CN113385157A - Silicon dioxide grafted alkyl end-capped ionic liquid - Google Patents
Silicon dioxide grafted alkyl end-capped ionic liquid Download PDFInfo
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- CN113385157A CN113385157A CN202110260051.8A CN202110260051A CN113385157A CN 113385157 A CN113385157 A CN 113385157A CN 202110260051 A CN202110260051 A CN 202110260051A CN 113385157 A CN113385157 A CN 113385157A
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- chloropropyl
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 124
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 41
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 9
- 239000000741 silica gel Substances 0.000 claims abstract description 86
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 86
- 239000000945 filler Substances 0.000 claims abstract description 65
- -1 chloropropyl Chemical group 0.000 claims abstract description 52
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 7
- 238000007342 radical addition reaction Methods 0.000 claims abstract description 5
- 150000003254 radicals Chemical class 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 108
- 238000006243 chemical reaction Methods 0.000 claims description 89
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000007810 chemical reaction solvent Substances 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000007664 blowing Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 238000000967 suction filtration Methods 0.000 claims description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- 230000002194 synthesizing effect Effects 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 11
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 8
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 8
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000001308 synthesis method Methods 0.000 claims description 6
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- FZMJEGJVKFTGMU-UHFFFAOYSA-N triethoxy(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OCC)(OCC)OCC FZMJEGJVKFTGMU-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 15
- 238000012856 packing Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 230000005526 G1 to G0 transition Effects 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 229960001701 chloroform Drugs 0.000 description 3
- NTIGNJOEVBTPJJ-UHFFFAOYSA-N 3,3-dibromopentane Chemical compound CCC(Br)(Br)CC NTIGNJOEVBTPJJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DTOOTUYZFDDTBD-UHFFFAOYSA-N 3-chloropropylsilane Chemical compound [SiH3]CCCCl DTOOTUYZFDDTBD-UHFFFAOYSA-N 0.000 description 1
- TZFKFDQPHRPMKH-UHFFFAOYSA-N 4,4-dibromoheptane Chemical compound CCCC(Br)(Br)CCC TZFKFDQPHRPMKH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004186 food analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
Abstract
The invention discloses a silicon dioxide grafted alkyl end-capped ionic liquid, wherein a filler is prepared by the following method, and specifically, a dicationic ionic liquid functional monomer is synthesized firstly; modifying the surface of the silica gel with chloropropyl to obtain chloropropyl silica gel; then, the dication ionic liquid is bonded to chloropropyl silica gel through free radical addition reaction to prepare the dication ionic liquid functionalized silica gel filler; finally, end capping is carried out on the imidazolyl dicationic ionic liquid functionalized silica gel by using halogenated alkane to obtain alkyl end capped ionic liquid bonded silica filler; the chromatographic packing prepared by the method has excellent separation performance, the chromatographic property of the packing can be adjusted by changing the chemical structure of the functional monomer or the end-capping reagent to adjust the chromatographic property of the packing, and the method has good application potential.
Description
Technical Field
The invention belongs to the field of preparation of high performance liquid chromatography packing, relates to a high performance preparation separation technology, and particularly relates to a silicon dioxide grafted alkyl end-capped ionic liquid.
Background
HPLC is not only an effective analysis and separation means, but also an important efficient preparation and separation technology, has good selectivity and high separation efficiency, and is widely applied to the fields of biology, chemical industry, medical food, environmental protection, petrochemical industry and the like. The chromatographic column is the core of the HPLC system, and the development of the chromatographic packing technology capable of generating effective separation is an effective driving force for the development of the HPLC technology.
The preparation of novel chromatography packing materials is the most central and inventive part of the chromatography field. The ionic liquid has unique physical and chemical properties, such as wide liquid range, low vapor pressure, excellent dissolving performance and the like, and is widely applied to the fields of catalysis, organic synthesis, separation analysis and the like. Has been applied to the preparation of novel high performance liquid chromatography packing by modifying silica gel and shows excellent chromatographic characteristics.
Ionic liquids have evolved from novel gas chromatography stationary phases to practical stationary phases with an ever-expanding range of applications. Ionic liquids complement traditional stationary phases because they combine thermophysical and solvating properties that are only applicable to ionic solvents. Their high thermal stability and low vapor pressure make them suitable as polar stationary phases for separations requiring high temperatures. Ionic liquids are good solvents and can be used to expand the chemical space of separation. They are the only commonly used stationary phases with significant hydrogen bonding acidity; they extend the hydrogen bonding basicity of traditional stationary phases; they are dipolar/polar as the most polar conventional stationary phases; and some ionic liquids are much less cohesive than traditional polar stationary phases.
The existing preparation method of the ionic liquid functionalized silica gel filler improves the chromatographic separation performance mainly by changing the branch chain of cations or changing anions, and the obtained filler only contains one cationic group. The dicationic ionic liquid is different from common ionic liquid, two cations are arranged in a molecular structure and are connected by a carbon chain, the difference of the molecular structure enables the dicationic ionic liquid to provide more interaction than single-cation ionic liquid, and the filler prepared by the functionalized silica gel has stronger separation capability.
The ionic liquid modified silica gel shows good characteristics as a high performance liquid chromatography filler, and has separation performance of reversed phase chromatography and ion chromatography. The ionic liquid has a polar separation effect, the end-capped halogenated alkane long carbon chain has hydrophobicity, the end-capped halogenated alkane long carbon chain and the silica gel filler are bonded, the filler can be expected to have polar separation and hydrophobicity at the same time so as to obtain better separation selectivity, and the ionic liquid can be suitable for related detection of pharmaceutical ingredients in the field of medicine, and can also be applied to the fields of environmental analysis, food analysis and the like.
Patent No. 2012102378025 discloses a dicationic ionic liquid; the same patent with the patent number of '2011103771089' also discloses a preparation method of ionic liquid functionalized silica gel filler with different anions; there are corresponding drawbacks.
Disclosure of Invention
The invention aims to provide a silicon dioxide grafted alkyl-terminated ionic liquid.
The purpose of the invention can be realized by the following technical scheme:
the silicon dioxide grafted alkyl end capping ionic liquid is prepared by the following method, and specifically comprises the following steps:
firstly, synthesizing a dicationic ionic liquid functional monomer;
modifying the surface of the silica gel with chloropropyl to obtain chloropropyl silica gel;
then, the dication ionic liquid is bonded to chloropropyl silica gel through free radical addition reaction to prepare the dication ionic liquid functionalized silica gel filler;
and finally, end capping the imidazolyl dicationic ionic liquid functionalized silica gel by using halogenated alkane to obtain the alkyl end capped ionic liquid bonded silica filler.
Further, the preparation method of the alkyl-terminated ionic liquid bonded silica filler comprises the following A, B, C, D four steps:
a: synthesizing dicationic ionic liquid;
adding any one of imidazole, vinylimidazole or dimethylimidazole into a reaction vessel, adding a first reaction solvent, slowly adding sodium hydrogen, adding a proper amount of dihaloalkane after stabilization, and mechanically stirring; the whole system is subjected to argon protection and reacts for a sixth designated time at a preset temperature;
after the reaction is finished, removing the reaction solvent by reduced pressure distillation, and purifying the product by recrystallization to obtain the dicationic imidazolyl ionic liquid;
b: synthesizing chloropropyl silica gel;
c: synthesizing a dicationic ionic liquid functional silica gel filler;
d: synthesizing an alkyl-terminated ionic liquid bonded silica filler;
adding chloropropyl silica gel into a reaction container, taking anhydrous toluene as a reaction solvent, slowly adding a proper amount of mixed liquid of octadecyl triethoxy silane and the anhydrous toluene by means of a constant-pressure funnel, blowing nitrogen below the liquid surface into a protection reaction system, reacting for a fourth specified time at a second preset temperature, cooling after the reaction is finished, performing suction filtration, washing with acetone and methanol, and performing vacuum drying for a fifth specified time at a third preset temperature to obtain the alkyl-terminated ionic liquid bonded silica filler.
Further, the first reaction solvent in step a is THF or toluene.
Further, the synthesis method of the chloropropyl silica gel in the step B comprises the following steps:
adding silica gel into a reaction container, taking anhydrous toluene as a reaction solvent, carrying out ultrasonic treatment on the mixed solution, and mechanically stirring uniformly;
and adding 3-chloropropyltriethoxysilane, refluxing at a second preset temperature for a third preset time, cooling after the reaction is finished, centrifuging, washing with acetone and methanol in sequence, and drying in vacuum to obtain chloropropyl silica gel.
Further, the synthesis method of the dicationic ionic liquid functionalized silica gel filler in the step C specifically comprises the following steps:
adding chloropropyl silica gel into a reaction container, taking dried toluene as a reaction solvent, adding a proper amount of dication type imidazolyl ionic liquid, mechanically stirring uniformly, blowing nitrogen below the liquid surface into a protective reaction system, carrying out reflux reaction at a third preset temperature for a first preset time, cooling after the reaction is finished, carrying out suction filtration, washing, and carrying out vacuum drying at a specified temperature for a second preset time to obtain the 3-chloropropyl trimethoxy silane bonded dication type imidazolyl ionic liquid filler.
The invention has the beneficial effects that:
the invention discloses a preparation method of an alkyl-terminated ionic liquid bonded silica filler, and particularly relates to a method for preparing a liquid chromatography filler by chemically modifying silica gel by using dicationic ionic liquid as a functional monomer. The preparation method comprises the steps of firstly utilizing dimethyl imidazole or imidazole and dihaloalkane to react to prepare dication ionic liquid serving as a functional monomer, modifying silica gel with chloropropyl silane reagent to obtain chloropropyl silica gel, then bonding the ionic liquid to the chloropropyl silica gel through free radical addition reaction to obtain dication ionic liquid functionalized silica gel chromatographic filler, and finally carrying out end capping on the imidazolyl dication ionic liquid functionalized silica gel by using halogenated alkane to obtain alkyl end capped ionic liquid bonded silica filler. The chromatographic packing prepared by the method has excellent separation performance, the chromatographic property of the packing can be adjusted by changing the chemical structure of the functional monomer or the end-capping reagent to adjust the chromatographic property of the packing, and the method has good application potential.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 is a synthetic chemical structural formula of chloropropyl silica gel and dicationic ionic liquid functionalized silica gel filler of the invention;
FIG. 2 is a synthetic chemical structural formula of an alkyl-capped ionic liquid bonded silica filler of the present invention;
fig. 3 is a table listing alternative anionic species for dicationic ionic liquids.
Detailed Description
As shown in the figures 1-3 of the drawings,
the first embodiment is as follows: preparation of alkyl-terminated ionic liquid bonded silica fillers
Comprising the following A, B, C, D steps in sequence: (the preparation reaction process is shown in the attached figure)
A. Synthesis of dicationic ionic liquids
Adding 50mmol of imidazole into a reaction vessel, taking 40mL of trichloromethane as a reaction solvent, slowly adding 80mmol of sodium hydrogen, adding 24mmol of dibromopentane after 8h of stabilization, mechanically stirring, reacting at 85 ℃ under the protection of argon in the whole system for 72h, removing trichloromethane under reduced pressure after the reaction is finished, and purifying the product through recrystallization to obtain the dicationic imidazolyl ionic liquid.
B. Synthesis of chloropropyl silica gel
Adding 10.0g of silica gel into a reaction vessel, carrying out ultrasonic treatment on the mixed solution for 15min by using 50mL of anhydrous toluene as a reaction solvent, uniformly stirring the mixed solution mechanically, adding 5mL of 3-chloropropyltriethoxysilane, refluxing the mixed solution at 80 ℃ for 12h, cooling the mixed solution after the reaction is finished, centrifuging the mixed solution, washing the mixed solution, and carrying out vacuum drying at 90 ℃ to obtain chloropropyl silica gel.
C. Synthesis of dication type ionic liquid functional silica gel filler
Adding 10.0g of chloropropyl silica gel into a reaction container, taking dry toluene as a reaction solvent, adding 6.0g of dication type imidazolyl ionic liquid, mechanically stirring uniformly, blowing nitrogen below the liquid surface into a protective reaction system, carrying out reflux reaction at 85 ℃ for 48h, cooling after the reaction is finished, carrying out suction filtration, washing with acetone and methanol, and carrying out vacuum drying at 90 ℃ for 24h to obtain the 3-chloropropyl trimethoxy silane bonded dication type imidazolyl ionic liquid filler.
D. Synthesis of alkyl-terminated ionic liquid bonded silica filler
Adding 6g of chloropropyl silica gel into a reaction container, taking 50mL of anhydrous toluene as a reaction solvent, slowly adding a mixed solution of 7.5mL of octadecyl trichlorosilane and 10mL of anhydrous toluene into a constant-pressure funnel, blowing nitrogen below the liquid surface into a protected reaction system, reacting for 36h at 85 ℃, cooling after the reaction is finished, performing suction filtration, washing with toluene, methanol and dichloromethane, and performing vacuum drying for 24h at 90 ℃ to obtain the alkyl-terminated ionic liquid bonded silica filler.
Example two: preparation of alkyl-terminated ionic liquid bonded silica fillers
Comprising the following A, B, C, D steps in sequence:
A. synthesis of dicationic ionic liquids
Adding 92mmol of dimethyl imidazole into a reaction vessel, taking 100mL of acetonitrile as a reaction solvent, slowly adding 40mmol of dibromopentane, mechanically stirring, reacting for 48 hours at 105 ℃ under the protection of argon in the whole system, removing the acetonitrile by reduced pressure distillation after the reaction is finished, and purifying the product by recrystallization to obtain the dicationic imidazolyl ionic liquid.
B. Synthesis of chloropropyl silica gel
Adding 5.0g of silica gel into a reaction vessel, using 100mL of THF as a reaction solvent, carrying out ultrasonic treatment on the mixed solution for 15min, mechanically stirring uniformly, adding 5mL of 3-chloropropyltriethoxysilane, refluxing at 85 ℃ for 12h, cooling after the reaction is finished, centrifuging, washing, and carrying out vacuum drying at 90 ℃ to obtain chloropropyl silica gel.
C. Synthesis of dication type ionic liquid functional silica gel filler
Adding 3.0g of chloropropyl silica gel into a reaction vessel, taking dry toluene as a reaction solvent, adding 1.5g of dicationic imidazolyl ionic liquid, mechanically stirring uniformly, blowing nitrogen into a protective reaction system below the liquid surface, carrying out reflux reaction at 85 ℃ for 12h, cooling after the reaction is finished, carrying out suction filtration, washing with toluene, methanol and dichloromethane, and carrying out vacuum drying at 90 ℃ for 24h to obtain the 3-chloropropyl trimethoxy silane bonded dicationic imidazolyl ionic liquid filler.
D. Synthesis of alkyl-terminated ionic liquid bonded silica filler
Adding 3g of chloropropyl silica gel into a reaction container, taking 30mL of anhydrous toluene as a reaction solvent, slowly adding a mixed solution of 3mL of octadecyl trichlorosilane and 10mL of anhydrous toluene into a constant-pressure funnel, blowing nitrogen below the liquid surface into a protective reaction system, reacting for 36h at 85 ℃, cooling after the reaction is finished, performing suction filtration, washing with acetone and methanol, and performing vacuum drying for 24h at 90 ℃ to obtain the alkyl-terminated ionic liquid bonded silica filler.
Example three: preparation of alkyl-terminated ionic liquid bonded silica fillers
Comprising the following A, B, C, D steps in sequence:
A. synthesis of dicationic ionic liquids
Adding 50mmol of dimethyl imidazole into a reaction vessel, taking 100ml of THF as a reaction solvent, slowly adding 24mmol of dibromoheptane, mechanically stirring, reacting for 12 hours at 105 ℃ under the protection of argon in the whole system, removing THF through reduced pressure distillation after the reaction is finished, and purifying the product through recrystallization to obtain the dicationic imidazolyl ionic liquid.
B. Synthesis of chloropropyl silica gel
Adding 10.0g of silica gel into a reaction vessel, carrying out ultrasonic treatment on the mixed solution for 15min by using 50mL of anhydrous toluene as a reaction solvent, uniformly stirring the mixed solution mechanically, adding 5mL of 3-chloropropyltriethoxysilane, refluxing the mixed solution at 80 ℃ for 12h, cooling the mixed solution after the reaction is finished, centrifuging the mixed solution, washing the mixed solution, and carrying out vacuum drying at 90 ℃ to obtain chloropropyl silica gel.
C. Synthesis of dication type ionic liquid functional silica gel filler
Adding 4.0g of chloropropyl silica gel into a reaction vessel, taking dry toluene as a reaction solvent, adding 2.0g of dication type imidazolyl ionic liquid, mechanically stirring uniformly, blowing nitrogen below the liquid surface into a protective reaction system, carrying out reflux reaction at 85 ℃ for 12h, cooling after the reaction is finished, carrying out suction filtration, washing with toluene, dichloromethane and absolute ethyl alcohol, and carrying out vacuum drying at 90 ℃ for 24h to obtain the 3-chloropropyl trimethoxy silane bonded dication type imidazolyl ionic liquid filler.
D. Synthesis of alkyl-terminated ionic liquid bonded silica filler
Adding 3g of chloropropyl silica gel into a reaction container, taking 30mL of anhydrous toluene as a reaction solvent, slowly adding a mixed solution of 2mL of octadecyl trichlorosilane and 20mL of anhydrous toluene into a constant-pressure funnel, blowing nitrogen below the liquid surface into a protective reaction system, reacting for 12h at 85 ℃, cooling after the reaction is finished, performing suction filtration, washing with acetone and methanol, and performing vacuum drying for 24h at 90 ℃ to obtain the alkyl-terminated ionic liquid bonded silica filler.
Example four: preparation of alkyl-terminated ionic liquid bonded silica fillers
Comprising the following A, B, C, D steps in sequence:
A. synthesis of dicationic ionic liquids
Adding 38mmol of dimethyl imidazole into a reaction vessel, taking 60mL of acetonitrile as a reaction solvent, slowly adding 15mmol of p-dichlorobenzyl, mechanically stirring, reacting for 48 hours at 105 ℃ under the protection of argon in the whole system, removing the acetonitrile by reduced pressure distillation after the reaction is finished, and purifying the product by recrystallization to obtain the dicationic imidazolyl ionic liquid.
B. Synthesis of chloropropyl silica gel
Adding 10.0g of silica gel into a reaction vessel, carrying out ultrasonic treatment on the mixed solution for 15min by using 50mL of anhydrous toluene as a reaction solvent, uniformly stirring the mixed solution mechanically, adding 5mL of 3-chloropropyltriethoxysilane, refluxing the mixed solution at 80 ℃ for 12h, cooling the mixed solution after the reaction is finished, centrifuging the mixed solution, washing the mixed solution, and carrying out vacuum drying at 90 ℃ to obtain chloropropyl silica gel.
C. Synthesis of dication type ionic liquid functional silica gel filler
Adding 8.0g of chloropropyl silica gel into a reaction container, adding 2.0g of dication type imidazolyl ionic liquid by taking dry toluene as a reaction solvent, uniformly stirring by a machine, blowing nitrogen below the liquid surface into a protection reaction system, carrying out reflux reaction at 85 ℃ for 12h, cooling after the reaction is finished, carrying out suction filtration, washing by dichloromethane and methanol, and carrying out vacuum drying at 90 ℃ for 24h to obtain the 3-chloropropyl trimethoxy silane bonded dication type imidazolyl ionic liquid filler.
D. Synthesis of alkyl-terminated ionic liquid bonded silica filler
Adding 3g of chloropropyl silica gel into a reaction container, taking 30mL of anhydrous toluene as a reaction solvent, slowly adding a mixed solution of 3mL of octadecyl trichlorosilane and 20mL of anhydrous toluene into a constant-pressure funnel, blowing nitrogen below the liquid surface into a protective reaction system, reacting for 36h at 85 ℃, cooling after the reaction is finished, performing suction filtration, washing with acetone and methanol, and performing vacuum drying for 24h at 90 ℃ to obtain the alkyl-terminated ionic liquid bonded silica filler.
Example five: preparation of alkyl-terminated ionic liquid bonded silica fillers
Comprising the following A, B, C, D steps in sequence:
A. synthesis of dicationic ionic liquids
Adding 36mmol of dimethyl imidazole into a reaction vessel, taking 100mL of acetonitrile as a reaction solvent, slowly adding 7mmol of p-dichlorobenzyl, mechanically stirring, reacting for 12 hours at 115 ℃ under the protection of argon in the whole system, removing the acetonitrile by reduced pressure distillation after the reaction is finished, and purifying the product by recrystallization to obtain the dicationic imidazolyl ionic liquid.
B. Synthesis of chloropropyl silica gel
Adding 10.0g of silica gel into a reaction vessel, using 100mL of trichloromethane as a reaction solvent, carrying out ultrasonic treatment on the mixed solution for 5min, mechanically stirring uniformly, adding 4mL of 3-chloropropyltriethoxysilane, refluxing at 85 ℃ for 12h, cooling after the reaction is finished, centrifuging, washing, and carrying out vacuum drying at 90 ℃ to obtain chloropropyl silica gel.
C. Synthesis of dication type ionic liquid functional silica gel filler
Adding 7.0g of chloropropyl silica gel into a reaction container, taking dry toluene as a reaction solvent, adding 5.0g of dication type imidazolyl ionic liquid, mechanically stirring uniformly, blowing nitrogen below the liquid surface into a protective reaction system, carrying out reflux reaction at 85 ℃ for 12h, cooling after the reaction is finished, carrying out suction filtration, washing with acetone and methanol, and carrying out vacuum drying at 90 ℃ for 24h to obtain the 3-chloropropyl trimethoxy silane bonded dication type imidazolyl ionic liquid filler.
D. Synthesis of alkyl-terminated ionic liquid bonded silica filler
Adding 10g of chloropropyl silica gel into a reaction container, taking 10mL of anhydrous toluene as a reaction solvent, slowly adding a mixed solution of 10mL of trimethylchlorosilane and 10mL of anhydrous toluene into a constant-pressure funnel, blowing nitrogen below the liquid surface into a protective reaction system, reacting for 36h at 85 ℃, cooling after the reaction is finished, performing suction filtration, washing with acetone and methanol, and performing vacuum drying for 24h at 90 ℃ to obtain the alkyl-terminated ionic liquid bonded silica filler.
Example six: the silicon dioxide grafted alkyl end-capped ionic liquid is prepared by the following method:
firstly, synthesizing a dicationic ionic liquid functional monomer;
modifying the surface of the silica gel with chloropropyl to obtain chloropropyl silica gel;
then, the dication ionic liquid is bonded to chloropropyl silica gel through free radical addition reaction to prepare the dication ionic liquid functionalized silica gel filler;
and finally, end capping the imidazolyl dicationic ionic liquid functionalized silica gel by using halogenated alkane to obtain the alkyl end capped ionic liquid bonded silica filler.
The preparation method of the alkyl-terminated ionic liquid bonded silica filler comprises the following A, B, C, D four steps:
a: synthesizing dicationic ionic liquid;
adding any one of imidazole, vinylimidazole or dimethylimidazole into a reaction vessel, adding a first reaction solvent, slowly adding sodium hydrogen, adding a proper amount of dihaloalkane after stabilization, and mechanically stirring; the whole system is subjected to argon protection and reacts for a sixth designated time at a preset temperature;
after the reaction is finished, removing the reaction solvent by reduced pressure distillation, and purifying the product by recrystallization to obtain the dicationic imidazolyl ionic liquid;
b: synthesizing chloropropyl silica gel;
c: synthesizing a dicationic ionic liquid functional silica gel filler;
d: synthesizing an alkyl-terminated ionic liquid bonded silica filler;
adding chloropropyl silica gel into a reaction container, taking anhydrous toluene as a reaction solvent, slowly adding a proper amount of mixed liquid of octadecyl triethoxy silane and the anhydrous toluene by means of a constant-pressure funnel, blowing nitrogen below the liquid surface into a protection reaction system, reacting for a fourth specified time at a second preset temperature, cooling after the reaction is finished, performing suction filtration, washing with acetone and methanol, and performing vacuum drying for a fifth specified time at a third preset temperature to obtain the alkyl-terminated ionic liquid bonded silica filler.
The first reaction solvent in step a is THF or toluene.
The synthesis method of the chloropropyl silica gel in the step B comprises the following steps:
adding silica gel into a reaction container, taking anhydrous toluene as a reaction solvent, carrying out ultrasonic treatment on the mixed solution, and mechanically stirring uniformly;
and adding 3-chloropropyltriethoxysilane, refluxing at a second preset temperature for a third preset time, cooling after the reaction is finished, centrifuging, washing with acetone and methanol in sequence, and drying in vacuum to obtain chloropropyl silica gel.
The synthesis method of the dicationic ionic liquid functionalized silica gel filler in the step C comprises the following specific steps:
adding chloropropyl silica gel into a reaction container, taking dried toluene as a reaction solvent, adding a proper amount of dication type imidazolyl ionic liquid, mechanically stirring uniformly, blowing nitrogen below the liquid surface into a protective reaction system, carrying out reflux reaction at a third preset temperature for a first preset time, cooling after the reaction is finished, carrying out suction filtration, washing, and carrying out vacuum drying at a specified temperature for a second preset time to obtain the 3-chloropropyl trimethoxy silane bonded dication type imidazolyl ionic liquid filler.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the following claims.
Claims (5)
1. The silicon dioxide grafted alkyl end-capped ionic liquid is characterized by being prepared by the following method:
firstly, synthesizing a dicationic ionic liquid functional monomer;
modifying the surface of the silica gel with chloropropyl to obtain chloropropyl silica gel;
then, the dication ionic liquid is bonded to chloropropyl silica gel through free radical addition reaction to prepare the dication ionic liquid functionalized silica gel filler;
and finally, end capping the imidazolyl dicationic ionic liquid functionalized silica gel by using halogenated alkane to obtain the alkyl end capped ionic liquid bonded silica filler.
2. The silica-grafted alkyl terminated ionic liquid according to claim 1, wherein the preparation method of the alkyl terminated ionic liquid bonded silica filler comprises the following A, B, C, D four steps:
a: synthesizing dicationic ionic liquid;
adding any one of imidazole, vinylimidazole or dimethylimidazole into a reaction vessel, adding a first reaction solvent, slowly adding sodium hydrogen, adding a proper amount of dihaloalkane after stabilization, and mechanically stirring; the whole system is subjected to argon protection and reacts for a sixth designated time at a preset temperature;
after the reaction is finished, removing the reaction solvent by reduced pressure distillation, and purifying the product by recrystallization to obtain the dicationic imidazolyl ionic liquid;
b: synthesizing chloropropyl silica gel;
c: synthesizing a dicationic ionic liquid functional silica gel filler;
d: synthesizing an alkyl-terminated ionic liquid bonded silica filler;
adding chloropropyl silica gel into a reaction container, taking anhydrous toluene as a reaction solvent, slowly adding a proper amount of mixed liquid of octadecyl triethoxy silane and the anhydrous toluene by means of a constant-pressure funnel, blowing nitrogen below the liquid surface into a protection reaction system, reacting for a fourth specified time at a second preset temperature, cooling after the reaction is finished, performing suction filtration, washing with acetone and methanol, and performing vacuum drying for a fifth specified time at a third preset temperature to obtain the alkyl-terminated ionic liquid bonded silica filler.
3. The silica-grafted alkyl-terminated ionic liquid of claim 2, wherein the first reaction solvent in step a is THF or toluene.
4. The silicon dioxide grafted alkyl terminated ionic liquid according to claim 2, wherein the synthesis method of chloropropyl silica gel in the step B is as follows:
adding silica gel into a reaction container, taking anhydrous toluene as a reaction solvent, carrying out ultrasonic treatment on the mixed solution, and mechanically stirring uniformly;
and adding 3-chloropropyltriethoxysilane, refluxing at a second preset temperature for a third preset time, cooling after the reaction is finished, centrifuging, washing with acetone and methanol in sequence, and drying in vacuum to obtain chloropropyl silica gel.
5. The silica-grafted alkyl-terminated ionic liquid according to claim 2, wherein the synthesis method of the dicationic ionic liquid functionalized silica filler in the step C comprises the following specific steps:
adding chloropropyl silica gel into a reaction container, taking dried toluene as a reaction solvent, adding a proper amount of dication type imidazolyl ionic liquid, mechanically stirring uniformly, blowing nitrogen below the liquid surface into a protective reaction system, carrying out reflux reaction at a third preset temperature for a first preset time, cooling after the reaction is finished, carrying out suction filtration, washing, and carrying out vacuum drying at a specified temperature for a second preset time to obtain the 3-chloropropyl trimethoxy silane bonded dication type imidazolyl ionic liquid filler.
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| CN101045201A (en) * | 2006-03-30 | 2007-10-03 | 中国科学院兰州化学物理研究所 | Method for preparing liquid phase chromatographic filling of imidazole bond linking silica gel |
| US20110220575A1 (en) * | 2008-11-19 | 2011-09-15 | Nandu Deorkar | New chromatographic media based on phenoxy alkyl and alkoxy-or phenoxy-phenyl alkyl ligands |
| CN102716727A (en) * | 2012-07-11 | 2012-10-10 | 济南大学 | Preparation method of dication type ion liquid functional silica-gel packing |
| CN109092275A (en) * | 2017-09-27 | 2018-12-28 | 江苏汉邦科技有限公司 | A kind of preparation method of the alkyl linked silica filler of novel hydrophilic |
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| CN101045201A (en) * | 2006-03-30 | 2007-10-03 | 中国科学院兰州化学物理研究所 | Method for preparing liquid phase chromatographic filling of imidazole bond linking silica gel |
| US20110220575A1 (en) * | 2008-11-19 | 2011-09-15 | Nandu Deorkar | New chromatographic media based on phenoxy alkyl and alkoxy-or phenoxy-phenyl alkyl ligands |
| CN102716727A (en) * | 2012-07-11 | 2012-10-10 | 济南大学 | Preparation method of dication type ion liquid functional silica-gel packing |
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