 10mL aluminium-foil paper wraps up, so
Add bromination 1- vinyl -3- dodecyl imidazole ionic liquid, TPO the and 1mL anhydrous chloroform of 4mmol, wherein, TPO afterwards
Addition be bromination 1- vinyl -3- dodecyl imidazole ionic liquid material amount 3%；Stirred with the rotating speed of 200rpm
Mix, after being passed through argon 5min, remove aluminium-foil paper, being placed in power at room temperature is under 45W uviol lamp (365nm), irradiates 24h, instead
Should finish, in vacuum drying oven, 40 DEG C of removal solvents, obtain yellow waxy product 1.29g, as target imidazole ionic liquid
Silane coupler, yield 79.2%.
Referring to Fig. 5, from fig. 5, it can be seen that institute in the prepared structure such as Fig. 1 of ionic liquid silane coupler of embodiment 4
Show structure.
Embodiment 5
Weigh 5mmol γ mercaptopropyitrimethoxy silane in the quartziferous round-bottomed flask that 10mL aluminium-foil paper wraps up, so
Add chlorination 1- pi-allyl -3- ethyl imidazol(e) ionic liquid, benzoin dimethylether and the 0.5mL absolute methanol of 5mmol afterwards, its
In, the addition of benzoin dimethylether is the 2% of chlorination 1- pi-allyl -3- ethyl imidazol(e) ionic liquid；Rotating speed with 300rpm
Stirring, after being passed through argon 5min, removes aluminium-foil paper, and being placed in power at room temperature is under 15W uviol lamp (365nm), irradiates 18h,
Reaction finishes, and in vacuum drying oven, 40 DEG C of removal solvents, obtain yellow, viscous liquid 1.49g, as target imidazole ion
Liquid silane coupling agent.
Referring to Fig. 6, from fig. 6, it can be seen that institute in the prepared structure such as Fig. 1 of ionic liquid silane coupler of embodiment 5
Show structure.
Embodiment 6
Take 5mmol γ mercaptopropyitrimethoxy silane in the quartziferous round-bottomed flask that 10mL aluminium-foil paper wraps up, then
Add 1- pi-allyl -3- 1-Butyl-1H-imidazole tetrafluoroborate ion liquid, TPO the and 0.7mL anhydrous acetonitrile of 5mmol, wherein,
The addition of TPO is the 3% of the amount of 1- pi-allyl -3- 1-Butyl-1H-imidazole tetrafluoroborate ion liquid material；Turning with 400rpm
Speed stirring, after being passed through argon 5min, removes aluminium-foil paper, and being placed in power at room temperature is under 50W uviol lamp (365nm), irradiates
24h, reaction finishes, and in vacuum drying oven, 40 DEG C of removal solvents, obtain yellow, viscous liquid 1.97g, as target imidazole
Ionic liquid silane coupler, yield 81.2%.
Referring to Fig. 7, from figure 7 it can be seen that institute in the prepared structure such as Fig. 1 of ionic liquid silane coupler of embodiment 6
Show structure.
Embodiment 7
Take 4mmol γ-Mercaptopropyltriethoxysilane in the quartziferous round-bottomed flask that 10mL aluminium-foil paper wraps up, then
Add bromination 1- pi-allyl -3- dodecyl imidazole ionic liquid, the 2,4,6- trimethylbenzoy-dipheny oxygen of 4mmol
Change phosphine (TPO) and 1mL anhydrous chloroform, wherein, the addition of TPO is bromination 1- pi-allyl -3- dodecyl imidazole ionic liquid
The 3% of the amount of body material；With the rotating speed stirring of 300rpm, after being passed through argon 5min, remove aluminium-foil paper, be placed in power at room temperature
For, under 15W uviol lamp (365nm), irradiating 12h, then 40 DEG C of removal solvents in vacuum drying oven, obtain yellow waxy product
1.41g, as target imidazole ionic liquid silane coupler, yield 59.4%.
Referring to Fig. 8, from figure 8, it is seen that institute in the prepared structure such as Fig. 1 of ionic liquid silane coupler of embodiment 7
Show structure.
Because glyoxaline ion liquid silane coupler has the double properties of imidazole ion liquid and silane coupler concurrently, can
Carry out chemical bonding with the material of surface hydroxylation, thus giving material excellent physicochemical properties.The present invention be based on mercaptan-
Alkene clicking chemistry has been synthesized the glyoxaline ion liquid silane coupler of different alkyl chain lengths, using γ-mercaptopropyi three
It is anti-that the thiazolinyl functionalization imidazole ion liquid of alkoxy silane alkyl chain length different from equimolar passes through mercaptan-alkene clicking chemistry
Should, synthesize glyoxaline ion liquid silane coupler under the conditions of ultraviolet light.Efficient, reliability, height using click chemistry
The features such as selectivity, speed are fast, yield is high, product can be easily separated, carries for synthesizing such glyoxaline ion liquid silane coupler
Supplied one kind simply and effectively synthetic route, and yield and purity higher.Light-initiated sulfydryl-alkene click-reaction can for this ultraviolet
To carry out under mild conditions, efficiently avoid the use of a large amount of solvents, harsh reaction condition, loaded down with trivial details purification side
Method, is that the glyoxaline ion liquid silane coupler of complex functionality provides one kind efficiently and effectively method.Gained ionic liquid
Body silane coupler is used for material surface modifying, can widen application in Surface Science for the ionic liquid, is especially separating
The fields such as science, heterogeneous catalysiss, electrochemistry, bioscience.
Claims (10)
1. a kind of preparation method of the glyoxaline ion liquid silane coupler based on mercaptan-alkene clicking chemistry reaction, its feature
It is, the thiazolinyl functionalization imidazole ion liquid of different alkyl chain lengths is added in flask, is subsequently adding equimolar γ-mercapto
Flask is wrapped up by base propyl trialkoxy silane with aluminium-foil paper, is subsequently adding light trigger, removes aluminium-foil paper after discharging oxygen,
Under agitation, at room temperature with power be 15～50W, the ultra violet lamp 12～24h of wavelength 365nm, obtain different alkyl chains
Long glyoxaline ion liquid silane coupler；Wherein, the amount of the material of light trigger is the thiazolinyl function of different alkyl chain lengths
The 2～3% of the amount of change imidazole ion liquid material.
2. a kind of glyoxaline ion liquid based on mercaptan-alkene clicking chemistry reaction according to claim 1 is silane coupled
If the preparation method of agent is not it is characterised in that the thiazolinyl functionalization imidazole ion liquid of different alkyl chain length dissolves in γ-sulfydryl third
In base trialkoxy silane, then add solvent, and the different thiazolinyl functionalization imidazole ion liquid of alkyl chain length and the ratio of solvent
For (1～1.25) mmol：(0.125～0.25) mL.
3. a kind of glyoxaline ion liquid based on mercaptan-alkene clicking chemistry reaction according to claim 2 is silane coupled
If the preparation method of agent, it is characterised in that adding solvent in course of reaction, after the completion of ultra violet lamp, is removed under vacuo
Remove solvent, obtain the glyoxaline ion liquid silane coupler of different alkyl chain lengths.
4. a kind of glyoxaline ion liquid based on mercaptan-alkene clicking chemistry reaction according to claim 1 is silane coupled
The preparation method of agent is it is characterised in that the thiazolinyl functionalization imidazole ion liquid of described difference alkyl chain length is vinyl imidazole
Any one in class ionic liquid, allyl imidazole class ionic liquid.
5. a kind of glyoxaline ion liquid based on mercaptan-alkene clicking chemistry reaction according to claim 4 is silane coupled
The preparation method of agent is it is characterised in that the structural formula of described vinyl imidazole class ionic liquid is：
In formula, n takes any one integer in 0-11；X-Represent Cl-、Br-、PF6 -Or BF4 -.
6. a kind of glyoxaline ion liquid based on mercaptan-alkene clicking chemistry reaction according to claim 4 is silane coupled
The preparation method of agent is it is characterised in that the structural formula of described allyl imidazole class ionic liquid is：
In formula, n takes any one integer in 0-11；X-Represent Cl-、Br-、PF6 -Or BF4 -.
7. a kind of glyoxaline ion liquid based on mercaptan-alkene clicking chemistry reaction according to claim 1 is silane coupled
The preparation method of agent it is characterised in that described γ-mercaptopropyi trialkoxy silane be γ mercaptopropyitrimethoxy silane,
One of γ-Mercaptopropyltriethoxysilane.
8. a kind of glyoxaline ion liquid based on mercaptan-alkene clicking chemistry reaction according to claim 1 is silane coupled
The preparation method of agent it is characterised in that described solvent be absolute methanol, any one in chloroform, acetonitrile.
9. a kind of glyoxaline ion liquid based on mercaptan-alkene clicking chemistry reaction according to claim 1 is silane coupled
The preparation method of agent it is characterised in that described light trigger be benzoin dimethylether, 2,4,6- trimethylbenzoyls-hexichol
Any one in base phosphine oxide；The rotating speed of stirring is 200～400rpm.
10. a kind of glyoxaline ion liquid based on mercaptan-alkene clicking chemistry reaction of the preparation of method according to claim 1
Silane coupler is it is characterised in that the structural formula of this glyoxaline ion liquid silane coupler is：
In formula, R representative-CH2CH3Or-CH3；M takes 0 or 1；N takes any one integer in 0-11；X-Represent Cl-、Br-、PF6 -Or
BF4 -.
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| CN113336787A (en) * | 2021-06-21 | 2021-09-03 | 湖北固润科技股份有限公司 | Thioether-oxygen heterocyclic butane silane coupling agent and preparation method thereof |
| CN115010747A (en) * | 2022-05-24 | 2022-09-06 | 沈阳化工大学 | Preparation method of aminoimidazole tetrafluoroborate ionic liquid |
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