CN102675209B - Hydroxyl-containing bivalent imidazole type ionic liquid, preparation method thereof, and application thereof - Google Patents
Hydroxyl-containing bivalent imidazole type ionic liquid, preparation method thereof, and application thereof Download PDFInfo
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 44
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229920002678 cellulose Polymers 0.000 claims abstract description 39
- 239000001913 cellulose Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 40
- 150000002500 ions Chemical class 0.000 claims description 28
- 230000005855 radiation Effects 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000002604 ultrasonography Methods 0.000 abstract description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 32
- 239000000243 solution Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 13
- -1 nitrogen-containing heterocycle compound Chemical class 0.000 description 9
- 238000011160 research Methods 0.000 description 6
- 230000006837 decompression Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- PFZPMLROUDTELO-UHFFFAOYSA-N 1-methyl-1h-imidazol-1-ium;acetate Chemical compound CC(O)=O.CN1C=CN=C1 PFZPMLROUDTELO-UHFFFAOYSA-N 0.000 description 1
- 238000005712 Baylis-Hillman reaction Methods 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 230000000191 radiation effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
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Abstract
The invention discloses a hydroxyl-containing bivalent imidazole type ionic liquid, having the following structural formula, wherein R1, R2 and X are defined as the claims and the specification. A preparation method of the hydroxyl-containing bivalent imidazole type ionic liquid comprises the following steps of: dissolving a certain amount of 1-alkyl imidazole into absolute ethyl alcohol, adding acid HX in batches in case of stirring under room temperature, naturally cooling to the room temperature after adding, and dropwise adding 3-chlorine epoxypropane into reaction solution in case of stirring; and putting a reaction bottle into an ultrasonic cleaner for a laboratory, in case of ultrasound irradiation, reacting for a while under a certain temperature, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain the ionic liquid. The invention further relates to the application of the hydroxyl-containing bivalent imidazole type ionic liquid which is independently taken as solvent in the aspect of cellulose dissolving.
Description
Technical field:
The invention belongs to chemical material preparing technical field, relate to a kind of hydroxyl divalence imidazole type ion liquid and its preparation method and application.
Background technology:
Ionic liquid is owing to almost there is no vapour pressure, high chemistry and thermostability, wide electrochemical window, inorganics, organism, catalyzer and polymkeric substance are had to good solubility, and can regulate and control its performance by the cationic moiety of design ionic liquid, become the extensive concern of Chinese scholars research.At present the research interest of ionic liquid is just being presented to unprecedented surge trend, in a large number about ionic liquid is delivered (Deetlefs M successively in article and the patent of the aspect application such as organic synthesis and catalytic chemistry, biotechnology, electrochemistry and materials chemistry, Kenneth R, Seddon.Improved preparations of ionic liquids usingmicrowave irradiation.Green Chemistry, 2003,5:181-186; Jain N, Kumar A, Chauhan S, Chauhan S M S.Chemical and biochemical transformations in ionicliquids, Tetrahedron 2005,61:1015-1060; Mi X, Luo S, Xu H, Zhang L, Cheng J.Hydroxyl ionic liquid-immobilized quinuclidine for Baylis-Hillman catalysis:Synergistic effect of ionic liquidsas organocatalyst support, Tetrahedron 2006,62:2537-2544.).Conventionally the synthetic of ionic liquid is that nitrogen-containing heterocycle compound is carried out to continuous quaternization, carries out subsequently negatively charged ion and replaced.First the first step prepares alkylating halide ions liquid, and it is through replacing or reacted and can be prepared the corresponding ionic liquid that contains different anions by acid-base neutralisation with metal-salt.While adopting the synthetic ionic liquid of method of conventional heating, the first step not only the time used long, and in order to ensure that high yield need to add excessive haloalkane (excessive about 10-400% molar weight) conventionally; The second step of synthetic ionic liquid can produce halogenide (MX or the MH) impurity of stoichiometric in addition, thereby causes the more difficult purifying of product.Obviously from the angle of Green Chemistry, the conventional synthetic method of ionic liquid does not also meet its requirement.Given this, chemists attempt by (Law M C such as microwave radiation, ultrasonic auxiliary, alternative alkylating reagents, Wong K, Chan T H.Solvent-free route to ionic liquid precursors using a water-moderatedmicrowave process, Green Chem.2002,4:328-330;
j, Luche J, P é trier C, Roux R, Bonrath W.An improved preparation of ionic liquids by ultrasound, GreenChem.2002,4:357-360; Liu Gang, Liu Chunping, Sun Lin, Wen Quanwu, Xue Jiantao, synthesizing of the strong .N-methyl-N-of Li Ming (2-hydroxyl-3-benzoyloxy propyl group) imidazole salts ionic liquid. Shandong chemical industry, 2008,37 (4): 1-3.), adopt " one kettle way " synthetic ionic liquid of clean environment firendly, what the research work in this field was carried out is not a lot, belongs to the starting stage, has very bright prospect.
Mierocrystalline cellulose is that occurring in nature is contained the abundantest natural reproducible resource, and storage is about 7,000 hundred million tons, but also regenerates with the speed of annual 40000000000 tons.Because there is no suitable solvent, being often only has 100,000,000 tons of Mierocrystalline celluloses further to be processed as raw material.Conventional solvent that can dissolving cellulos comprises polyoxymethylene, N, the mixture of dinethylformamide and lithium chloride, polyphosphoric acid, inorganic salt solution, dithiocarbonic anhydride etc., more or less there is the shortcomings such as the limited and complex process of toxicity, corrodibility, pollution, dissolving power in them.
Heat and chemically stable, non-volatile, dissolving power are strong, easily recovery, low cost and other advantages because having for ionic liquid, the green non-poisonous solvent system of Chang Zuowei is for cellulosic processing, the features such as the environmental protection, the technique that present due to the method are simple, products obtained therefrom excellent property, have been subject to extensive concern at present.As United States Patent (USP) (US6824599) first discloses the method for a class hydroxyl ion liquid and dissolving cellulos thereof, because the most crystallinity of this class ionic liquid are very strong, in actually operating, be difficult to more than 12% Mierocrystalline cellulose of dissolved ions liquid weight.Chinese patent (CN 100424259C) has been announced a kind of ionic liquid at room temperature containing unsaturated double-bond and its preparation method and application, wherein N-allyl group, N '-Methylimidazole villaumite is 70～100 DEG C of scopes, can reach 10% to cellulosic solubleness, and also do not separate out after cooling, N-allyl group, N '-Methylimidazole acetate also has good dissolving power to Mierocrystalline cellulose in the time of 100 DEG C.But due to the introducing of two keys, understand initiated polymerization and generate new polyelectrolyte, there is the shortcoming of heat and chemically unstable in the ionic liquid that therefore contains the alkylene of unsaturated double-bond, and in the time of dissolving cellulos, is easy to cause loss and the cellulosic degraded of ionic liquid.
Current research shows, ionic liquid is presenting good development momentum as green solvent aspect non-derivative cellulose dissolution, but still there are many deficiencies, and at present selected ionic liquid mostly is conventional glyoxaline ion liquid, and about hydroxyl divalence imidazole type ion liquid and preparation method with have not been reported in the research aspect dissolving cellulos.
Summary of the invention:
For the demand of the deficiencies in the prior art and this area research and application, the object of the present invention is to provide a kind of hydroxyl divalence imidazole type ion liquid and preparation method thereof and the application aspect dissolving cellulos.
A kind of hydroxyl divalence imidazole type ion liquid provided by the invention, its chemical structural formula is as follows:
Wherein: R
1for the saturated hydrocarbyl containing 1～10 carbon atom; R
2for hydrogen or containing the saturated hydrocarbyl of 1～4 carbon atom; X
-for F
-, Cl
-, Br
-, I
-, BF
4 -, CH
3oO
-, CF
3cOO
-, HSO
4 -, PF
6 -, CF
3sO
3 -, [(CF
3sO
2)
2n]
-, PhCOO
-, PhSO
3 -one of.
Preferred R
1for methyl; R
2for hydrogen.
Preferred X
-for Cl
-, BF
4 -, CH
3oO
-, CF
3cOO
-.
The preparation method of a kind of hydroxyl divalence imidazole type ion liquid provided by the present invention, a certain amount of 1-alkyl imidazole is dissolved in dehydrated alcohol, under stirring at room temperature condition, add sour HX in batches, add rear reaction solution and naturally cool to room temperature, under agitation condition, 3-epichlorohydrin is added drop-wise in reaction solution; Reaction flask is put into use for laboratory ultrasonic cleaning instrument, under ultrasonic radiation condition, and in certain temperature reaction for some time, underpressure distillation, vacuum-drying obtains described ionic liquid.
In the preparation method of described a kind of hydroxyl divalence imidazole type ion liquid, sour HX is selected from HF, HCl, HBr, HI, HBF
4, CH
3oOH, CF
3cOOH, H
2sO
4, HPF
6, CF
3sO
3h, [(CF
3sO
2)
2n] H, PhCOOH, PhSO
3one of H.
In the preparation method of described a kind of hydroxyl divalence imidazole type ion liquid, sour HX is preferably HCl, HBF
4, CH
3oOH, CF
3cOOH.
In the preparation method of described a kind of hydroxyl divalence imidazole type ion liquid, X in alkyl imidazole, 3-epichlorohydrin and claim 1
-corresponding sour mol ratio is selected from 1.5: 1: 1～and 7.5: 1: 1; Dehydrated alcohol volume is 1～6 times of 1-alkyl imidazole volume used.
In the preparation method of described a kind of hydroxyl divalence imidazole type ion liquid, it is 300W that ultrasonic radiation condition is selected from power, and frequency is 40KHz.
In the preparation method of described a kind of hydroxyl divalence imidazole type ion liquid, temperature of reaction is selected from 25～100 DEG C; Reaction times is selected from 0.5～24 hour.
In the preparation method of described a kind of hydroxyl divalence imidazole type ion liquid, related reaction equation is as follows:
In the preparation method of described a kind of hydroxyl divalence imidazole type ion liquid, related reaction mechanism is as follows:
Hydroxyl divalence imidazole type ion liquid of the present invention can be applied to separately the cellulosic dissolving of polymer substance, for the preparation of the cellulose solution of spinning.In the cellulose solution of preparation, the mass percent 1%～30% of Mierocrystalline cellulose in solution, preferably 5%～25%.
Prepare the method for described cellulose solution, the cellulose pulp after pulverizing need be dissolved in described hydroxyl divalence imidazole type ion liquid, make uniform cellulose solution by the technique that heats up, stirs and mediate.The solvent temperature of described cellulose pulp in described hydroxyl divalence imidazole type ion liquid is 90～170 DEG C, preferably 110～150 DEG C.In the described cellulose solution process of preparation, in described temperature-rise period, need decompression to remove volatile impunty and the bubble in cellulose solution, finally obtain the cellulose ionic liquid solution of homogeneous transparent.Dissolution time is with the variation such as solvent temperature and alr mode.
Beneficial effect of the present invention is embodied in: hydroxyl divalence imidazole type ion liquid provided by the invention is a kind of new variety, in molecular structure, can there are two kinds of negatively charged ion simultaneously, under such ionic liquid room temperature, be liquid, there is electrochemical stability high, Heat stability is good, the features such as steam forces down, and solubility property is good, are expected to become the type material that has actual application value in Green Chemistry field; Compared with the preparation method of existing ionic liquid, the present invention is taking 1-alkyl imidazole, acid and 3-epichlorohydrin as raw material, under ultrasonic radiation effect, green has been synthesized such ionic liquid cleanly, reaction raw materials is easy to get, easy to operate, good product quality, combined coefficient is high, is applicable to industrial scale and produces; Prepared hydroxyl divalence imidazole type ion liquid has good solubility energy as solvent to Mierocrystalline cellulose separately, is expected to be used widely in the dissolving field of polymer substance.
Embodiment:
Following examples can make the present invention of those skilled in the art comprehend, but do not limit the present invention in any way.Illustrate the preparation method of hydroxyl divalence imidazole type ion liquid of the present invention below by experiment.
embodiment 1: the preparation of 1,3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate ionic liquid
By 40mL1-Methylimidazole (20.6g, 0.50mol) be dissolved in 80mL ethanol, under stirring at room temperature, add 21mL concentrated hydrochloric acid (0.25mol) in batches, add rear reaction solution and naturally cool to room temperature, under agitation condition, chloro-19.6mL 3-propylene oxide (23.12g, 0.25mol) is added drop-wise in reaction solution.Be equipped with after drying tube, reaction flask is placed in the water-bath of experiment ultrasonic cleaning instrument, ultrasonic radiation under 30 DEG C of conditions (power 300W, frequency 40KHz) reaction 2.5h.60 DEG C of rotating pressure-decreasing evaporations, except desolventizing, obtain colourless liquid (59.33g, 83%) after vacuum-drying.
1h-NMR (500MHz, D
2o): δ 8.47 (s, 1H), 8.39 (s, 1H), 7.30 (m, 4H), 4.22 (dd, J=2.10,13.20Hz, 1H), 4.20 (m, 2H), 3.66 (s, 3H), 3.70 (s, 3H), 3.45 (m, 2H).
13c-NMR (500MHz, D
2o): δ 136.34 (CH), 134.82 (CH), 123.44 (CH), 122.78 (CH), 122.69 (CH), 119.36 (CH), 67.84 (CH), 51.88 (CH
2), 45.50 (CH
2), 36.24 (CH
3), 35.26 (CH
3). ultimate analysis, C
11h
18cl
2n
4o, experimental value (calculated value): C, 45.12 (45.06); H, 6.24 (6.19); N, 19.07 (19.11).
embodiment 2: the preparation of 1,3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate tetrafluoroborate ion liquid
By 40mL1-Methylimidazole (20.6g, 0.50mol) be dissolved in 90mL ethanol, under stirring at room temperature, add 33mL Tetrafluoroboric acid (0.25mol) in batches, add rear reaction solution and naturally cool to room temperature, under agitation condition, chloro-19.6mL 3-propylene oxide (23.12g, 0.25mol) is added drop-wise in reaction solution.Be equipped with after drying tube, reaction flask is placed in the water-bath of experiment ultrasonic cleaning instrument, ultrasonic radiation under 40 DEG C of conditions (power 300W, frequency 40KHz) reaction 1.5h.60 DEG C of rotating pressure-decreasing evaporations, except desolventizing, obtain weak yellow liquid (71.48g, 83%) after vacuum-drying.
1h-NMR (500MHz, D
2o): δ 8.58 (s, 1H), 8.43 (s, 1H), 7.30 (m, 4H), 4.29 (dd, J=2.25,13.25Hz, 1H), 4.127 (m, 2H), 3.74 (s, 3H), 3.73 (s, 3H), 3.52 (m, 2H).
13c-NMR (500MHz, D
2o): δ 136.71 (CH), 135.01 (CH), 123.64 (CH), 122.97 (CH), 122.91 (CH), 119.47 (CH), 68.99 (CH), 51.98 (CH
2), 45.52 (CH
2), 35.77 (CH
3), 35.43 (CH
3). ultimate analysis, C
11h
18bClF
4n
4o, experimental value (calculated value): C, 38.31 (38.35); H, 5.29 (5.27); N, 16.22 (16.26).
embodiment 3: the preparation of 1,3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate acetate ions liquid
By 40mL1-Methylimidazole (20.6g, 0.50mol) be dissolved in 90mL ethanol, under stirring at room temperature, add 14mL acetic acid (0.25mol) in batches, add rear reaction solution and naturally cool to room temperature, under agitation condition, chloro-19.6mL3-propylene oxide (23.12g, 0.25mol) is added drop-wise in reaction solution.Be equipped with after drying tube, reaction flask is placed in the water-bath of experiment ultrasonic cleaning instrument, ultrasonic radiation under 25 DEG C of conditions (power 300W, frequency 40KHz) reaction 3.5h.60 DEG C of rotating pressure-decreasing evaporations, except desolventizing, obtain colourless liquid (68.11g, 86%) after vacuum-drying.
1h-NMR (500MHz, D
2o): δ 8.62 (s, 1H), 8.48 (s, 1H), 7.36 (m, 4H), 4.34 (dd, J=2.36,13.40Hz, 1H), 4.22 (m, 2H), 3.84 (s, 3H), 3.76 (s, 3H), 3.60 (m, 2H), 2.22 (s, 3H).
13c-NMR (500MHz, D
2o): δ 188.14 (C=O), 138.88 (CH), 136.24 (CH), 125.44 (CH), 124.48 (CH), 123.86 (CH), 120.28 (CH), 69.88 (CH), 52.76 (CH
2), 46.92 (CH
2), 36.86 (CH
3), 36.21 (CH
3), 21.24 (CH
3). ultimate analysis, C
13h
21clN
4o
3, experimental value (calculated value): C, 49.24 (49.29); H, 6.72 (6.68); N, 17.62 (17.69).
embodiment 4: the preparation of 1,3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate trifluoroacetate ionic liquid
By 40mL1-Methylimidazole (20.6g, 0.50mol) be dissolved in 80mL ethanol, under stirring at room temperature, add 18.6mL trifluoroacetic acid (0.25mol) in batches, add rear reaction solution and naturally cool to room temperature, under agitation condition, chloro-19.6mL 3-bad Ethylene Oxide (23.12g, 0.25mol) is added drop-wise in reaction solution.Be equipped with after drying tube, reaction flask is placed in the water-bath of experiment ultrasonic cleaning instrument, ultrasonic radiation under 50 DEG C of conditions (power 300W, frequency 40KHz) reaction 2.0h.60 DEG C of rotating pressure-decreasing evaporations, except desolventizing, obtain weak yellow liquid (74.15g, 80%) after vacuum-drying.
1h-NMR (500MHz, D
2o): δ 8.76 (s, 1H), 8.28 (s, 1H), 7.16 (m, 4H), 4.18 (dd, J=2.55,13.75Hz, 1H), 4.08 (m, 2H), 3.66 (s, 3H), 3.62 (s, 3H), 3.34 (m, 2H).
13c-NMR (500MHz, D
2o): δ 164.24 (C=O), 138.94 (CH), 137.55 (CH), 125.16 (CH), 123.38 (CH), 122.13 (CH), 120.48 (CH), 115.84 (CF
3), 67.36 (CH), 52.52 (CH
2), 46.69 (CH
2), 36.07 (CH
3), 35.86 (CH
3). ultimate analysis, C
13h
18clF
3n
4o
3, experimental value (calculated value): C, 42.08 (42.11); H, 4.95 (4.89); N, 15.16 (15.11).
embodiment 5: Mierocrystalline cellulose is 1, after 6 grams of cellulose pulps are pulverized in dissolving in 3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate ionic liquid, add while stirring 94 gram 1, in 3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate ionic liquid, mix, sealing is warming up to 140 DEG C under stirring gradually, and in this process, volatile impunty and the bubble in cellulose solution removed in decompression, the final cellulose ionic liquid solution that obtains homogeneous transparent, concentration is 6%.
embodiment 6: the dissolving of Mierocrystalline cellulose in 1,3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate tetrafluoroborate ion liquid
After 14 grams of cellulose pulps are pulverized, add while stirring 86 gram 1, in 3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate tetrafluoroborate ion liquid, mix, sealing is warming up to 120 DEG C under stirring gradually, in this process, volatile impunty and the bubble in cellulose solution removed in decompression, the final cellulose ionic liquid solution that obtains homogeneous transparent, and concentration is 14%.
embodiment 7: the dissolving of Mierocrystalline cellulose in 1,3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate acetate ions liquid
After 12 grams of cellulose pulps are pulverized, add while stirring 88 gram 1, in 3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate acetate ions liquid, mix, sealing is warming up to 150 DEG C under stirring gradually, in this process, volatile impunty and the bubble in cellulose solution removed in decompression, the final cellulose ionic liquid solution that obtains homogeneous transparent, and concentration is 12%.
embodiment 8: the dissolving of Mierocrystalline cellulose in 1,3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate trifluoroacetate ionic liquid
After 8 grams of cellulose pulps are pulverized, add while stirring 92 gram 1, in 3-bis--(1-alkyl imidazole base)-2-propylate hydrochlorate trifluoroacetate ionic liquid, mix, sealing is warming up to 125 DEG C under stirring gradually, in this process, volatile impunty and the bubble in cellulose solution removed in decompression, the final cellulose ionic liquid solution that obtains homogeneous transparent, and concentration is 8%.
Claims (6)
1. a hydroxyl divalence imidazole type ion liquid, is characterized in that the chemical structural formula of this ionic liquid is as follows:
Wherein: R
1for methyl; R
2for hydrogen; X
-for BF
4 -, CH
3cOO
-, CF
3cOO
-one of.
2. the preparation method of hydroxyl divalence imidazole type ion liquid as claimed in claim 1, it is characterized in that: a certain amount of 1-Methylimidazole is dissolved in dehydrated alcohol, under stirring at room temperature condition, add sour HX in batches, add rear reaction solution and naturally cool to room temperature, under agitation condition, 3-epichlorohydrin is added drop-wise in reaction solution; Reaction flask is put into use for laboratory ultrasonic cleaning instrument, under ultrasonic radiation condition, and in certain temperature reaction for some time, underpressure distillation, vacuum-drying obtains described ionic liquid;
Wherein sour HX is selected from HBF
4, CH
3cOOH, CF
3cOOH.
3. the preparation method of hydroxyl divalence imidazole type ion liquid as claimed in claim 2, is characterized in that the mol ratio of 1-Methylimidazole, 3-epichlorohydrin and sour HX is selected from 1.5: 1: 1～7.5: 1: 1; Dehydrated alcohol volume is 1～6 times of 1-Methylimidazole volume used.
4. the preparation method of hydroxyl divalence imidazole type ion liquid as claimed in claim 2, is characterized in that it is 300W that ultrasonic radiation condition is selected from power, and frequency is 40KHz.
5. the preparation method of hydroxyl divalence imidazole type ion liquid as claimed in claim 2, is characterized in that temperature of reaction is selected from 25～100 DEG C; Reaction times is selected from 0.5～24 hour.
6. the application of hydroxyl divalence imidazole type ion liquid as claimed in claim 1 in cellulose dissolution.
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| CN101798286A (en) * | 2009-12-25 | 2010-08-11 | 青岛科技大学 | 1-(3-chlorine-2-hydroxyl-propyl)-3-alkyl imidazole ionic liquid and preparation method thereof |
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| CN101759647A (en) * | 2010-01-08 | 2010-06-30 | 青岛科技大学 | 1, 3-di-(1-methylimidazole)-2-propanol tetrafluoroborate ion liquid and preparation method thereof |
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| 含羟基手臂双咪唑鎓氯盐的合成及其Pd络合物对Suzuki-Miyaura交叉偶联反应的催化活性;康泰然等;《合成化学》;20071231;第15卷(第3期);第301-303页 * |
| 康泰然等.含羟基手臂双咪唑鎓氯盐的合成及其Pd络合物对Suzuki-Miyaura交叉偶联反应的催化活性.《合成化学》.2007,第15卷(第3期),第301-303页. |
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