CN109174181B - Preparation and application of mesoporous polymer loaded with bifunctional ionic liquid - Google Patents
Preparation and application of mesoporous polymer loaded with bifunctional ionic liquid Download PDFInfo
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- CN109174181B CN109174181B CN201810907784.4A CN201810907784A CN109174181B CN 109174181 B CN109174181 B CN 109174181B CN 201810907784 A CN201810907784 A CN 201810907784A CN 109174181 B CN109174181 B CN 109174181B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 28
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 115
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 amine compounds Chemical class 0.000 claims abstract description 12
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 10
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims abstract description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000007210 heterogeneous catalysis Methods 0.000 claims abstract description 8
- 239000001632 sodium acetate Substances 0.000 claims abstract description 8
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000543 intermediate Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 125000006497 3-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C(OC([H])([H])[H])=C1[H])C([H])([H])* 0.000 claims description 7
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000010520 demethylation reaction Methods 0.000 claims description 3
- 239000008098 formaldehyde solution Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- OWYXVLZOHHQSAF-UHFFFAOYSA-N 4-[(chloroamino)methyl]aniline Chemical compound NC1=CC=C(CNCl)C=C1 OWYXVLZOHHQSAF-UHFFFAOYSA-N 0.000 claims 1
- FGHDDLYDTJEWEQ-UHFFFAOYSA-N 4-[(fluoroamino)methyl]aniline Chemical compound NC1=CC=C(CNF)C=C1 FGHDDLYDTJEWEQ-UHFFFAOYSA-N 0.000 claims 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 239000013335 mesoporous material Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 238000006170 formylation reaction Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000022244 formylation Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- IDWXQRMUCRXFAK-UHFFFAOYSA-N (2-phenyldiazenylhydrazinyl)benzene Chemical compound C=1C=CC=CC=1N=NNNC1=CC=CC=C1 IDWXQRMUCRXFAK-UHFFFAOYSA-N 0.000 description 1
- HEONFBNOPUNGFB-UHFFFAOYSA-N CON=NCC(C=C1)=CC=C1N Chemical compound CON=NCC(C=C1)=CC=C1N HEONFBNOPUNGFB-UHFFFAOYSA-N 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000010792 warming Methods 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
Abstract
The invention discloses a preparation method and application of a loaded bifunctional ionic liquid mesoporous polymer, which is characterized in that an imidazole functionalized ordered mesoporous polymer is taken as a carrier, 1, 2-dibromoethane and triethylamine are connected in a covalent bond mode, sodium acetate and bifunctional ionic liquid are used for carrying out ion exchange to prepare the loaded bifunctional ionic liquid mesoporous polymer which is taken as a catalyst in CO2Heterogeneous catalysis with amine compounds to synthesize formamide. Compared with the prior art, the mesoporous material has the characteristics of high specific surface area, uniform pore channel, good thermal stability and chemical stability and the like, and can catalyze CO under mild conditions2The catalyst has high catalytic activity when reacting with an amino compound, is easy to separate, recover and separate, can be recycled, is a novel environment-friendly catalyst, and has great development potential in the field of heterogeneous catalysis.
Description
Technical Field
The invention relates to the technical field of porous organic polymer catalysts, in particular to a catalyst capable of being recycled for catalyzing CO2Preparation and application of a load bifunctional ionic liquid mesoporous polymer for formamide reaction.
Background
Carbon dioxide causes global warming and is also a cheap, abundant C1Resources, therefore excessive CO2The product is converted into valuable chemical products and has good industrial development prospect. Formamide is an important medical intermediate, and can be used as a medicine,usually by formylation of amines with carbon monoxide using CO2The formylation of N-H bonds instead of toxic carbon monoxide is a green and safe synthetic route.
At present, the reaction of carbon dioxide and amine compounds has been widely reported in various catalytic systems, and great progress has been made. However, the problems with these reported synthetic routes are: a metal catalyst, an inert gas atmosphere, a complicated reaction system, high temperature and pressure, difficulty in catalyst separation, and the like are required. Therefore, it is still highly desirable to explore simple, recyclable, green catalytic systems. The ionic liquid functionalized ordered mesoporous polymer material is a kind of ordered mesoporous polymer material which well combines the advantages of the mesoporous material such as high specific surface area, high thermal stability, uniform aperture, multifunctional catalysis of the ionic liquid and the like. Therefore, the prepared ionic liquid supported ordered mesoporous material can effectively catalyze organic synthesis reaction, and is easy to recycle and conforms to the green chemical concept.
The synthesis process of the porous organic polymer in the prior art is complex, the cost of raw materials is high, and the porous organic polymer is difficult to be widely applied, so that the porous organic polymer with simple preparation, high catalytic activity and good cycling stability is developed for CO2Chemical conversion research is of great significance.
Disclosure of Invention
The invention aims at the defects of the prior art to provide a preparation method and application of a mesoporous polymer loaded with bifunctional ionic liquid, the mesoporous polymer is prepared by using imidazole functionalized ordered mesoporous polymer as a carrier, sequentially connecting 1, 2-dibromoethane and triethylamine in a covalent bond form, and carrying out ion exchange on sodium acetate and a bifunctional ionic liquid material, and the mesoporous polymer is used as a catalyst in carbon dioxide formylation reaction, has excellent reaction activity and recycling capability, can obtain very high yield under mild reaction conditions, has simple synthesis operation and good repeatability, can change the specific surface area, pore volume and the like by regulating the molar ratio of monomers, has good product selectivity, strong substrate universality, mild reaction conditions, and easy separation and recovery of the catalyst, is a recyclable high-efficiency catalyst and has great development potential in the field of heterogeneous catalysis.
The specific technical scheme for realizing the purpose of the invention is as follows: a preparation method of a mesoporous polymer loaded with dual-functionalized ionic liquid is characterized in that imidazole functionalized ordered mesoporous polymer is used as a carrier, 1, 2-dibromoethane and triethylamine are connected in a covalent bond mode, and sodium acetate and the dual-functionalized ionic liquid are used for ion exchange to obtain the mesoporous polymer loaded with the dual-functionalized ionic liquid, and the preparation method specifically comprises the following steps:
preparation of imidazole functionalized ordered mesoporous polymer
a. Preparation of 1- (3-methoxybenzyl) -1-hydro-imidazole intermediates
Mixing tetrahydrofuran and sodium hydride according to the proportion of 1-6: mixing the raw materials according to a molar ratio of 1, dropwise adding the mixture into a mixed solution of imidazole and tetrahydrofuran, stirring for 40-60 min, adding 1- (chloromethyl) -3-anisole, refluxing for 24h at the temperature of 70 ℃, and carrying out a synthetic reaction according to the following reaction structural formula:
washing with deionized water and extracting with dichloromethane after the reaction is finished, washing the extract with deionized water and saturated saline water in sequence, drying and separating by column chromatography to obtain a product 1- (3-methoxybenzyl) -1-hydrogen-imidazole intermediate, wherein the mixed solution of imidazole and tetrahydrofuran is a mixture of imidazole and tetrahydrofuran according to the weight ratio of 1: mixing at a molar ratio of 8-15; the molar ratio of the 1- (chloromethyl) -3-anisole to the imidazole is 1-5: 1.
b. preparation of 3- ((1-hydro-imidazole-1-) methyl) phenol
The intermediate prepared above was reacted with hydrobromic acid in a 1: mixing the components according to the molar ratio of 6-10, refluxing for 24 hours at the temperature of 120 ℃, and performing demethylation reaction of the following reaction structural formula:
after the reaction is finished, Na is used2CO3Neutralizing hydrobromic acid, adding saturated NaHCO when pH is 73And (3) regulating the pH value of the reaction solution to 7.5, washing with water, and filtering to obtain the product 3- ((1-hydrogen-imidazole-1-) methyl) phenol.
c. Preparation of imidazole functionalized precursor
Mixing the prepared 3- ((1-hydrogen-imidazole-1-) methyl) phenol with 38 wt% of formaldehyde solution and 10 wt% of sodium hydroxide solution, stirring for 10-20 min at normal temperature, adding phenol, stirring for 1-2 h at 70-75 ℃, cooling to normal temperature after reaction, adjusting the pH value of reaction liquid to 7 by hydrochloric acid, and performing rotary evaporation to obtain an imidazole functionalized precursor, wherein the molar ratio of the 3- ((1-hydrogen-imidazole-1-) methyl) phenol to the formaldehyde to the sodium hydroxide is 1: 8-10: 14-18: 2 to 4.
d. Preparation of imidazole functionalized ordered mesoporous polymer
Mixing the imidazole functionalized precursor prepared above with polyether (F127) and ethanol according to the ratio of 1: 1: 18-25, stirring for 20-50 min, spreading the mixture on a glass plate, volatilizing at room temperature for 8-12 h, drying in an oven at 100-120 ℃ for 18-24 h, and calcining the cured film in a nitrogen tube furnace at 350 ℃ for 3h to obtain the imidazole functionalized ordered mesoporous polymer.
(II) ionization of imidazole functionalized ordered mesoporous polymer
a. Preparation of 3-IMP-MPs-Et-Br
Mixing the prepared imidazole functionalized ordered mesoporous polymer with 1, 2-dibromoethane and acetonitrile according to the weight ratio of 4-6: 1: mixing the components according to the mass ratio of 35-45, stirring and refluxing the mixture at the temperature of 70-83 ℃ for 12-24 hours, filtering the reaction solution, washing the filtrate with acetone and deionized water alternately for three times in sequence, and then drying the washed product in vacuum at the temperature of 60-80 ℃ for 12-24 hours to obtain the product of 3-IMP-MPs-Et-Br.
b. Preparation of 3-IMP-MPs-Et- (NEt4) Br
3-IMP-MPs-Et-Br prepared above was mixed with triethylamine and deionized water in a ratio of 5: 2-8: mixing the components according to the mass ratio of 35-45, stirring and refluxing the mixture at the temperature of 60-80 ℃ for 12-24 hours, filtering the reaction solution, washing the filtrate with acetone and deionized water alternately for three times in sequence, and then drying the filtrate in vacuum at the temperature of 60-80 ℃ for 12-24 hours to obtain the product 3-IMP-MPs-Et- (NEt4) Br.
c. Preparation of 3-IMP-MPs-Et- (NEt4) AcO
3-IMP-MPs-Et- (NEt4) Br prepared above was mixed with sodium acetate and deionized water at a ratio of 5: 2-8: mixing the components in a mass ratio of 35-45, stirring the mixture at normal temperature for 12-24 hours, filtering the reaction solution, washing the filtrate with deionized water, and drying the filtrate in vacuum at the temperature of 60-80 ℃ for 12-24 hours to obtain the product, namely the mesoporous polymer (3-IMP-MPs-Et- (NEt4) AcO) loaded with the bifunctional ionic liquid.
The application of the supported dual-functionalized ionic liquid mesoporous polymer is characterized in that the supported dual-functionalized ionic liquid mesoporous polymer is applied to CO as a catalyst2The reaction of the formamide synthesized by heterogeneous catalysis with an amino compound is carried out at the heterogeneous catalysis synthesis reaction temperature of 30-40 ℃ for 18-24 hours, and the molar ratio of the catalyst to the amino compound, the phenylsilane and the acetonitrile is 0.03-0.06: 1: 2-4: 35-45; the pressure of the carbon dioxide is 0.5-2 MPa; the amino compound is azoaniline, methyl azoaniline, methoxy azoaniline, p-chloro azoaniline or p-fluoro azoaniline, and the structural general formula is as follows:
wherein:
compared with the prior art, the mesoporous material has the characteristics of high specific surface area, uniform pore channel, good thermal stability and chemical stability and the like, and can catalyze CO under mild conditions2The catalyst has high catalytic activity when reacting with an amino compound, is easy to separate, recover and separate, can be recycled, is a novel environment-friendly catalyst, and has great development potential in the field of heterogeneous catalysis.
Drawings
FIG. 1 is an X-ray diffraction diagram of a supported bifunctional ionic liquid mesoporous polymer prepared in example 1;
FIG. 2 shows a mesoporous polymer N loaded with a bifunctional ionic liquid prepared in example 12Adsorption-desorption isotherms;
FIG. 3 is a transmission electron microscope image of the supported bifunctional ionic liquid mesoporous polymer prepared in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Preparation of imidazole functionalized ordered mesoporous material
a. Preparation of 1- (3-methoxybenzyl) -1-hydro-imidazole intermediates
Mixing 5mL of tetrahydrofuran with the mass concentration of 99.9% and 4.3g (0.18mol) of sodium hydride, dropwise adding the mixture into 40mL of a mixed solution of tetrahydrofuran with the mass concentration of 99.9% and 6.8g (0.1mol) of imidazole, stirring and mixing for 40min, adding 15.7g (0.1mol) of 1- (chloromethyl) -3-anisole with the mass concentration of 99.9%, and refluxing at 70 ℃ for 24h, wherein the reaction structural formula is as follows:
washing the reaction product with deionized water for three times, extracting with dichloromethane, washing the organic phase with deionized water twice and saturated brine once after extraction, drying with anhydrous sodium sulfate, spin-drying dichloromethane, and separating by column chromatography to obtain 15.3g of 1- (3-methoxybenzyl) -1-hydrogen-imidazole intermediate with a yield of 81%.
b. Preparation of 3- ((1-hydro-imidazol-1-) methyl) phenol (3-IMP)
Taking 10g of the 1- (3-methoxybenzyl) -1-hydro-imidazole intermediate prepared above, adding the intermediate into 50mL of 33% hydrobromic acid, and refluxing at 120 ℃ for 24h to perform demethylation reaction of the following reaction structural formula:
after the reaction is finished, Na is used2CO3The hydrobromic acid is neutralized and saturated NaHCO is added when the pH reaches a value as fast as 73And (3) adjusting the pH value of the reaction solution to 7.5, filtering, washing with water and filtering again to obtain 9.2g of product 3- ((1-hydrogen-imidazole-1-) methyl) phenol, wherein the yield is 100%.
c. Preparation of imidazole functionalized precursor
0.19g of the prepared 3- ((1-hydrogen-imidazole-1-) methyl) phenol, 2.9g of formaldehyde solution with the mass concentration of 38 wt% and 1.15g of sodium hydroxide solution with the mass concentration of 10 wt% are mixed, stirred for 10min at normal temperature, 1.15g of phenol with the mass concentration of 99.9% is added, then stirred for 2h at the temperature of 75 ℃, a functionalized precursor is synthesized by a one-pot method, the reaction solution is cooled to normal temperature, then the pH value is adjusted to 7 by using 2mol/L HCl solution, and water in the system is removed by rotary evaporation for 2h to obtain 2g of imidazole functionalized precursor.
d. Preparation of imidazole functionalized ordered mesoporous polymer
Dissolving 2g F127 in 50mL of ethanol solution with the mass concentration of 99%, adding 1.6g of the prepared imidazole functionalized precursor, stirring and mixing for 45min, spreading the mixture on a glass plate, volatilizing for 8h at room temperature, drying in an oven at 120 ℃ for 24h, calcining the cured film in a nitrogen tube furnace at 350 ℃ for 3h, and removing a template agent F127 to obtain 1.5g of imidazole functionalized ordered mesoporous polymer (3-IMP-MPs).
(II) ionization of imidazole functionalized ordered mesoporous polymer
a. Preparation of 3-IMP-MPs-Et-Br
Ionizing the prepared 3-IMP-MPs and 1, 2-dibromoethane to obtain 3-IMP-MPs-Et-Br, wherein the specific operation process comprises the following steps: 5g of 3-IMP-MPs and 50ml of acetonitrile with the mass concentration of 99.9 percent and 1g of 1, 2-dibromoethane with the mass concentration of 99.9 percent are added into a round-bottom flask, stirred and refluxed for 24 hours at the temperature of 83 ℃, filtered after reaction and washed by acetone and deionized water alternately for three times, and then placed in a vacuum drying oven at the temperature of 80 ℃ for drying for 24 hours to obtain 1.51g of product 3-IMP-MPs-Et-Br.
b. Preparation of 3-IMP-MPs-Et- (NEt4) Br
5g of 3-IMP-MPs-Et-Br, 2g of 99.9% strength by mass aqueous triethylamine and 50ml of deionized water were placed in a round-bottomed flask, stirred at 60 ℃ under reflux for 24 hours, filtered after the reaction and washed three times with alternating mixtures of acetone and deionized water, and then dried in a vacuum oven at 80 ℃ for 24 hours to give 1.51g of 3-IMP-MPs-Et- (NEt4) Br as the product.
c. Preparation of 3-IMP-MPs-Et- (NEt4) AcO
5g of 3-IMP-MPs-Et- (NEt)4) Br and 50ml deionized water and 2g sodium acetate solid are respectively added into a round-bottom flask, stirred for 24 hours at normal temperature, filtered and washed with deionized water for three times after reaction to fully remove the sodium acetate attached to the material, and dried for 24 hours in a vacuum drying oven at 80 ℃ to obtain 1.51g mesoporous polymerization (3-IMP-MPs-Et- (NEt4) AcO) taking the product as the loaded bifunctional ionic liquid.
Referring to FIG. 1, the 3-IMP-MPs-Et- (NEt4) AcO product was characterized by X-ray diffraction and the resulting material was an ordered two-dimensional hexagonal structure.
With reference to FIG. 2, the 3-IMP-MPs-Et- (NEt4) AcO product was characterized by nitrogen desorption isothermally and the specific surface area of the material was 398m2Per g, pore volume 0.43cm3/g。
Referring to FIG. 3, the above-mentioned 3-IMP-MPs-Et- (NEt4) AcO product was characterized by transmission electron microscopy, and the obtained material was an ordered mesoporous material.
Example 2
100mg (4 mol%) of 3-IMP-MPs-Et- (NEt) prepared in example 1 above were weighed4) AcO is a catalyst, 107mg (1mmol) of azomethylaniline, 210mg (2mmol) of phenylsilane and 2ml of acetonitrile are put into a high-pressure reaction kettle, carbon dioxide with the pressure of 1MPa is filled, the reaction is heated to 30 ℃ and reacts for 18 hours, and the reaction structural formula is as follows:
in the reaction processIn-process CO2The pressure is kept unchanged all the time, after the reaction is finished, the reaction kettle is cooled to room temperature, 20ml of deionized water is added for washing and quenching the phenylsilane, and the catalyst separated by suction filtration can be recycled. The filtrate was extracted three times with 60ml of dichloromethane, the organic layers were combined, dried over anhydrous sodium sulfate for half an hour, and the oily mixture obtained by rotary evaporation was separated by column chromatography (petroleum ether: ethyl acetate 4: 1) to give 128mg of N-methylformamide with a yield of 95%.
Example 3
100mg (4 mol%) of 3-IMP-MPs-Et- (NEt4) AcO prepared in example 1 above as a catalyst, 121mg (1mmol) of p-methylanilide, 210mg (2mmol) of phenylsilane and 2ml of acetonitrile were weighed into a 15ml autoclave and charged with carbon dioxide under a pressure of 1MPa, heated to 30 ℃ and reacted for 18 hours, the reaction formula of which is:
CO during the reaction2The pressure is kept unchanged all the time, after the reaction is finished, the reaction kettle is cooled to room temperature, 20ml of deionized water is added for washing and quenching the phenylsilane, and the catalyst separated by suction filtration can be recycled. The filtrate was extracted three times with 60ml of dichloromethane, organic layers were collected, combined, dried over anhydrous sodium sulfate for half an hour, and the oily mixture obtained by rotary evaporation was separated by column chromatography (petroleum ether: ethyl acetate 4: 1), yielding 138.6mg of p-methylazamethylcarboxamide, which was 93%.
Example 4
100mg (4 mol%) of 3-IMP-MPs-Et- (NEt) prepared in example 1 above were weighed4) AcO is used as a catalyst, 137mg (1mmol) of p-methoxyazomethylaniline, 210mg (2mmol) of phenylsilane and 2ml of acetonitrile are put into a high-pressure reaction kettle, carbon dioxide with the pressure of 1MPa is filled, the reaction is heated to 30 ℃ and reacts for 18 hours, and the reaction structural formula is as follows:
CO during the reaction2The pressure is kept unchanged all the time, after the reaction is finished, the reaction kettle is cooled to room temperature, 20ml of deionized water is added for washing and quenching the phenylsilane, and the catalyst separated by suction filtration can be recycled. The filtrate was extracted three times with 60ml of dichloromethane, the organic layers were combined, dried over anhydrous sodium sulfate for half an hour, and the oily mixture obtained by rotary evaporation was separated by column chromatography (petroleum ether: ethyl acetate 4: 1), yielding 158.4mg of p-methoxyazomethylformamide with a yield of 96%.
Example 5
100mg (4 mol%) of 3-IMP-MPs-Et- (NEt4) AcO prepared in example 1 above as a catalyst, 141mg (1mmol) of p-chloroanilide, 210mg (2mmol) of phenylsilane and 2ml of acetonitrile were weighed into a high-pressure reaction vessel, charged with carbon dioxide at a pressure of 1MPa, heated to 30 ℃ and reacted for 18 hours, the reaction formula of which is:
CO during the reaction2The pressure is kept unchanged all the time, after the reaction is finished, the reaction kettle is cooled to room temperature, 20ml of deionized water is added for washing and quenching the phenylsilane, and the catalyst separated by suction filtration can be recycled. The filtrate was extracted three times with 60ml of dichloromethane, the organic layers were combined, dried over anhydrous sodium sulfate for half an hour, and the oily mixture obtained by rotary evaporation was separated by column chromatography (petroleum ether: ethyl acetate 4: 1) to obtain 152.1mg of the product as p-chloroformamides in a yield of 90%.
Example 6
100mg (4 mol%) of 3-IMP-MPs-Et- (NEt) prepared in example 1 above were weighed4) AcO is used as a catalyst, 125mg (1mmol) of p-fluoroanilide, 210mg (2mmol) of phenylsilane and 2ml of acetonitrile are placed in a high-pressure reaction kettle, carbon dioxide with the pressure of 1MPa is filled, the reaction kettle is heated to 30 ℃ and reacts for 18 hours, and the reaction structural formula is as follows:
CO during the reaction2The pressure is kept unchanged all the time, after the reaction is finished, the reaction kettle is cooled to room temperature, 20ml of deionized water is added for washing and quenching the phenylsilane, and the catalyst separated by suction filtration can be recycled. The filtrate was extracted three times with 60ml of dichloromethane, the organic layers were combined, dried over anhydrous sodium sulfate for half an hour, and the oily mixture obtained by rotary evaporation was separated by column chromatography (petroleum ether: ethyl acetate 4: 1) to obtain 134.6mg of the product p-fluoroazamethylamide in 88% yield.
The above embodiments are only for further illustration of the present invention and are not intended to limit the present invention, and all equivalent implementations of the present invention should be included in the scope of the claims of the present invention.
Claims (2)
1. The preparation method of the mesoporous polymer loaded with the bifunctional ionic liquid is characterized in that the mesoporous polymer loaded with the bifunctional ionic liquid is prepared by taking an imidazole functionalized ordered mesoporous polymer as a carrier, connecting 1, 2-dibromoethane and triethylamine in a covalent bond mode, and carrying out ion exchange on sodium acetate and the bifunctional ionic liquid, and comprises the following specific steps:
preparation of imidazole functionalized ordered mesoporous polymer
a. Preparation of 1- (3-methoxybenzyl) -1-hydro-imidazole intermediates
Mixing tetrahydrofuran and sodium hydride according to the proportion of 1-6: mixing the raw materials according to a molar ratio of 1, dropwise adding the mixture into a mixed solution of imidazole and tetrahydrofuran, stirring for 40-60 min, adding 1- (chloromethyl) -3-anisole, refluxing for 24h at the temperature of 70 ℃, and carrying out a synthetic reaction according to the following reaction structural formula:
washing with deionized water and extracting with dichloromethane after the reaction is finished, washing the extract with deionized water and saturated saline water in sequence, drying and separating by column chromatography to obtain a product 1- (3-methoxybenzyl) -1-hydrogen-imidazole intermediate, wherein the mixed solution of imidazole and tetrahydrofuran is a mixture of imidazole and tetrahydrofuran according to the weight ratio of 1: mixing at a molar ratio of 8-15; the molar ratio of the 1- (chloromethyl) -3-anisole to the imidazole is 1-5: 1;
b. preparation of 3- ((1-hydro-imidazole-1-) methyl) phenol
The intermediate prepared above was reacted with hydrobromic acid in a 1: mixing the components according to the molar ratio of 6-10, refluxing for 24 hours at the temperature of 120 ℃, and performing demethylation reaction of the following reaction structural formula:
after the reaction is finished, Na is used2CO3Neutralizing hydrobromic acid, adding saturated NaHCO when pH is 73Adjusting the pH value of the reaction solution to 7.5, washing with water, and filtering to obtain a product, namely 3- ((1-hydrogen-imidazole-1-) methyl) phenol;
c. preparation of imidazole functionalized precursor
Mixing the prepared 3- ((1-hydrogen-imidazole-1-) methyl) phenol with 38 wt% of formaldehyde solution and 10 wt% of sodium hydroxide solution, stirring for 10-20 min at normal temperature, adding phenol, stirring for 1-2 h at 70-75 ℃, cooling to normal temperature after reaction, adjusting the pH value of reaction liquid to 7 by hydrochloric acid, and performing rotary evaporation to obtain an imidazole functionalized precursor, wherein the molar ratio of the 3- ((1-hydrogen-imidazole-1-) methyl) phenol to the formaldehyde to the sodium hydroxide is 1: 8-10: 14-18: 2-4;
d. preparation of imidazole functionalized ordered mesoporous polymer
Mixing the prepared imidazole functionalized precursor with polyether and ethanol according to the weight ratio of 1: 1: 18-25, stirring for 20-50 min, spreading the mixture on a glass plate, volatilizing at room temperature for 8-12 h, drying in an oven at 100-120 ℃ for 18-24 h, and calcining the cured film in a nitrogen tube furnace at 350 ℃ for 3h to obtain the imidazole functionalized ordered mesoporous polymer;
(II) ionization of imidazole functionalized ordered mesoporous polymer
a. Preparation of 3-IMP-MPs-Et-Br
Mixing the prepared imidazole functionalized ordered mesoporous polymer with 1, 2-dibromoethane and acetonitrile according to the weight ratio of 4-6: 1: mixing the components according to the mass ratio of 35-45, stirring and refluxing the mixture at the temperature of 70-83 ℃ for 12-24 hours, filtering the reaction solution, washing the filtrate with acetone and deionized water alternately for three times in sequence, and then drying the filtrate in vacuum at the temperature of 60-80 ℃ for 12-24 hours to obtain a product of 3-IMP-MPs-Et-Br;
b. preparation of 3-IMP-MPs-Et- (NEt4) Br
3-IMP-MPs-Et-Br prepared above was mixed with triethylamine and deionized water in a ratio of 5: 2-8: mixing the components according to the mass ratio of 35-45, stirring and refluxing the mixture at the temperature of 60-80 ℃ for 12-24 hours, filtering the reaction solution, washing the filtrate with acetone and deionized water alternately for three times in sequence, and then drying the filtrate in vacuum at the temperature of 60-80 ℃ for 12-24 hours to obtain a product of 3-IMP-MPs-Et- (NEt4) Br;
c. preparation of 3-IMP-MPs-Et- (NEt4) AcO
3-IMP-MPs-Et- (NEt4) Br prepared above was mixed with sodium acetate and deionized water at a ratio of 5: 2-8: mixing the components in a mass ratio of 35-45, stirring the mixture at normal temperature for 12-24 hours, filtering the reaction solution, washing the filtrate with deionized water, and drying the filtrate in vacuum at the temperature of 60-80 ℃ for 12-24 hours to obtain the product, namely the bifunctional ionic liquid loaded mesoporous polymer 3-IMP-MPs-Et- (NEt4) AcO.
2. The application of the mesoporous polymer with the supported bifunctional ionic liquid prepared by the preparation method of the mesoporous polymer with the supported bifunctional ionic liquid as claimed in claim 1 is characterized in that the mesoporous polymer with the supported bifunctional ionic liquid is applied to CO as a catalyst2The reaction of the formamide synthesized by heterogeneous catalysis with an amino compound is carried out at the heterogeneous catalysis synthesis reaction temperature of 30-40 ℃ for 18-24 hours, and the molar ratio of the catalyst to the amino compound, the phenylsilane and the acetonitrile is 0.03-0.06: 1: 2-4: 35-45; the amino compound is azomethylaniline, methylaniline or methoxy azomethineAniline, p-chloroaminomethylaniline or p-fluoroaminomethylaniline; the pressure of the carbon dioxide is 0.5-2 MPa.
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