CN109174181A - A kind of preparation and its application loading difunctional ionic liquid mesoporous polymer - Google Patents
A kind of preparation and its application loading difunctional ionic liquid mesoporous polymer Download PDFInfo
- Publication number
- CN109174181A CN109174181A CN201810907784.4A CN201810907784A CN109174181A CN 109174181 A CN109174181 A CN 109174181A CN 201810907784 A CN201810907784 A CN 201810907784A CN 109174181 A CN109174181 A CN 109174181A
- Authority
- CN
- China
- Prior art keywords
- imidazoles
- reaction
- preparation
- hours
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 25
- 238000011068 loading method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 amine compound Chemical class 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 11
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007210 heterogeneous catalysis Methods 0.000 claims abstract description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-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
- 239000000706 filtrate Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 239000000543 intermediate Substances 0.000 claims description 10
- 238000007306 functionalization reaction Methods 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 238000003756 stirring 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000002242 deionisation method Methods 0.000 claims description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- FUTMKZAQTUAHTF-UHFFFAOYSA-N CNC1=CC=CC=C1.[F] Chemical compound CNC1=CC=CC=C1.[F] FUTMKZAQTUAHTF-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 238000010520 demethylation reaction Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 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
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 2
- ZPOLNCDBPYJDSE-UHFFFAOYSA-N 3-[4-[bis(2-chloroethyl)amino]phenyl]-2-formamidopropanoic acid Chemical compound O=CNC(C(=O)O)CC1=CC=C(N(CCCl)CCCl)C=C1 ZPOLNCDBPYJDSE-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000013335 mesoporous material Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 125000003963 dichloro group Chemical group Cl* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 3
- FCPMCNMAPNVXSZ-UHFFFAOYSA-N CNC1=CC=CC=C1.[Cl] Chemical compound CNC1=CC=CC=C1.[Cl] FCPMCNMAPNVXSZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NMDCOIMMSBBPCK-UHFFFAOYSA-N [Cl].CNC=O Chemical compound [Cl].CNC=O NMDCOIMMSBBPCK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparations and its application for loading difunctionalization ionic liquid mesoporous polymer, its main feature is that using imidazoles functional ordered mesopore polymer as carrier, and 1 is connected in the form of covalent bond, 2- Bromofume and triethylamine, and ion exchange is carried out with sodium acetate and difunctionalization ionic liquid, load difunctionalization ionic liquid mesoporous polymer is made as catalyst in CO2The reaction of formamide is synthesized with the heterogeneous catalysis of amine compound.The present invention has the characteristics that the uniform high-specific surface area of mesoporous material, duct, thermal stability and chemical stabilization are good compared with prior art, can be catalyzed CO under mild conditions2It is reacted with amine compound, catalytic activity is high, and easily separated recycling separation can be recycled, be a kind of novel environmental friendly catalyst, has huge development potentiality in heterogeneous catalysis field.
Description
Technical field
The present invention relates to porous organic polymer catalyst technical field, especially one kind can be recycled in catalysis CO2
The preparation and its application of the load difunctionalization ionic liquid mesoporous polymer of formamide reaction.
Background technique
Carbon dioxide leads to global warming, while being also cheap, C abundant1Resource, therefore by excessive CO2It is converted into
Valuable chemical products has extraordinary Industry Development Prospect.Formamide is important medicine intermediate, usually with an oxygen
The formylated for changing carbon amine generates, and utilizes CO2It is a green and safety for the formylated of N-H key instead of toxic carbon monoxide
Synthetic route.
Currently, the reaction about carbon dioxide that and amine compound has extensive report in various catalyst systems, and
And achieve huge progress.However, these report synthetic route the problem is that: need metallic catalyst, indifferent gas
Body atmosphere, complex reaction system, high moderate pressure and catalyst separation difficulty etc..Therefore, it explores simple, recyclable, green
Catalyst system, be still very desirable.The ordered mesoporous polymer material of ion liquid functionalization is a kind of extraordinary
Combine the advantages that high-specific surface area, high thermal stability, aperture be uniform and ionic liquid multi-functional catalysis of mesoporous material.Cause
This, prepares ionic liquid loaded type ordered mesoporous material, not only can effectively be catalyzed organic synthesis, and is easy recycling benefit
With meeting green chemical concept.
The porous organic polymer synthesis technology of the prior art is complicated, and cost of material is high, it is difficult to be widely used, therefore send out
Open up it is a kind of prepare simple, catalytic activity is high and the porous organic polymer of good cycling stability is to CO2Chemical conversion research has
Important meaning.
Summary of the invention
The purpose of the present invention is in view of the deficiencies of the prior art and the difunctional ionic liquid of a kind of load that provides is mesoporous poly-
The preparation and its application for closing object, are used using imidazoles functional ordered mesopore polymer as carrier, are connected successively in the form of covalent bond
1,2- Bromofume and triethylamine are connect, and carries out ion exchange with sodium acetate and difunctionalization ionic liquid material, what is obtained is double
Functionalized ion liquid mesoporous polymer, the mesoporous polymer are applied in carbon dioxide formylation reaction as catalyst, tool
There are excellent reactivity and recyclability, very high yield, synthetic operation can be obtained under mild reaction conditions
Simply, reproducible, the specific surface area of itself, hole appearance etc., good product selectivity, bottom can be changed by regulating and controlling the molar ratio of monomer
Object universality is strong, and reaction condition is mild, and the easily separated recycling of catalyst is a kind of effective catalyst that can be recycled, in multiphase
Catalytic field has huge development potentiality.
Realizing the specific technical solution of the object of the invention is: a kind of system loading difunctionalization ionic liquid mesoporous polymer
It is standby, its main feature is that using imidazoles functional ordered mesopore polymer as carrier, and 1,2- Bromofume is connected in the form of covalent bond
And triethylamine, and ion exchange is carried out with sodium acetate and difunctionalization ionic liquid, Jie of difunctionalization ionic liquid must be loaded
Pore polymer, specific step is as follows for preparation:
(1), the preparation of imidazoles functional ordered mesopore polymer
A, 1- (3- methoxybenzyl) -1- hydrogen-imidazole intermediates preparation
It is added drop-wise in imidazoles and tetrahydrofuran mixed liquor, stirs after tetrahydrofuran is mixed with sodium hydride by 1~6:1 molar ratio
1- (chloromethyl) -3- methyl phenyl ethers anisole is added after mixing 40~60min, flows back at a temperature of 70 DEG C for 24 hours, carries out following reaction structure formula
Synthetic reaction:
It is washed with deionized and is extracted with methylene chloride after reaction, extract liquor successively uses deionization and saturated salt to wash
Through dry and column chromatography for separation after washing, obtaining product is 1- (3- methoxybenzyl) -1- hydrogen-imidazole intermediates, the imidazoles and tetrahydro
Furans mixed liquor is that imidazoles is mixed with tetrahydrofuran by the molar ratio of 1:8~15；1- (the chloromethyl) -3- methyl phenyl ethers anisole and imidazoles
Molar ratio is by 1~5:1.
B, the preparation of 3- ((1- hydrogen-imidazoles -1-) methyl) phenol
The intermediate of above-mentioned preparation is mixed with hydrobromic acid by the molar ratio of 1:6~10, flow back at a temperature of 120 DEG C for 24 hours, into
The demethylation reaction of the following reaction structure formula of row:
Na is used after reaction2CO3Hydrobromic acid is neutralized, saturation NaHCO is added when pH value is 73Solution, by reaction solution
PH value is adjusted to 7.5, and it is 3- ((1- hydrogen-imidazoles -1-) methyl) phenol that product is obtained after then being washed, being filtered.
C, the preparation of imidazoles functionalization presoma
The formalin and concentration for being 38wt% by 3- ((1- hydrogen-imidazoles -1-) methyl) phenol of above-mentioned preparation and concentration
It is mixed for the sodium hydroxide solution of 10wt%, phenol is added after stirring 10~20min under room temperature, is stirred at a temperature of 70~75 DEG C
1~2h is cooled to room temperature after reaction, reaction solution pH value is adjusted to 7 with hydrochloric acid after through rotary evaporation, obtaining product is imidazoles function
Can change presoma, the molar ratio of 3- ((1- hydrogen-imidazoles -1-) methyl) phenol and phenol, formaldehyde and sodium hydroxide be 1:8~
10:14~18:2~4.
D, the preparation of imidazoles functional ordered mesopore polymer
The imidazoles functionalization presoma of above-mentioned preparation is mixed with polyethers (F127) and ethyl alcohol by 1:1:18~25, stirring 20
It being tiled after~50min on a glass, the 8~12h that volatilizees at room temperature is placed in 100~120 DEG C of baking ovens dry 18~
For 24 hours, cured film is then calcined into 3h in 350 DEG C of nitrogen tube furnaces, obtains product as the polymerization of imidazoles functional ordered mesopore
Object.
(2), the ionization of imidazoles functional ordered mesopore polymer
A, the preparation of 3-IMP-MPs-Et-Br
By the imidazoles functional ordered mesopore polymer of above-mentioned preparation and glycol dibromide and acetonitrile by 4~6:1:35~
The mixing of 45 mass ratioes, is stirred at reflux 12~24 hours, after filtering, much filtrate successively uses third to reaction solution at a temperature of 70~83 DEG C
Alternately washing three times, is then dried in vacuo 12~24 hours at a temperature of 60~80 DEG C for ketone and deionized water, and obtaining product is 3-
IMP-MPs-Et-Br。
B, the preparation of 3-IMP-MPs-Et- (NEt4) Br
The 3-IMP-MPs-Et-Br of above-mentioned preparation is mixed with triethylamine and deionized water by the mass ratio of 5:2~8:35~45
It closes, is stirred at reflux at a temperature of 60~80 DEG C 12~24 hours, after filtering, much filtrate successively uses acetone and deionization to reaction solution
Alternately washing three times, is then dried in vacuo 12~24 hours at a temperature of 60~80 DEG C water, and obtaining product is 3-IMP-MPs-Et-
(NEt4)Br。
C, the preparation of 3-IMP-MPs-Et- (NEt4) AcO
3-IMP-MPs-Et- (NEt4) Br of above-mentioned preparation and sodium acetate and deionized water are pressed into the matter of 5:2~8:35~45
Amount stirs 12~24 hours than mixing, under room temperature, reaction solution after filtering, much filtrate be washed with deionized after at 60~80 DEG C
At a temperature of be dried in vacuo 12~24 hours, obtain product be load difunctionalization ionic liquid mesoporous polymer (3-IMP-MPs-
Et-(NEt4)AcO)。
A kind of application of the load difunctionalization ionic liquid mesoporous polymer, its main feature is that load is contained difunctionalization
Ionic liquid mesoporous polymer is applied as catalyst in CO2The reaction of formamide is synthesized with the heterogeneous catalysis of amine compound,
The reaction temperature of its heterogeneous catalysis synthesis is 30~40 DEG C, and the reaction time is 18~24 hours, and the heterogeneous catalysis synthesizes formyl
The molar ratio of the reaction of amine, catalyst and amine compound, phenylsilane and acetonitrile is 0.03~0.06:1:2~4:35~45；
The pressure of the carbon dioxide is 0.5~2MPa；The amine compound is N-methyl aniline, methyl N-methyl aniline, methoxy
Base N-methyl aniline, to chlorine N-methyl aniline or to fluorine N-methyl aniline, general structure is as follows:
Wherein:
The present invention has the uniform high-specific surface area of mesoporous material, duct, thermal stability and chemistry compared with prior art
The features such as having stablized can be catalyzed CO under mild conditions2It is reacted with amine compound, catalytic activity is high, easily separated recycling
Separation, can be recycled, be a kind of novel environmental friendly catalyst, have huge development potentiality in heterogeneous catalysis field.
Detailed description of the invention
Fig. 1 is load difunctionalization ionic liquid mesoporous polymer X-ray diffractogram prepared by embodiment 1；
Fig. 2 is load difunctionalization ionic liquid mesoporous polymer N prepared by embodiment 12Adsorption-desorption isothermal；
Fig. 3 is load difunctionalization ionic liquid mesoporous polymer transmission electron microscope picture prepared by embodiment 1.
Specific embodiment
By following specific embodiments, the present invention is described in further detail.
Embodiment 1
(1), the preparation of imidazoles functional ordered mesopore material
A, 1- (3- methoxybenzyl) -1- hydrogen-imidazole intermediates preparation
After the tetrahydrofuran that 5mL mass concentration is 99.9% is mixed with 4.3g (0.18mol) sodium hydride, it is added dropwise to
In the mixed liquor of tetrahydrofuran and 6.8g (0.1mol) imidazoles that 40mL mass concentration is 99.9%, add after being stirred 40min
Entering 15.7g (0.1mol) mass concentration is 99.9%1- (chloromethyl) -3- methyl phenyl ethers anisole, is flowed back at a temperature of 70 DEG C for 24 hours, reaction
Structural formula is as follows:
Reaction product is extracted with dichloromethane after deionized water is washed three times, and organic phase is washed with deionized after extraction
It washed once twice with saturated brine, it is then dry with anhydrous sodium sulfate, it is spin-dried for obtaining after methylene chloride through column chromatography for separation
15.3g product is 1- (3- methoxybenzyl) -1- hydrogen-imidazole intermediates, yield 81%.
B, the preparation of 3- ((1- hydrogen-imidazoles -1-) methyl) phenol (3-IMP)
Taking 1- (3- methoxybenzyl) -1- hydrogen-imidazole intermediates of the above-mentioned preparation of 10g to be added to 50mL mass concentration is 33%
In hydrobromic acid, flows back at a temperature of 120 DEG C and carries out the demethylation reaction of following reaction structure formula for 24 hours:
Na is used after reaction2CO3Hydrobromic acid is neutralized, when saturation NaHCO is added near 7 when for pH value3Solution, by reaction solution
PH value be adjusted to 7.5, then filtered, wash after refilter, obtain 9.2g product be 3- ((1- hydrogen-imidazoles -1-) methyl) phenol,
Its yield is 100%.
C, the preparation of imidazoles functionalization presoma
Take 3- ((1- hydrogen-imidazoles -1-) methyl) phenol and the 2.9g mass concentration of the above-mentioned preparation of 0.19g for the first of 38wt%
The sodium hydroxide solution that aldehyde solution and 1.15g mass concentration are 10wt% mixes, and 1.15g matter is added after 10min is stirred under room temperature
Amount concentration is 99.9% phenol, and 2h is then stirred at a temperature of 75 DEG C, and one pot process functionalization presoma is cooling by reaction solution
Being adjusted to pH with 2mol/L HCl solution after to room temperature is 7, rotary evaporation 2h remove after the water in system before 2g imidazoles functionalization
Drive body.
D, the preparation of imidazoles functional ordered mesopore polymer
2g F127 is dissolved in the ethanol solution that 50mL mass concentration is 99%, the above-mentioned preparation of 1.6g is then added
Imidazoles functionalization presoma is tiled on a glass after being stirred 45min, and the 8h that volatilizees at room temperature is placed on 120 DEG C of bakings
It is dry in case that cured film is calcined into 3h in nitrogen tube furnace at a temperature of 350 DEG C for 24 hours, it is obtained after removing template agent removing F127
1.5g imidazoles functional ordered mesopore polymer (3-IMP-MPs).
(2), the ionization of imidazoles functional ordered mesopore polymer
A, the preparation of 3-IMP-MPs-Et-Br
By the 3-IMP-MPs of above-mentioned preparation and 1,2- Bromofume ionizes to obtain 3-IMP-MPs-Et-Br, specific to grasp
Make process are as follows: the 1,2- for being 99.9% by 5g 3-IMP-MPs and 50ml the mass concentration acetonitrile for being 99.9% and 1g mass concentration
Bromofume is added in round-bottomed flask, is stirred at reflux at a temperature of 83 DEG C 24 hours, filtering and with acetone and deionization after reaction
Alternately washing three times, is then placed within drying 24 hours in 80 DEG C of vacuum ovens to water, and obtaining 1.51g product is 3-IMP-MPs-
Et-Br。
B, the preparation of 3-IMP-MPs-Et- (NEt4) Br
By the deionization of 5g 3-IMP-MPs-Et-Br and 2g the mass concentration triethylamine aqueous solution and 50ml for being 99.9%
Water is added in round-bottomed flask, is stirred at reflux at a temperature of 60 DEG C 24 hours, and filtering acetone and deionized water are alternately washed after reaction
It washs three times, then 24 hours dry in 80 DEG C of vacuum ovens, obtaining 1.51g product is 3-IMP-MPs-Et- (NEt4) Br.
C, the preparation of 3-IMP-MPs-Et- (NEt4) AcO
By 5g 3-IMP-MPs-Et- (NEt4) deionized water and 2g sodium acetate solid of Br and 50ml be separately added into round bottom
It in flask, is stirred 24 hours under room temperature, filtering is washed with deionized three times after reaction, is attached on material with sufficiently getting rid of
Sodium acetate obtain Jie that 1.51g product be load difunctionalization ionic liquid dry 24 hours in 80 DEG C of vacuum ovens
Hole polymerize (3-IMP-MPs-Et- (NEt4) AcO).
Refering to attached drawing 1, above-mentioned 3-IMP-MPs-Et- (NEt4) AcO product is characterized through X-ray diffraction, and resulting materials are to have
Sequence two dimension hexagonal structure.
Refering to attached drawing 2, above-mentioned 3-IMP-MPs-Et- (NEt4) AcO product is characterized through isothermal nitrogen adsorption desorption, resulting materials
Specific surface area be 398m2/ g, pore volume 0.43cm3/g。
Refering to attached drawing 3, above-mentioned 3-IMP-MPs-Et- (NEt4) AcO product is characterized through transmission electron microscope, resulting materials
For ordered mesoporous material.
Embodiment 2
Weigh the 3-IMP-MPs-Et- (NEt of the preparation of 100mg (4mol%) above-described embodiment 14) AcO be catalyst with
107mg (1mmol) N-methyl aniline, 210mg (2mmol) phenylsilane and 2ml acetonitrile are put into autoclave, and charged pressure
For the carbon dioxide of 1MPa, 30 DEG C are heated to, is reacted 18 hours, reaction structure formula are as follows:
CO during the reaction2Pressure is always maintained at constant, is after reaction cooled to room temperature reaction kettle, adds 20ml's
Phenylsilane is washed and be quenched to deionized water, and filtering the catalyst isolated can be recycled.The dichloro of 60ml is added in filtrate
Methane is extracted takes organic layer three times, and anhydrous sodium sulfate dry half an hour, the oily rotated is added after merging organic layer
Mixture obtains 128mg N-methyl formamide, yield 95% through column chromatography for separation (petroleum ether: ethyl acetate=4:1).
Embodiment 3
Weigh 100mg (4mol%) above-described embodiment 1 preparation 3-IMP-MPs-Et- (NEt4) AcO be catalyst with
121mg (1mmol) is put into the autoclave of 15ml to methyl N-methyl aniline, 210mg (2mmol) phenylsilane and 2ml acetonitrile
In, and charged pressure is the carbon dioxide of 1MPa, is heated to 30 DEG C, is reacted 18 hours, reaction structure formula are as follows:
CO during the reaction2Pressure is always maintained at constant, is after reaction cooled to room temperature reaction kettle, adds 20ml's
Phenylsilane is washed and be quenched to deionized water, and filtering the catalyst isolated can be recycled.The dichloro of 60ml is added in filtrate
Methane is extracted takes organic layer three times, and anhydrous sodium sulfate dry half an hour, the oily rotated is added after merging organic layer
Mixture obtains 138.6mg to methyl N-methyl formamide, yield is through column chromatography for separation (petroleum ether: ethyl acetate=4:1)
93%.
Embodiment 4
Weigh the 3-IMP-MPs-Et- (NEt of the preparation of 100mg (4mol%) above-described embodiment 14) AcO be catalyst with
137mg (1mmol) is put into autoclave methoxyl group N-methyl aniline, 210mg (2mmol) phenylsilane and 2ml acetonitrile, and
Charged pressure is the carbon dioxide of 1MPa, is heated to 30 DEG C, is reacted 18 hours, reaction structure formula are as follows:
CO during the reaction2Pressure is always maintained at constant, is after reaction cooled to room temperature reaction kettle, adds 20ml's
Phenylsilane is washed and be quenched to deionized water, and filtering the catalyst isolated can be recycled.The dichloro of 60ml is added in filtrate
Methane is extracted takes organic layer three times, and anhydrous sodium sulfate dry half an hour, the oily rotated is added after merging organic layer
Mixture through column chromatography for separation (petroleum ether: ethyl acetate=4:1), obtain 158.4mg product be to methoxyl group N-methyl formamide,
Its yield is 96%.
Embodiment 5
Weigh 100mg (4mol%) above-described embodiment 1 preparation 3-IMP-MPs-Et- (NEt4) AcO be catalyst with
141mg (1mmol) is put into autoclave chlorine N-methyl aniline, 210mg (2mmol) phenylsilane and 2ml acetonitrile, and is filled with
Pressure is the carbon dioxide of 1MPa, is heated to 30 DEG C, is reacted 18 hours, reaction structure formula are as follows:
CO during the reaction2Pressure is always maintained at constant, is after reaction cooled to room temperature reaction kettle, adds 20ml's
Phenylsilane is washed and be quenched to deionized water, and filtering the catalyst isolated can be recycled.The dichloro of 60ml is added in filtrate
Methane is extracted takes organic layer three times, and anhydrous sodium sulfate dry half an hour, the oily rotated is added after merging organic layer
For mixture through column chromatography for separation (petroleum ether: ethyl acetate=4:1), obtaining 152.1mg product is to produce to chlorine N-methyl formamide
Rate is 90%.
Embodiment 6
Weigh the 3-IMP-MPs-Et- (NEt of the preparation of 100mg (4mol%) above-described embodiment 14) AcO be catalyst with
125mg (1mmol) is put into autoclave fluorine N-methyl aniline, 210mg (2mmol) phenylsilane and 2ml acetonitrile, and is filled with
Pressure is the carbon dioxide of 1MPa, is heated to 30 DEG C, is reacted 18 hours, reaction structure formula are as follows:
CO during the reaction2Pressure is always maintained at constant, is after reaction cooled to room temperature reaction kettle, adds 20ml's
Phenylsilane is washed and be quenched to deionized water, and filtering the catalyst isolated can be recycled.The dichloro of 60ml is added in filtrate
Methane is extracted takes organic layer three times, and anhydrous sodium sulfate dry half an hour, the oily rotated is added after merging organic layer
For mixture through column chromatography for separation (petroleum ether: ethyl acetate=4:1), obtaining 134.6mg product is to produce to fluorine N-methyl formamide
Rate is 88%.
Only the present invention will be further described for the above various embodiments, is not intended to limit the invention patent, all is this hair
Bright equivalence enforcement, is intended to be limited solely by within the scope of the claims of the invention patent.
Claims (2)
1. a kind of preparation for loading difunctionalization ionic liquid mesoporous polymer, it is characterised in that with imidazoles functional ordered mesopore
Polymer is carrier, and 1,2- Bromofume and triethylamine are connected in the form of covalent bond, and with sodium acetate and difunctionalization from
Sub- liquid carries out ion exchange, must load the mesoporous polymer of difunctionalization ionic liquid, specific step is as follows for preparation:
(1), the preparation of imidazoles functional ordered mesopore polymer
A, 1- (3- methoxybenzyl) -1- hydrogen-imidazole intermediates preparation
It is added drop-wise to after tetrahydrofuran is mixed with sodium hydride by 1~6:1 molar ratio in imidazoles and tetrahydrofuran mixed liquor, stirring 40
1- (chloromethyl) -3- methyl phenyl ethers anisole is added after~60min, flows back at a temperature of 70 DEG C for 24 hours, carries out the synthesis of following reaction structure formula
Reaction:
It is washed with deionized and is extracted with methylene chloride after reaction, after extract liquor is successively washed with deionization and saturated brine
Through dry and column chromatography for separation, obtaining product is 1- (3- methoxybenzyl) -1- hydrogen-imidazole intermediates, the imidazoles and tetrahydrofuran
Mixed liquor is that imidazoles is mixed with tetrahydrofuran by the molar ratio of 1:8~15；Mole of 1- (the chloromethyl) -3- methyl phenyl ethers anisole and imidazoles
Than for by 1~5:1；
B, the preparation of 3- ((1- hydrogen-imidazoles -1-) methyl) phenol
The intermediate of above-mentioned preparation is mixed with hydrobromic acid by the molar ratio of 1:6~10, flows back for 24 hours, is carried out such as at a temperature of 120 DEG C
The demethylation reaction of lower reaction structure formula:
Na is used after reaction2CO3Hydrobromic acid is neutralized, saturation NaHCO is added when pH value is 73Solution, by the pH value of reaction solution
7.5 are adjusted to, it is 3- ((1- hydrogen-imidazoles -1-) methyl) phenol that product is obtained after then being washed, being filtered；
C, the preparation of imidazoles functionalization presoma
It is by formalin and concentration that 3- ((1- hydrogen-imidazoles -1-) methyl) phenol of above-mentioned preparation is 38wt% with concentration
The sodium hydroxide solution of 10wt% mixes, and phenol is added after stirring 10~20min under room temperature, stirs 1 at a temperature of 70~75 DEG C
~2h, is cooled to room temperature after reaction, reaction solution pH value is adjusted to 7 with hydrochloric acid after through rotary evaporation, obtaining product is imidazoles function
Can change presoma, the molar ratio of 3- ((1- hydrogen-imidazoles -1-) methyl) phenol and phenol, formaldehyde and sodium hydroxide be 1:8~
10:14~18:2~4；
D, the preparation of imidazoles functional ordered mesopore polymer
The imidazoles functionalization presoma of above-mentioned preparation is mixed with polyethers and ethyl alcohol by 1:1:18~25, after stirring 20~50min
It being tiled on a glass, the 8~12h that volatilizees at room temperature is placed in 100~120 DEG C of baking ovens dry 18~for 24 hours, then it will consolidate
The film of change calcines 3h in 350 DEG C of nitrogen tube furnaces, and obtaining product is imidazoles functional ordered mesopore polymer；
(2), the ionization of imidazoles functional ordered mesopore polymer
A, the preparation of 3-IMP-MPs-Et-Br
The imidazoles functional ordered mesopore polymer of above-mentioned preparation and glycol dibromide and acetonitrile are pressed into the matter of 4~6:1:35~45
Amount than mixing, be stirred at reflux at a temperature of 70~83 DEG C 12~24 hours, reaction solution after filtering, much filtrate successively use acetone and
Alternately washing three times, is then dried in vacuo 12~24 hours at a temperature of 60~80 DEG C deionized water, and obtaining product is 3-IMP-
MPs-Et-Br；
B, the preparation of 3-IMP-MPs-Et- (NEt4) Br
The 3-IMP-MPs-Et-Br of above-mentioned preparation is mixed with triethylamine and deionized water by the mass ratio of 5:2~8:35~45,
It is stirred at reflux at a temperature of 60~80 DEG C 12~24 hours, after filtering, much filtrate successively uses acetone and deionized water to hand over to reaction solution
Three times for washing, it is then dried in vacuo 12~24 hours at a temperature of 60~80 DEG C, obtaining product is 3-IMP-MPs-Et- (NEt4)
Br；
C, the preparation of 3-IMP-MPs-Et- (NEt4) AcO
3-IMP-MPs-Et- (NEt4) Br of above-mentioned preparation and sodium acetate and deionized water are pressed into the mass ratio of 5:2~8:35~45
Mixing is stirred 12~24 hours under room temperature, reaction solution after filtering, much filtrate be washed with deionized after in 60~80 DEG C of temperature
Lower vacuum drying 12~24 hours, obtaining product is the mesoporous polymer (3-IMP-MPs-Et- for loading difunctionalization ionic liquid
(NEt4)AcO)。
2. loading the application of difunctionalization ionic liquid mesoporous polymer described in a kind of claim 1, it is characterised in that will load
The ionic liquid mesoporous polymer containing difunctionalization is applied as catalyst in CO2Formyl is synthesized with the heterogeneous catalysis of amine compound
The reaction of amine, the reaction temperature of heterogeneous catalysis synthesis are 30~40 DEG C, and the reaction time is 18~24 hours, the heterogeneous catalysis
Synthesize the reaction of formamide, the molar ratio of catalyst and amine compound, phenylsilane and acetonitrile be 0.03~0.06:1:2~
4:35~45；The amine compound be N-methyl aniline, methyl N-methyl aniline, methoxyl group N-methyl aniline, to chlorine n-formyl sarcolysine
Base aniline or to fluorine N-methyl aniline；The pressure of the carbon dioxide is 0.5~2MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810907784.4A CN109174181B (en) | 2018-08-10 | 2018-08-10 | Preparation and application of mesoporous polymer loaded with bifunctional ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810907784.4A CN109174181B (en) | 2018-08-10 | 2018-08-10 | Preparation and application of mesoporous polymer loaded with bifunctional ionic liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109174181A true CN109174181A (en) | 2019-01-11 |
| CN109174181B CN109174181B (en) | 2021-05-25 |
Family
ID=64920955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810907784.4A Active CN109174181B (en) | 2018-08-10 | 2018-08-10 | Preparation and application of mesoporous polymer loaded with bifunctional ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109174181B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111229320A (en) * | 2020-01-16 | 2020-06-05 | 辽宁大学 | Metal organic framework composite material grafted with ionic liquid and preparation method and application thereof |
| CN117624052A (en) * | 2024-01-26 | 2024-03-01 | 四川益能康生环保科技有限公司 | Ionic liquid for capturing carbon dioxide and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092771A (en) * | 1992-12-10 | 1994-09-28 | 美国辉瑞有限公司 | The non-aromatic heterocycles that aminomethylene replaces |
| CN101790413A (en) * | 2007-10-19 | 2010-07-28 | 川崎重工业株式会社 | Separation membrane comprising polyethersulfone, process for production thereof, and stock solution for production of film |
| CN103041866A (en) * | 2013-01-18 | 2013-04-17 | 绍兴文理学院 | Preparation method of titanium dioxide-mesoporous polymer nano porous composite visible light catalytic material |
| JP2014005418A (en) * | 2012-06-27 | 2014-01-16 | Central Glass Co Ltd | Thermal transfer medium containing fluorination unsaturated hydrocarbon |
| CN104448381A (en) * | 2014-11-07 | 2015-03-25 | 华东师范大学 | Preparation and application of imidazole functionalized ordered mesoporous phenolic resin material |
| US20160296484A1 (en) * | 2014-02-03 | 2016-10-13 | Quadriga Biosciences, Inc. | Beta-substituted beta-amino acids and analogs as chemotherapeutic agents |
| CN106977676A (en) * | 2017-03-14 | 2017-07-25 | 华东师范大学 | A kind of synthesis and its application of nitrogenous functional mesoporous polymer |
| CN108456276A (en) * | 2018-05-17 | 2018-08-28 | 华东师范大学 | A kind of preparation and its application of imidazole salts porous organic polymer |
-
2018
- 2018-08-10 CN CN201810907784.4A patent/CN109174181B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092771A (en) * | 1992-12-10 | 1994-09-28 | 美国辉瑞有限公司 | The non-aromatic heterocycles that aminomethylene replaces |
| CN101790413A (en) * | 2007-10-19 | 2010-07-28 | 川崎重工业株式会社 | Separation membrane comprising polyethersulfone, process for production thereof, and stock solution for production of film |
| JP2014005418A (en) * | 2012-06-27 | 2014-01-16 | Central Glass Co Ltd | Thermal transfer medium containing fluorination unsaturated hydrocarbon |
| CN103041866A (en) * | 2013-01-18 | 2013-04-17 | 绍兴文理学院 | Preparation method of titanium dioxide-mesoporous polymer nano porous composite visible light catalytic material |
| US20160296484A1 (en) * | 2014-02-03 | 2016-10-13 | Quadriga Biosciences, Inc. | Beta-substituted beta-amino acids and analogs as chemotherapeutic agents |
| CN104448381A (en) * | 2014-11-07 | 2015-03-25 | 华东师范大学 | Preparation and application of imidazole functionalized ordered mesoporous phenolic resin material |
| CN106977676A (en) * | 2017-03-14 | 2017-07-25 | 华东师范大学 | A kind of synthesis and its application of nitrogenous functional mesoporous polymer |
| CN108456276A (en) * | 2018-05-17 | 2018-08-28 | 华东师范大学 | A kind of preparation and its application of imidazole salts porous organic polymer |
Non-Patent Citations (2)
| Title |
|---|
| TAO WANG ET AL: "Highly recyclable polymer supported ionic liquids as efficient heterogeneous catalysts for batch and flow conversion of CO2 to cyclic carbonates", 《RSC ADVANCES》 * |
| 卢小伟: "咪唑功能化介孔聚合物的合成及其在二氧化碳转化中的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111229320A (en) * | 2020-01-16 | 2020-06-05 | 辽宁大学 | Metal organic framework composite material grafted with ionic liquid and preparation method and application thereof |
| CN111229320B (en) * | 2020-01-16 | 2022-07-19 | 辽宁大学 | Metal organic framework composite material grafted with ionic liquid and preparation method and application thereof |
| CN117624052A (en) * | 2024-01-26 | 2024-03-01 | 四川益能康生环保科技有限公司 | Ionic liquid for capturing carbon dioxide and preparation method thereof |
| CN117624052B (en) * | 2024-01-26 | 2024-04-12 | 四川益能康生环保科技有限公司 | Ionic liquid for capturing carbon dioxide and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109174181B (en) | 2021-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yi et al. | Synthesis, structure, luminescence and catalytic properties of cadmium (II) coordination polymers with 9 H-carbazole-2, 7-dicarboxylic acid | |
| Chang et al. | One-pot synthesis of dimethyl carbonate and glycols from supercritical CO2, ethylene oxide or propylene oxide, and methanol | |
| CN106378109B (en) | A kind of porous polycarbazole polymer and its preparation method and application | |
| CN109174181A (en) | A kind of preparation and its application loading difunctional ionic liquid mesoporous polymer | |
| Sani et al. | A study of contemporary progress relating to COF materials for CO 2 capture and fixation reactions | |
| CN107880079B (en) | Cyclic N-heterocyclic bis-carbene-palladium complex and preparation method and application thereof | |
| Ren et al. | Amine-grafted on lanthanide metal-organic frameworks: Three solid base catalysts for Knoevenagel condensation reaction | |
| WO2023065714A1 (en) | Pyrimidine- and cyano group-based bifunctional conjugated microporous polymer, and preparation method therefor and application thereof | |
| CN103304393B (en) | A kind of synthetic method of benzil analog derivative | |
| CN104447700A (en) | Binaphthol-bridged n-heterocyclic bis-carbene metal complex as well as preparation method and application thereof | |
| CN110270133A (en) | A kind of integral post plate preparation method and application based on PE sieve plate conjugation chemistry group | |
| CN110372862B (en) | Triphenylphenanthroimidazole triazine polymer and preparation method and application thereof | |
| CN102755901B (en) | Preparation and application of composite solid acid catalyst used for condensation reaction | |
| CN114989196A (en) | Terbium-based complex and preparation method and application thereof | |
| CN109988079A (en) | A kind of three phase catalyst Pd@COF-QA and the preparation method and application thereof | |
| Zhang et al. | Constructing [Co6 (μ3-OH) 6]-based pillar-layered MOF with open metal sites via steric-hindrance effect on ligand for CO2 adsorption and fixation | |
| Yuan et al. | Constructing a 3D porous Co (II)-organic framework: Synthesis, characterization and chemical transformation of epoxide and CO2 into cyclic carbonate | |
| CN110152739A (en) | Porous organic double compound, synthetic method and the application of load palladium nano-particles in situ | |
| CN110156988A (en) | A kind of phenanthro- imidazole radicals aerotex and its preparation method and application | |
| CN106380579B (en) | The organic porous polymer and its preparation method and application of a kind of azo-based benzene | |
| CN106268954B (en) | A kind of Au@MnPS catalyst and its preparation method and application | |
| CN104262127A (en) | Brush-type difluoro monomer and synthetic method thereof | |
| CN108623493A (en) | With CO under a kind of temperate condition2For the N- formylated synthetic methods of carbon source | |
| JP6011769B2 (en) | Polystyrene-supported pyridine bisoxazoline derivative-calcium catalyst | |
| CN107935803B (en) | Synthetic method of 1, 2-diketone compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |