CN103394372A - Heteropoly ionic liquid catalyst with Br*nsted-Lewis dual acidity - Google Patents
Heteropoly ionic liquid catalyst with Br*nsted-Lewis dual acidity Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 230000009977 dual effect Effects 0.000 title abstract 4
- 239000002253 acid Substances 0.000 claims abstract description 67
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- -1 aluminum ion Chemical class 0.000 claims abstract description 7
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 150000001450 anions Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 34
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 15
- 229920000831 ionic polymer Polymers 0.000 claims description 14
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 abstract description 5
- 150000002892 organic cations Chemical class 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- YHBZSVUULYGVEI-UHFFFAOYSA-N 1-methyl-3-(3-sulfopropyl)-2H-imidazole-2-sulfonic acid Chemical compound CN1C=CN(C1S(=O)(=O)O)CCCS(=O)(=O)O YHBZSVUULYGVEI-UHFFFAOYSA-N 0.000 abstract 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 238000005574 benzylation reaction Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000007306 functionalization reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000013019 agitation Methods 0.000 description 8
- 239000011964 heteropoly acid Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000003918 potentiometric titration Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- IVKBORPKIXVHRI-UHFFFAOYSA-N acetonitrile;butan-1-amine Chemical compound CC#N.CCCCN IVKBORPKIXVHRI-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Abstract
The invention relates to a heteropoly ionic liquid catalyst with Br*nsted-Lewis dual acidity and a preparation method thereof, belonging to the technical field of novel chemical materials and preparation thereof. The synthesis method comprises the following steps: (1) reacting 1,3-propane sultone with N-methylimidazole in toluene in a nitrogen protective atmosphere to obtain an intermediate 1-methyl-3-(3-sulfopropyl)imidazolyl sulfonate (MIMPS); and (2) by using the intermediate MIMPS and Al(NO3)3.9H2O as counter cation sources and phosphotungstate as an anion source, reacting in a water solution under certain conditions by regulating the anion-cation ratio to obtain the heteropoly ionic liquid catalytic material with Br*nsted-Lewis dual acidity. The organic cation with sulfo-group, metal aluminum ion and proton are simultaneously used as the counter cations to prepare the heteropoly salt strong-acid functional ionic liquid with Br*nsted-Lewis dual acidity at the cation part; and the preparation process is simple and easy to implement, and can be used as a benzylation reaction high efficiency catalyst for benzalcohol route.
Description
Technical field
The present invention relates to a kind of method of acid functionalization ionic-liquid catalyst and preparation thereof, a kind of cationic moiety has assorted polyion liquid catalyst of strong acid functionalization of Br nsted-Lewis bisgallic acid and preparation method thereof concurrently specifically, belongs to new material and preparing technical field thereof.
Background technology
Functionalized ion liquid refers to introduce the ionic liquid of functional group in ion (anion or cation), and the existence of this functional group has a great impact ionic liquid, make this ionic liquid have some unique character or can meet the selectivity requirement, comprise for the functionalization of physical property (as mobility, conducting power, liquid scope, dissolubility) with for the functionalization of chemical property (polarity, acidity, chirality, coordination ability).Can realize design to the ionic liquid specific function by introducing different functional groups, as contain Bronsted acid ionic liquid, contain chiral centre ionic liquid, have the ionic liquid of part character etc.Wherein the acid functionalization ionic liquid is a study hotspot in recent years.
The acid functionalization ionic liquid is divided into Lewis acid usually, Br nsted acid and Br nsted-Lewis bisgallic acid type three classes, and typical Lewis acid, Br nsted acid and Br nsted-Lewis bisgallic acid type ionic liquid chemical formula are as follows:
Above-mentioned traditional Br nsted acid type ionic liquid acid strength is not high, to the active deficiency of some acid catalyzed reaction; And by the Lewis acid that anion is introduced, have hydrolabil shortcoming, be difficult to realize good separation and recycling in esterification, dehydration etc. has the acid catalyzed reaction of water generates.Therefore, in the process of development of new acid functionalization ionic-liquid catalyst, wish to research and develop to have acid strength high, the advantage that water stability is good, preferably have Br nsted-Lewis bisgallic acid concurrently, to meet the demand of various acid catalyzed reactions.
Cause in recent years researcher's concern based on the hybrid inorganic-organic materials of heteropoly acid.Wherein, the heteropoly acid organic salt that has an ionic liquid structure is one of hot subject.Shi Jiehua etc. have prepared 1-butyl-3-methylimidazole phosphotungstate ([BMIM]
3PW
12O
40) catalyst, and be used for esterification (catalysis journal, 2008,29 (7): 629-632) of ethanol and acetic acid; Cold scorching the grade prepared acid PVP-heteropoly acid hybrid catalyst, adopt the Hammett indicator method record the acid strength Jin Wei – 3.0 of its catalyst＜
H0＜0.8(catalysis journal, 2012,33 (7): 1224-1228).Yan Leng etc. introduces sulfonic acid group in organic cation, prepares more highly acid [MIMPS]
3PW
12O
40, [PyPS]
3PW
12O
40, [TEAPS]
3PW
12O
40Ionic liquid, (Angew. Chem. Int. Ed. 2009,48:168-171), cause researcher's concern to catalyst to can be used as efficiently " reaction guiding self-separation " in specific esterification.
In sum, having the synthetic and application in acid catalyzed reaction of the design of heteropolyacid salt of ionic liquid structure is a present hot issue, but still is in the starting stage.The method that the most effectively improves at present assorted polyion liquid acid intensity is namely partly to introduce the strong-acid type sulfonic acid group at organic cation.And modulation acid site type how further effectively improves acid strength, is the key issue of research.Up to now, relevant to Lewis acid site introducing cationic moiety, and with the combination of traditional B r nsted acid cation, formulate out have Br nsted-Lewis bisgallic acid, hydrostable, the assorted polyion liquid of highly acid at home and abroad is not reported in document.
Summary of the invention
The objective of the invention is the lower problem of acid strength that exists in order to solve existing acid functionalization ionic liquid, a kind of novel strong acid with Br nsted-Lewis bisgallic acid polyion liquid catalyst of mixing is provided, and the preparation method of this ionic liquid is provided.The present invention also provides the application of this catalyst in the benzyl reaction of methyl phenyl ethers anisole and phenmethylol.
According to the present invention, the assorted polyion liquid catalyst general molecular formula of the strong acid with Br nsted-Lewis bisgallic acid that provides is as follows:
H
X[MIMPS]
YAl
(3-X-Y)/3PW
12O
40
In formula, MIMPS is 1-methyl-3-(3-sulfonic group propyl group) glyoxaline cation.X, Y represent the degree that proton is replaced by cation, and generally, the value of X is that 0 to 1, Y value is 1 to 2, and X+Y＜3.
According to a further aspect in the invention, the present invention also provides the synthetic method of the assorted polyion liquid of strong acid of the above-mentioned Br of having nsted-Lewis bisgallic acid, and its synthesis step is as follows:
(1) intermediate is synthetic:
With 1,3-propane sultone 0.10 mol adds in there-necked flask (250 mL), add 100 mL toluene to make its dissolving, add again 0.10 mol N-methylimidazole, under 50 ℃ of magnetic agitation, logical nitrogen reaction 24 h, carry out suction filtration with reactant liquor, and resulting white precipitate washs three times with ethyl acetate, 60 ℃ of lower vacuum drying 4 h, obtain 1-methyl-3-(3-sulfonic group propyl group) interior sulfonate (MIMPS) the white precipitate pulverulent solids of imidazoles.
(2) the assorted polyion liquid of Br nsted-Lewis bisgallic acid type strong acid is synthetic:
Intermediate MIMPS, Al (NO that step (1) is obtained
3)
39H
2O adds in there-necked flask (100 mL) according to a certain percentage, and take in proportion phosphotungstic acid and add 40 mL deionized waters to make its dissolving in beaker, phosphotungstic acid aqueous solution is added in there-necked flask, room temperature under magnetic agitation (25 ℃) reaction 24 h, decompression distillation, 80 ℃ of vacuum drying 6 h, obtain having concurrently the assorted polyion liquid catalyst material of strong acid functionalization of Br nsted-Lewis bisgallic acid.
The chemical process formula that ionic liquid of the present invention synthesizes is as follows:
The invention also discloses the application of the assorted polyion liquid catalyst of above-mentioned strong acid in take methyl phenyl ethers anisole and phenmethylol as the benzyl reaction of raw material.
The assorted polyion liquid catalyst of the strong acid of the Br of having nsted-Lewis bisgallic acid provided by the invention is compared and is had following characteristics with existing acid functionalization ionic liquid and technology thereof:
(1) the invention provides a kind ofly with proton, metallic aluminium ion, with sulfonic glyoxaline cation,, jointly as the cationic method of anti-lotus of heteropolyanion, synthesize novel ion liquid, enriched the kind of ionic liquid;
(2) technology of preparing of ionic liquid provided by the invention is take alkyl imidazole, sultones, aluminum nitrate, phosphotungstic acid as raw material, have with low cost, the simple advantage of preparation method;
(3) in ionic liquid provided by the invention, organic cation is with the sulfonic acid group of Br nsted acidity; The metallic aluminium ion has Lewis acidity; It is acid that proton in heteropoly acid acid salt also has Br nsted.Triplicity, Br nsted-Lewis bisgallic acid type ionic liquid provided by the invention has the acid strength that approaches free heteropoly acid, have simultaneously the fusing point and the solubility property that are different from free heteropoly acid and common heteropolyacid salt, can be easily as needing strong acid catalyzed catalytic reaction materials'use;
(4) the present invention also provides a kind of with metal cation, and organic cation and proton are simultaneously as the cationic novel organic-inorganic hybrid material of the anti-lotus of heteropolyanion, and the new way that for this reason provides a kind of hybrid inorganic-organic materials to prepare;
(5) the assorted polyion liquid of Br nsted-Lewis bisgallic acid type provided by the present invention is at room temperature solid, is slightly soluble in water, is insoluble to toluene.Be the liquid of thickness at the temperature of benzyl course of reaction, have mobility.Reaction is cooled to room temperature after finishing, and catalyst falls to reactor bottom mutually, and upper organic phase is easy to topple over out, and the catalyst that is colloidal solid can be directly used in reaction next time.
Description of drawings
Fig. 1 is the prepared ionic liquid 1 of embodiment 1
1H NMR spectrogram.
Fig. 2 is the FT-IR spectrogram of the prepared ionic liquid 1 of embodiment 1; Wherein
(a) H 3 PW 12 O 40 (b) MIMPS(c)Ionic liquid 1 [MIMPS] Al
2/3PW
12O
40 (d)[MIMPS]
3PW
12O
40
Fig. 3 is the acetonitrile-n-butylamine potentiometric titration curve figure of the prepared ionic liquid 1 of embodiment 1.
Fig. 4 is embodiment 1,2 prepared ionic liquids 1,2 Py
-IRSpectrogram; Wherein
(a)Ionic liquid 1 [MIMPS] Al
2/3PW
12O
40 (b) H 2 [MIMPS] PW
12O
40 (c)Ionic liquid 2
H[MIMPS] Al
1/3PW
12O
40
Fig. 5 is the acetonitrile-n-butylamine potentiometric titration curve figure of the prepared ionic liquid 2 of embodiment 2.
Fig. 6 is the acetonitrile-n-butylamine potentiometric titration curve figure of the prepared ionic liquid 3 of embodiment 3.
The specific embodiment
The following example is used for further illustrating the present invention, but does not therefore limit the present invention.
Synthesizing of [embodiment 1] ionic liquid 1:
(1) take 1,3-propane sultone 12.21 g (0.10 mol) add in there-necked flask (250 mL), add 100 mL toluene to make its dissolving, add again 9.02 g(0.10 mol) the N-methylimidazole, logical nitrogen reaction 24 h under 50 ℃ of magnetic agitation, reactant liquor is carried out suction filtration, resulting white precipitate washs three times with ethyl acetate, 60 ℃ of lower vacuum drying 4 h, resulting white powder solid is 1-methyl-3-(3-sulfonic group propyl group) the interior sulfonate (MIMPS) of imidazoles.
(2) take Al (NO
3)
39H
2O 1.00g(2.67 mmol), MIMPS 0.82 g (4 mmol) adds in there-necked flask (100 mL), taking phosphotungstic acid 11.52 g (4 mmol) adds 40 mL deionized waters to make its dissolving in beaker, phosphotungstic acid aqueous solution is added in there-necked flask, room temperature under magnetic agitation (25 ℃) reaction 24 h, decompression distillation, 80 ℃ of vacuum drying 6 h, the white green solid of gained, note is done ionic liquid 1, and its structural formula is:
Its fusing point is 101-103 ℃, is slightly soluble in water, is insoluble to toluene.As shown in Figure 1:
1 H-NMR (500MHz, DMSO) characterization result is: δ 2.21 (quint, 2H), 2.83 (t, 2H), (3.83 s, 3H), 4.26 (t, 2H), 7.38 (d, 1H), 7.46 (d, 1H), 8.70 (s, 1H); As shown in Fig. 2 (c), IR (KBr, v/cm -1 ) characterization result is: 3416,1624,1470,1384,1296,1170,1080,1044,981,893,800,620,595,524; Adopt its acid strength of n-butylamine potentiometric determination and acid amount, as shown in Figure 3, its acid strength is that under the 684mV(equal conditions, phosphotungstic acid is 702 mV), total acid content is that under the 0.3416mmol/g(equal conditions, phosphotungstic acid is 0.7913 mmol/g); Adopt pyridine-IR (KBr, v/cm -1 ) characterize the acid site type, as shown in Figure 4,1540 peak indicationsBr nsted
Acid site, 1450 indication Lewis acid sites, peak, prove that this ionic liquid hasBr nsted-Lewis bisgallic acid feature.
Synthesizing of [embodiment 2] ionic liquid 2:
(1) take 1,3-propane sultone 12.21 g (0.10 mol) add in there-necked flask (250 mL), add 100 mL toluene to make its dissolving, add again 9.02 g(0.10 mol) the N-methylimidazole, under 50 ℃ of magnetic agitation, logical nitrogen reaction 24 h, carry out suction filtration with reactant liquor, and resulting white precipitate washs three times with ethyl acetate, 60 ℃ of lower vacuum drying 4 h, resulting white powder solid is MIMPS.
(2) take Al (NO
3)
39H
2O 0.50g(1.33 mmol), MIMPS 1.64 g (4 mmol) add in there-necked flask (100 mL), taking phosphotungstic acid 11.52 g (4 mmol) adds 40 mL deionized waters to make its dissolving in beaker, phosphotungstic acid aqueous solution is added in there-necked flask, room temperature under magnetic agitation (25 ℃) reaction 24 h, decompression distillation, 80 ℃ of vacuum drying 6 h, the gained white solid is designated as ionic liquid 2, and its structural formula is:
Its fusing point is 187-190 ℃, is slightly soluble in water, is insoluble to toluene.
As shown in Figure 5, its acid strength is 625mV, and total acid content is 0.1708mmol/g.
Synthesizing of [embodiment 3] ionic liquid 3:
(1) take 1,3-propane sultone 12.21 g (0.10 mol) add in there-necked flask (250 mL), add 100 mL toluene to make its dissolving, add again 9.02 g(0.10 mol) the N-methylimidazole, under 50 ℃ of magnetic agitation, logical nitrogen reaction 24 h, carry out suction filtration with reactant liquor, and resulting white precipitate washs three times with ethyl acetate, 60 ℃ of lower vacuum drying 4 h, resulting white powder solid is MIMPS.
(2) take Al (NO
3)
39H
2O 0.50g(1.33 mmol), MIMPS 1.64 g (8 mmol) add in there-necked flask (100 mL), taking phosphotungstic acid 11.52 g (4 mmol) adds 40 mL deionized waters to make its dissolving in beaker, phosphotungstic acid aqueous solution is added in there-necked flask, room temperature under magnetic agitation (25 ℃) reaction 24 h, decompression distillation, 80 ℃ of vacuum drying 6 h, the gained white solid is designated as ionic liquid 3, and its structural formula is:
Its fusing point is 95-99 ℃, is slightly soluble in water, is insoluble to toluene.
As shown in Figure 6, its acid strength is 673mV, and total acid content is 0.1812mmol/g.
[embodiment 4] in the 100 mL there-necked flasks that thermometer, magneton, reflux condensing tube are housed, add 0.05 mol methyl phenyl ethers anisole, 0.05 mol phenmethylol and 0.10 mmol ionic liquid 1.Be heated to reflux temperature in constant-temperature heating magnetic stirring apparatus hollow gas bath, after reaction 2 h, stop reaction, cooling, decant separates upper organic phase, by the gas chromatograph analysis.The reaction result of ionic liquid 1 catalysis is in Table 1.
[embodiment 5] in the 100 mL there-necked flasks that thermometer, magneton, reflux condensing tube are housed, add 0.05 mol methyl phenyl ethers anisole, 0.05 mol phenmethylol and 0.10 mmol ionic liquid 2.Be heated to reflux temperature in constant-temperature heating magnetic stirring apparatus hollow gas bath, after reaction 2 h, stop reaction, cooling, decant separates upper organic phase, by the gas chromatograph analysis.The reaction result of ionic liquid 2 catalysis is in Table 1.
[embodiment 6] in the 100 mL there-necked flasks that thermometer, magneton, reflux condensing tube are housed, add 0.05 mol methyl phenyl ethers anisole, 0.05 mol phenmethylol and 0.10 mmol ionic liquid 3.Be heated to reflux temperature in constant-temperature heating magnetic stirring apparatus hollow gas bath, after reaction 2 h, stop reaction, cooling, decant separates upper organic phase, by the gas chromatograph analysis.The reaction result of ionic liquid 3 catalysis is in Table 1.
[Comparative Examples 1] in the 100 mL there-necked flasks that thermometer, magneton, reflux condensing tube are housed, adds 0.05 mol methyl phenyl ethers anisole, 0.05 mol phenmethylol and 0.10 mmol ionic liquid [MIMPS]
3PW
12O
40Be heated to reflux temperature in constant-temperature heating magnetic stirring apparatus hollow gas bath, after reaction 2 h, stop reaction, cooling, decant separates upper organic phase, by the gas chromatograph analysis.Ionic liquid [MIMPS]
3PW
12O
40The reaction result of catalysis is in Table 1.
[Comparative Examples 2] in the 100 mL there-necked flasks that thermometer, magneton, reflux condensing tube are housed, adds 0.05 mol methyl phenyl ethers anisole, 0.05 mol phenmethylol and 0.10 mmol ionic liquid [BMIM]
3PW
12O
40Be heated to reflux temperature in constant-temperature heating magnetic stirring apparatus hollow gas bath, after reaction 2 h, stop reaction, cooling, decant separates upper organic phase, by the gas chromatograph analysis.Ionic liquid [BMIM]
3PW
12O
40The reaction result of catalysis is in Table 1.
Table 1 Br nsted-Lewis bisgallic acid ionic-liquid catalyst reactivity worth is estimated
Illustrate: under reaction condition provided by the invention, ionic liquid [BMIM]
3PW
12O
40Benzyl reaction to methyl phenyl ethers anisole and phenmethylol does not have activity; And ionic liquid [MIMPS]
3PW
12O
40Though have greater activity, the benzyl reaction selectivity is lower, has most phenmethylol generation dehydration to generate the accessory substance benzyl oxide; Under ionic-liquid catalyst catalysis provided by the invention, in embodiment 4,5,6, not only phenmethylol approaches fully and transforms, and selectively raising greatly of benzylization, and the accessory substance benzyl oxide generates ratio and greatly reduces; In embodiment 4,5,6, the catalysis benzyl reactivity worth of three kinds of ionic liquids is just corresponding with the acid strength data that characterize out of n-butylamine potentiometric titration in Fig. 3,5,6.
Claims (4)
1. assorted polyion liquid catalyst with Br nsted-Lewis bisgallic acid is characterized in that molecular formula is as follows:
H
X[MIMPS]
YAl
(3-X-Y)/3PW
12O
40
In formula, MIMPS is 1-methyl-3-(3-sulfonic group propyl group) glyoxaline cation; X, Y represent the degree that proton is replaced by cation, and the value of X is that 0 to 1, Y value is 1 to 2, and X+Y＜3.
2. ionic liquid as claimed in claim 1, is characterized in that in cation containing glyoxaline cation, metallic aluminium ion and the hydrogen proton of sulfonic functional, and anion is phosphotungstic acid root anion.
3., as the preparation method of claim 1,2 described ionic liquids, it is characterized in that preparation process is as follows:
(1) the intermediate 1-methyl-3-(3-sulfonic group propyl group) preparation of sulfonate (MIMPS) in imidazoles: react under nitrogen protection with the N-methylimidazole in toluene solvant with PS, obtain MIMPS white precipitate pulverulent solids;
(2) ionic liquid is synthetic: with intermediate MIMPS, Al (NO
3)
39H
2O is anti-lotus cationic source, and phosphotungstic acid is negative ion source, by adjusting the zwitterion ratio, and in the aqueous solution, the assorted polyion liquid catalyst that under room temperature condition, reaction obtains having Br nsted-Lewis bisgallic acid.
4. as claim 1, the application of 2 described ionic liquids in catalysis methyl phenyl ethers anisole and the reaction of phenmethylol benzyl.
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| CN105294407A (en) * | 2014-12-01 | 2016-02-03 | 青岛科技大学 | Benzyl alcohol route anisole benzylation reaction green catalysis method |
| CN106732778A (en) * | 2016-12-30 | 2017-05-31 | 常州大学 | A kind of immobilized heteropoly acid ionic-liquid catalyst and preparation method thereof |
| CN107051582A (en) * | 2017-05-19 | 2017-08-18 | 青岛科技大学 | The Benzylation reaction new method of one kind catalysis |
| CN107376994A (en) * | 2017-07-21 | 2017-11-24 | 闽江学院 | B/L bisgallic acid heteropoly acid ion hybrids and its preparation method and application |
| CN110090664A (en) * | 2019-06-03 | 2019-08-06 | 中国科学院过程工程研究所 | A kind of acidic ion liquid@COF material and its preparation method and application |
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| CN101191035A (en) * | 2007-11-16 | 2008-06-04 | 青岛科技大学 | Brphinsted-Lewis acidic ionic liquid and application thereof in rosin polymerization reaction |
| CN102060738A (en) * | 2010-12-10 | 2011-05-18 | 绍兴文理学院 | Ionic liquid combining B acid site and L acid site as well as preparation method and application thereof |
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| CN105294407A (en) * | 2014-12-01 | 2016-02-03 | 青岛科技大学 | Benzyl alcohol route anisole benzylation reaction green catalysis method |
| CN106732778A (en) * | 2016-12-30 | 2017-05-31 | 常州大学 | A kind of immobilized heteropoly acid ionic-liquid catalyst and preparation method thereof |
| CN106732778B (en) * | 2016-12-30 | 2019-10-11 | 常州大学 | A kind of preparation method of immobilized heteropoly acid ionic-liquid catalyst |
| CN107051582A (en) * | 2017-05-19 | 2017-08-18 | 青岛科技大学 | The Benzylation reaction new method of one kind catalysis |
| CN107051582B (en) * | 2017-05-19 | 2019-08-13 | 青岛科技大学 | A kind of Benzylation reaction new method of catalysis |
| CN107376994A (en) * | 2017-07-21 | 2017-11-24 | 闽江学院 | B/L bisgallic acid heteropoly acid ion hybrids and its preparation method and application |
| CN107376994B (en) * | 2017-07-21 | 2020-07-31 | 闽江学院 | B/L double-acid heteropoly acid ion hybrid and preparation method and application thereof |
| CN110090664A (en) * | 2019-06-03 | 2019-08-06 | 中国科学院过程工程研究所 | A kind of acidic ion liquid@COF material and its preparation method and application |
| CN113101970A (en) * | 2021-04-22 | 2021-07-13 | 福建工程学院 | Composite catalyst for producing methyl ethyl ketone and preparation method thereof |
| CN113578379A (en) * | 2021-07-21 | 2021-11-02 | 北京化工大学 | Bis-sulfonic acid functionalized heteropoly acid ionic liquid for acid catalysis and preparation method thereof |
| CN113603646A (en) * | 2021-08-24 | 2021-11-05 | 天津大学 | Ionic liquid with temperature response performance, preparation method and application in treatment of oily sludge |
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