CN117327301B - Ionic liquid and preparation method and application thereof - Google Patents
Ionic liquid and preparation method and application thereof Download PDFInfo
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- CN117327301B CN117327301B CN202311586569.6A CN202311586569A CN117327301B CN 117327301 B CN117327301 B CN 117327301B CN 202311586569 A CN202311586569 A CN 202311586569A CN 117327301 B CN117327301 B CN 117327301B
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 160
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 124
- 239000002904 solvent Substances 0.000 claims abstract description 87
- 239000000243 solution Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 125000001246 bromo group Chemical group Br* 0.000 claims abstract description 7
- 125000002346 iodo group Chemical group I* 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- -1 n-butylPropyl Chemical group 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 1
- 229920002678 cellulose Polymers 0.000 description 32
- 235000010980 cellulose Nutrition 0.000 description 32
- 239000001913 cellulose Substances 0.000 description 32
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 30
- 238000004090 dissolution Methods 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000002994 raw material Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 15
- 239000004973 liquid crystal related substance Substances 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 150000001768 cations Chemical class 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 230000001681 protective effect Effects 0.000 description 12
- 238000011084 recovery Methods 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 12
- 238000011069 regeneration method Methods 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 229920000875 Dissolving pulp Polymers 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 8
- 230000001112 coagulating effect Effects 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 4
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- IIEJGTQVBJHMDL-UHFFFAOYSA-N 2-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-[2-oxo-2-[3-(sulfamoylamino)pyrrolidin-1-yl]ethyl]-1,3,4-oxadiazole Chemical compound C1CN(CC1NS(=O)(=O)N)C(=O)CC2=NN=C(O2)C3=CN=C(N=C3)NC4CC5=CC=CC=C5C4 IIEJGTQVBJHMDL-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QMGYPNKICQJHLN-UHFFFAOYSA-M Carboxymethylcellulose cellulose carboxymethyl ether Chemical compound [Na+].CC([O-])=O.OCC(O)C(O)C(O)C(O)C=O QMGYPNKICQJHLN-UHFFFAOYSA-M 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011829 room temperature ionic liquid solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 125000001424 substituent group Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to an ionic liquid, a preparation method and application thereof, wherein the structural formula of the ionic liquid is as followsThe method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 、R 2 Each independently selected from chloro, bromo or iodo; r is R 3 Methyl, ethyl, n-propyl or n-butyl; x is Cl or Br; the preparation method comprises the following steps: under the protection of nitrogen or inert gas, in a solventAnd R is 3 X reacts, and is post-treated to obtain the ionic liquid, wherein R 3 X is represented by the formula R 3 And X; the application is as follows: and (3) adding cellulose fibers into a solvent at the temperature of not lower than 20 ℃ to obtain a cellulose fiber solution, or further adding the cellulose fiber solution into an ethanol aqueous solution to precipitate cellulose fibers, wherein the solvent is an ionic liquid or an ionic liquid aqueous solution. The invention can dissolve cellulose fiber in a short time at room temperature (20-35 ℃), and has stronger recycling capability.
Description
Technical Field
The invention belongs to the field of spinning solvents, and relates to an ionic liquid and a preparation method and application thereof.
Background
Because of a large amount of hydrogen bonding between cellulose molecules, cellulose has high crystallinity, is insoluble or insoluble in common solvents, and severely limits the conversion and utilization of cellulose. Therefore, development of various pretreatment techniques for cellulose has been receiving attention. It is well known that cellulose hydrolysis is a critical step prior to downstream processing. However, because of its highly crystalline structure and the extensive intermolecular and intramolecular hydrogen bond network between the fibers, cellulose is rendered insoluble in water and most common solvents.
In order to solve the difficult problem of cellulose processing, various solvent systems have been developed, including viscose solvents, cuprammonium solutions, N-methylmorpholine-N-oxide (NMMO), lithium chloride/methylacetamide, ammonium thiocyanate/liquid ammonia, paraformaldehyde/dimethyl sulfoxide, etc. However, these traditional solvent systems have the disadvantages of unstable solution, high toxicity, environmental pollution, difficult recovery, complex dissolution process, high dissolution temperature, poor product performance, high related cost (NMMO synthesis conditions are severe, the cost is high, and the recovery rate is required to be higher than 99.5% to have economic benefit) and the like.
Ionic liquids are molten salts consisting of organic cations and inorganic or organic anions that are liquid at or near room temperature. The ionic liquid has unique excellent properties such as low vapor pressure, non-volatility, incombustibility, large hot melting, good thermal stability, high ionic conductivity, wide electrochemical window, strong dissolving capacity and the like, so the ionic liquid is widely applied to a plurality of fields as a novel green solvent, and in addition, the ionic liquid has good adjustability, and can obtain the ionic liquid with rich structure and multiple functions by selecting proper anions or adjusting the structure of cations, so the ionic liquid is considered as a green designable solvent.
In document 1, rogers R D Dissolution of cellulose with ionic liquids [ J ]. J. Am. chem. Soc., 2002, 124:4974-4975, synthetic 1-butyl-3-methylimidazole chloride ([ BMIM ] [ Cl ]), is reported, and under room temperature conditions [ BMIM ] Cl does not dissolve untreated cellulose (DP. Apprxeq.1000), but only wets the cellulose to swell, and when the temperature reaches 100-110 ℃, a 10wt% transparent cellulose solution can be formed at maximum.
Document 2, "1-allyl-3-methylimidazole room temperature ionic liquid synthesis and preliminary study of cellulose dissolution property [ J ]. Polymer journal, 2003 (3): 448-450." reports that a novel ionic liquid [ AMIM ] Cl was synthesized by introducing a double bond group into imidazole cation, and was found to exhibit better cellulose dissolution property than [ BMIM ] Cl, and the synthesized ionic liquid had a lower melting point and viscosity, and can rapidly dissolve cellulose in a short time, however [ AMIM ] Cl also could not dissolve cellulose under room temperature conditions, and only made cellulose wet.
Document 3 [ solubility of cellulose in ionic liquid [ AMMor ] Cl/[ AMIM ] Cl mixed solvent [ J ]. Higher school chemistry report, 2009, 30 (7): 1469-1472. ], in order to solve the problems of high cost, high viscosity and the like of ionic liquids, the ionic liquids are mixed to obtain N-methyl-N-allyl morpholine chloride/3-methyl-1-allyl imidazole chloride composite solvent, and researches show that when the same mass fraction (4%) is reached at the same dissolution temperature, the time required for complete dissolution of cellulose in [ AMMor ] Cl/[ AMIM ] Cl mixed solution is much shorter than that in [ AMIM ] Cl, but the cellulose still cannot be dissolved at room temperature, and the maximum solubility of the [ AMMor ] Cl/[ AMIM ] Cl mixed solution to cellulose can reach 17wt% at 80 ℃.
In document 4 [ Extended dissolution studies of cellulose in imidazolium based ionic liquids [ J ]. Green Chemistry, 2009, 11:417-424 ], an alkyl imidazole fluoro salt ionic liquid [ EMIM ] F was synthesized, and the dissolution of microcrystalline cellulose was studied, but the prepared ionic liquid could not dissolve cellulose at room temperature, and only after dissolution for 1h at 100 ℃, a cellulose solution of 2wt% could be obtained.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides an ionic liquid and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an ionic liquid has the structural formula as follows:
；
wherein R is 1 、R 2 Each independently selected from chloro, bromo or iodo; r is R 3 Methyl, ethyl, n-propyl or n-butyl; x is Cl or Br.
The invention also provides a method for preparing the ionic liquid, which comprises the following steps of under the protection of nitrogen or inert gas in a solventAnd R is 3 X, and performing post-treatment (i.e. filtering and drying at 80-100 ℃ for 12-24 h), thereby obtaining the ionic liquid, wherein R 3 X is represented by the formula R 3 And X.
As a preferable technical scheme:
the method comprises the steps that the solvent is more than one of diethyl ether, isopropyl ether, tetrahydrofuran and 1, 4-dioxane;the molar ratio of the solvent to the solvent is 1:100-500->And R is 3 The molar ratio of X is 1:1.1-1.5; the reaction temperature is 20-30 ℃ and the reaction time is 24-72 h.
The invention also provides an application of the ionic liquid, wherein cellulose fibers are added into a solvent at the temperature of not lower than 20 ℃ to obtain a cellulose fiber solution, and the solvent is the ionic liquid or an aqueous solution of the ionic liquid.
Intramolecular or intermolecular hydrogen bonds in cellulose fibers are produced by the action of hydroxyl groups, and therefore, breaking the hydrogen bonds in cellulose fibers can promote dissolution of cellulose fibers. When the ionic liquid disclosed by the invention is used for dissolving cellulose fibers, both cations and anions of the ionic liquid can react with hydroxyl groups of the cellulose fibers, so that hydrogen bonds in the cellulose fiber structure are broken, and the dissolution of the cellulose fibers is promoted. As shown in fig. 1, the ionic liquid can form free anions and cations, hydroxyl groups O in the cellulose fiber interact with cations of the ionic liquid, hydroxyl groups H in the cellulose fiber interact with anions of the ionic liquid, so that hydrogen bonds in the cellulose fiber, including intramolecular hydrogen bonds and intermolecular hydrogen bonds, are broken, thereby causing cracking of molecular chains of the cellulose fiber, and finally, the cellulose fiber is dissolved in the ionic liquid. The cations and anions of the ionic liquid can dissolve cellulose fibers in a synergistic effect, the cations of the ionic liquid are initially combined with the side surface of the cellulose fiber bundles, and the anions of the ionic liquid are inserted into the bundles and form hydrogen bonds with hydroxyl groups, as a large amount of anions of the ionic liquid enter cellulose fiber chains, the cations of the ionic liquid begin to intercalate between the cellulose fiber chains due to strong interactions with the anions of the ionic liquid, and a large amount of ions can provide enough space to separate the cellulose fiber chains, so that the ionic liquid has strong dissolving capability and can efficiently promote cellulose fiber dissolution at room temperature.
The ionic liquid disclosed by the invention can make up for the defects of the ionic liquid in the prior art, and can dissolve cellulose fibers at room temperature because:
(1) the alkyl side chain of the ionic liquid is beneficial to reducing the viscosity of the ionic liquid, compared with the ionic liquid in the prior art, the ionic liquid has lower viscosity (50-60 cP, 20-30 ℃) at room temperature, promotes the contact and the material transmission between the ionic liquid and cellulose fibers, and increases the effective contact between the ionic liquid and the cellulose fibers;
(2) the electron-deficient central nitrogen atom electron cloud density of the cation of the ionic liquid is lower (due to R) 1 、R 2 Electron withdrawing effect of, -CN and the like, pi electrons and R 1 、R 2 -CN group forms p-pi conjugate), the function of forming hydrogen bond on cellulose fiber hydroxyl O is stronger;
(3) r of the ionic liquid of the invention 1 、R 2 Can form halogen bond interaction with hydroxyl H to synergistically promote the breakage of cellulose fiber hydrogen bonds;
(4) the-CN group of the cation of the ionic liquid of the present invention forms hydrogen bonds with-OH in cellulose fibers more easily than other cations;
(5) the imidazole ring in the cation of the ionic liquid has the function of promoting the dissolution of cellulose fiber, and the electron-rich pi system (R 1 And R is 2 Halogen groups such as chlorine group, bromine group and iodine group, and the like, has p-pi conjugation), can interact with oxygen atoms of cellulose fiber hydroxyl groups through non-bond or pi electrons, prevents interaction among cellulose fiber molecules, and promotes sufficient dissolution of cellulose fiber molecules.
As a preferable technical scheme:
for the above applications, the cellulose fiber is MCC, MC, CMC or EC and the degree of polymerization is 15-375.
In the application described above, the concentration of the aqueous solution of the ionic liquid is 15wt% or more.
The application is carried out at the temperature of 20-35 ℃; the ionic liquid can dissolve cellulose fibers at room temperature, overcomes the defects of the prior art, and is preferably 20-35 ℃ in view of low energy consumption at 20-35 ℃.
In the above-mentioned application, the cellulose fiber is added to the solvent and then stirred at 500 to 1500rpm, and the stirring method is not limited, and may be magnetic stirring, mechanical stirring, manual stirring, or the like.
In the application, the time for the cellulose fiber to reach a saturated state in the solvent is 2-5 min, and the solubility (namely, the mass of the dissolved cellulose fiber accounts for the mass of the total solution) is 15.19-28.46 wt%; if the stirring is not performed, the time for the cellulose fiber to reach a saturated state in the solvent is prolonged by 0.5-2 times.
After the cellulose fiber solution is obtained by the application as described above, the cellulose fiber solution is further added to an aqueous solution of ethanol, so that cellulose fibers are precipitated.
The beneficial effects are that:
(1) The ionic liquid of the invention has-CN group, alkyl side chain and imidazole ring, and the-CN group is easier to form hydrogen bond with-OH in cellulose fiber than other cations; the alkyl side chain can help the ionic liquid to keep lower viscosity at room temperature, promote the contact and substance transmission of the ionic liquid and cellulose fibers, and increase the effective contact of the ionic liquid and the cellulose fibers; the imidazole ring has the effect of promoting dissolution of cellulose fibers, and the imidazole cation can interact with oxygen atoms of cellulose hydroxyl groups through non-bond or pi electrons, so that the interaction among cellulose molecules is prevented, and the sufficient dissolution of the cellulose molecules is promoted.
(2) The ionic liquid can be applied to cellulose fiber regeneration, and the recovery rate of the ionic liquid can reach more than 95%, so that the ionic liquid has stronger recovery and utilization capacity.
Drawings
FIG. 1 is a schematic representation of the interaction of an ionic liquid with cellulose fibers of the present invention;
FIG. 2 shows the nuclear magnetic resonance hydrogen spectrum (NMR) of the ionic liquid of example 1 1 H) A figure;
FIG. 3 shows the nuclear magnetic resonance spectrum (NMR) of the ionic liquid of example 1 13 C) A figure;
FIG. 4 shows nuclear magnetic resonance hydrogen spectrum (NMR) of the ionic liquid of example 2 1 H) A figure;
FIG. 5 shows the nuclear magnetic resonance spectrum (NMR) of the ionic liquid of example 2 13 C) A figure;
FIG. 6 shows nuclear magnetic resonance hydrogen spectrum (NMR) of the ionic liquid of example 3 1 H) A figure;
FIG. 7 shows the nuclear magnetic resonance spectrum (NMR) of the ionic liquid of example 3 13 C) A figure;
FIG. 8 is a real viewNuclear magnetic hydrogen Spectrometry (NMR) of the ionic liquid of example 4 1 H) A figure;
FIG. 9 shows the nuclear magnetic resonance spectrum (NMR) of the ionic liquid of example 4 13 C) A figure;
FIG. 10 shows nuclear magnetic resonance hydrogen spectrum (NMR) of the ionic liquid of example 5 1 H) A figure;
FIG. 11 shows the nuclear magnetic resonance spectrum (NMR) of the ionic liquid of example 5 13 C) A figure;
FIG. 12 shows nuclear magnetic resonance hydrogen spectrum (NMR) of the ionic liquid of example 6 1 H) A figure;
FIG. 13 shows the nuclear magnetic resonance spectrum (NMR) of the ionic liquid of example 6 13 C) A drawing.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The following is a method for testing performance in each example:
solubility: the determination is carried out according to ISO 1833-6:2018 standard.
Recovery rate: firstly, dissolving cellulose in an ionic liquid solution with the mass of m1, then adding the ionic liquid solution into a coagulating bath prepared from ethanol and distilled water, dissolving the ionic liquid in the coagulating bath under magnetic stirring to separate out the dissolved cellulose, then pouring a mixed solution of an upper coagulating bath and the ionic liquid, repeatedly washing with a large amount of distilled water, obtaining regenerated cellulose after vacuum drying, finally, decompressing and distilling the mixed solution of the water from which the regenerated cellulose is separated and the ionic liquid, drying the distilled water in a vacuum dryer for more than 24 hours to remove water, and recovering the ionic liquid, wherein the mass of the ionic liquid is m2, and the calculated recovery rate is calculated as follows:×100%。
example 1
An ionic liquid has a structural formula:the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 Is chloro, R 2 Is chloro, R 3 Methyl and X is Cl.
The method for preparing the ionic liquid comprises the following steps:
(1) Preparing raw materials;
protective gas: nitrogen or inert gas;
solvent: diethyl ether;
: the catalyst is prepared by using the existing well-known reaction, namely the synthesis reaction of Debus-Radziszewski imidazole, and the reaction equation is as follows:
；
wherein, the liquid crystal display device comprises a liquid crystal display device,CAS number 4471-47-0, CH 3 NH 2 Has CAS number 74-89-5, < + >>Has a CAS number of 79-37-8;
R 3 x: CAS number 74-87-3;
(2) Under the protection of protective gas, in solvent, the mol ratio is 1:1.1And R is 3 X is reacted for 24 hours at 20 ℃, and the ionic liquid (NMR) is obtained after post treatment 1 FIG. 2 shows the H chart and NMR 13 C is shown in FIG. 3); wherein, the liquid crystal display device comprises a liquid crystal display device,the molar ratio to the solvent was 1:100.
Examples 2 to 6Synthesis of Compounds of the series of substituents of imidazole-4 (5) Using the well-known reaction [ D ]]) The reaction equation is as follows:
；
in the method, in the process of the invention,CAS number>。
Example 2
An ionic liquid has a structural formula:the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 Is bromo, R 2 Is chloro, R 3 Ethyl, X is Br.
The method for preparing the ionic liquid comprises the following steps:
(1) Preparing raw materials;
protective gas: nitrogen or inert gas;
solvent: isopropyl ether;
；
R 3 x: CAS number of；
(2) Under the protection of protective gas, in solvent, the mol ratio is 1:1.2And R is 3 X is reacted for 36 hours at 22 ℃, and the ionic liquid (NMR) is obtained after post treatment 1 FIG. 4 shows the H chart, NMR 13 C is shown in FIG. 5); wherein, the liquid crystal display device comprises a liquid crystal display device,the molar ratio to the solvent was 1:200.
Example 3
An ionic liquid has a structural formula:the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 Is chloro, R 2 Is iodo, R 3 Is n-propyl, X is Cl.
The method for preparing the ionic liquid comprises the following steps:
(1) Preparing raw materials;
protective gas: nitrogen or inert gas;
solvent: tetrahydrofuran;
；
R 3 x: CAS number 540-54-5;
(2) Under the protection of protective gas, in solvent, the mol ratio is 1:1.3And R is 3 X is reacted for 48 hours at 25 ℃, and the ionic liquid (NMR) is obtained after post treatment 1 FIG. 6 shows the H chart, NMR 13 C is shown in FIG. 7); wherein, the liquid crystal display device comprises a liquid crystal display device,the molar ratio to the solvent was 1:300.
Example 4
An ionic liquid has a structural formula:the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 Is bromo, R 2 Is chloro, R 3 Is n-butyl, X is Br.
The method for preparing the ionic liquid comprises the following steps:
(1) Preparing raw materials;
protective gas: nitrogen or inert gas;
solvent: 1, 4-dioxane;
；
R 3 x: CAS number 109-65-9;
(2) Under the protection of protective gas, in solvent, the mol ratio is 1:1.4And R is 3 X is reacted for 60 hours at the temperature of 27 ℃ and is post-treated to obtain the ionic liquid (NMR) 1 FIG. 8 shows the H-chart, NMR 13 C, shown in FIG. 9); wherein, the liquid crystal display device comprises a liquid crystal display device,the molar ratio to the solvent was 1:400.
Example 5
An ionic liquid has a structural formula:the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 Is iodo, R 2 Is bromo, R 3 Methyl and X is Cl.
The method for preparing the ionic liquid comprises the following steps:
(1) Preparing raw materials;
protective gas: nitrogen or inert gas;
solvent: 1, 4-dioxane;
；
R 3 x: CAS number 74-87-3;
(2) Under the protection of protective gas, in solvent, the mol ratio is 1:1.5And R is 3 X is reacted at 30 ℃ for 72h byPost-treatment to obtain an ionic liquid (NMR 1 FIG. 10 shows the H chart, NMR 13 C is shown in FIG. 11); wherein, the liquid crystal display device comprises a liquid crystal display device,the molar ratio to the solvent was 1:500.
Example 6
An ionic liquid has a structural formula:the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 1 Is iodo, R 2 Is iodo, R 3 N-butyl and X is Cl.
The method for preparing the ionic liquid comprises the following steps:
(1) Preparing raw materials;
protective gas: nitrogen or inert gas;
solvent: a mixture of isopropyl ether and 1, 4-dioxane in a mass ratio of 1:1;
；
R 3 x: CAS number 109-69-3;
(2) Under the protection of protective gas, in solvent, the mol ratio is 1:1.45And R is 3 X is reacted for 66h at 28 ℃, and the ionic liquid (NMR) is obtained after post treatment 1 FIG. 12 shows the H chart, NMR 13 C, shown in FIG. 13); wherein, the liquid crystal display device comprises a liquid crystal display device,the molar ratio to the solvent was 1:450.
Example 7
A method for dissolving cellulose fibers by using ionic liquid comprises the following steps:
(1) Preparing raw materials;
cellulose fibers: MCC, polymerization degree is 15;
solvent: the ionic liquid prepared in example 1;
(2) Under the conditions of 20 ℃ and 0.1MPa, 60g of cellulose fiber is added into 200g of solvent, and then the mixture is stirred at 500rpm, and after 2min, the cellulose fiber reaches a saturated state in the solvent, so that the dissolution of the cellulose fiber is realized.
The test showed that the cellulose fiber had a solubility of 15.19wt%.
Example 8
A method for dissolving cellulose fibers by using ionic liquid comprises the following steps:
(1) Preparing raw materials;
cellulose fibers: MC, polymerization degree 52;
solvent: the aqueous solution of the ionic liquid prepared in example 2 had a concentration of 15wt%;
(2) Under the conditions of the temperature of 23 ℃ and the pressure of 0.1MPa, 65g of cellulose fibers are added into 170g of solvent, and then the solvent is stirred at the rotating speed of 750rpm, and after 3min, the cellulose fibers reach a saturated state in the solvent, namely, the dissolution of the cellulose fibers is realized.
The test showed that the cellulose fiber had a solubility of 17.34wt%.
Example 9
A method for dissolving cellulose fibers by using ionic liquid comprises the following steps:
(1) Preparing raw materials;
cellulose fibers: CMC, degree of polymerization 143;
solvent: the aqueous solution of the ionic liquid prepared in example 3 had a concentration of 17wt%;
(2) 70g of cellulose fiber is added into 150g of solvent at the temperature of 27 ℃ and the pressure of 0.1MPa, and then the solvent is stirred at the speed of 1000rpm, and after 4min, the cellulose fiber reaches a saturated state in the solvent, namely, the dissolution of the cellulose fiber is realized.
The test showed that the cellulose fiber had a solubility of 19.67wt%.
Example 10
A method for dissolving cellulose fibers by using ionic liquid comprises the following steps:
(1) Preparing raw materials;
cellulose fibers: EC, degree of polymerization 269;
solvent: the aqueous solution of the ionic liquid prepared in example 4 had a concentration of 20wt%;
(2) Under the conditions of the temperature of 31 ℃ and the pressure of 0.1MPa, 75g of cellulose fibers are added into 130g of solvent, and then the mixture is stirred at 1250rpm, and after 5min, the cellulose fibers reach a saturated state in the solvent, namely, the dissolution of the cellulose fibers is realized.
The test showed that the cellulose fiber had a solubility of 24.23wt%.
Example 11
A method for dissolving cellulose fibers by using ionic liquid comprises the following steps:
(1) Preparing raw materials;
cellulose fibers: MCC with degree of polymerization 375;
solvent: the aqueous solution of the ionic liquid prepared in example 5 had a concentration of 24wt%;
(2) 80g of cellulose fiber is added into 100g of solvent at 35 ℃ and 0.1MPa, and then the solvent is stirred at 1500rpm, and after 5min, the cellulose fiber reaches a saturated state in the solvent, so that the dissolution of the cellulose fiber is realized.
The test showed that the cellulose fiber had a solubility of 28.46wt%.
Example 12
A method for dissolving cellulose fibers with an ionic liquid, substantially as herein described with reference to example 11, except that: the solvent in the step (1) was an aqueous solution of the ionic liquid prepared in example 6 at a concentration of 22wt%.
The test showed that the cellulose fiber had a solubility of 26.21wt%.
Example 13
A regeneration method of cellulose fiber comprises the following steps:
(1) Preparing raw materials;
a substance comprising cellulose fibers: MCC, manufacturer is national medicine control chemical reagent company, CAS number 9004-34-6;
solvent: the aqueous solution of the ionic liquid prepared in example 1 had a concentration of 15wt%;
aqueous ethanol solution: the concentration is 5wt%;
(2) Adding 60g of a substance containing cellulose fibers into 200g of a solvent at 20 ℃ and 0.1MPa, stirring at 500rpm, and filtering to remove insoluble substances after the cellulose fibers reach a saturated state in the solvent after 2min to obtain a cellulose fiber solution;
(3) Adding cellulose fiber solution into ethanol water solution, dissolving ionic liquid in coagulating bath under magnetic stirring, and separating out dissolved cellulose to realize cellulose fiber regeneration;
(4) Distilling the mixed solution of water and the ionic liquid after separating out cellulose fibers under reduced pressure, drying the mixed solution in a vacuum dryer for 24 hours to remove the water, and recovering to obtain the ionic liquid;
(5) Repeating the operations of the steps (1) - (4) for 10 times; wherein the ionic liquid in the solvent in the step (1) from the second operation is the ionic liquid recovered in the step (4) in the previous operation.
Tests show that the recovery rate of the ionic liquid is 95%.
Example 14
A regeneration method of cellulose fiber comprises the following steps:
(1) Preparing raw materials;
a substance comprising cellulose fibers: MC, manufacturer is Hubei Xinyuhong, CAS number 9004-67-5;
solvent: the ionic liquid prepared in example 2;
aqueous ethanol solution: the concentration is 10wt%;
(2) Adding 65g of a substance containing cellulose fibers into 170g of a solvent at 24 ℃ and 0.1MPa, stirring at 700rpm, and filtering to remove insoluble substances after the cellulose fibers reach a saturated state in the solvent after 3min to obtain a cellulose fiber solution;
(3) Adding cellulose fiber solution into ethanol water solution, dissolving ionic liquid in coagulating bath under magnetic stirring, and separating out dissolved cellulose to realize cellulose fiber regeneration;
(4) Distilling the mixed solution of water and the ionic liquid after separating out cellulose fibers under reduced pressure, drying the mixed solution in a vacuum dryer for 28 hours to remove water, and recovering to obtain the ionic liquid;
(5) Repeating the operations of the steps (1) - (4) for 15 times; wherein the ionic liquid in the solvent in the step (1) from the second operation is the ionic liquid recovered in the step (4) in the previous operation.
Tests show that the recovery rate of the ionic liquid is 96%.
Example 15
A regeneration method of cellulose fiber comprises the following steps:
(1) Preparing raw materials;
a substance comprising cellulose fibers: CMC, manufacturer is clamar reagent, CAS number 9004-32-4;
solvent: the aqueous solution of the ionic liquid prepared in example 3 had a concentration of 18wt%;
aqueous ethanol solution: the concentration is 18wt%;
(2) Adding 70g of a substance containing cellulose fibers into 150g of a solvent at 28 ℃ and 0.1MPa, stirring at 900rpm, and filtering to remove insoluble substances after the cellulose fibers reach a saturated state in the solvent after 4min to obtain a cellulose fiber solution;
(3) Adding cellulose fiber solution into ethanol water solution, dissolving ionic liquid in coagulating bath under magnetic stirring, and separating out dissolved cellulose to realize cellulose fiber regeneration;
(4) Distilling the mixed solution of water and the ionic liquid after separating out cellulose fibers under reduced pressure, drying the mixed solution in a vacuum dryer for 32 hours to remove the water, and recovering to obtain the ionic liquid;
(5) Repeating the operations of the steps (1) - (4) for 20 times; wherein the ionic liquid in the solvent in the step (1) from the second operation is the ionic liquid recovered in the step (4) in the previous operation.
The test shows that the recovery rate of the ionic liquid is 97%.
Example 16
A regeneration method of cellulose fiber comprises the following steps:
(1) Preparing raw materials;
a substance comprising cellulose fibers: EC, manufacturer is Hubei cloud magnesium science and technology Co., ltd, CAS number is 9004-57-3;
solvent: the ionic liquid prepared in example 4, or the aqueous solution of the ionic liquid prepared in example 4, had a concentration of 24wt%;
aqueous ethanol solution: the concentration is 24wt%;
(2) Adding 75g of a substance containing cellulose fibers into 130g of a solvent at the temperature of 32 ℃ and the pressure of 0.1MPa, stirring at the rotation speed of 1200rpm, and filtering to remove insoluble substances after the cellulose fibers reach a saturated state in the solvent after 5min to obtain a cellulose fiber solution;
(3) Adding cellulose fiber solution into ethanol water solution, dissolving ionic liquid in coagulating bath under magnetic stirring, and separating out dissolved cellulose to realize cellulose fiber regeneration;
(4) Distilling the mixed solution of water and the ionic liquid after separating out cellulose fibers under reduced pressure, drying the mixed solution in a vacuum dryer for 36 hours to remove the water, and recovering to obtain the ionic liquid;
(5) Repeating the operations of the steps (1) - (4) for 25 times; wherein the ionic liquid in the solvent in the step (1) from the second operation is the ionic liquid recovered in the step (4) in the previous operation.
Tests show that the recovery rate of the ionic liquid is 98%.
Example 17
A regeneration method of cellulose fiber comprises the following steps:
(1) Preparing raw materials;
a substance comprising cellulose fibers: MCC, manufacturer is national medicine control chemical reagent company, CAS number 9004-34-6;
solvent: the aqueous solution of the ionic liquid prepared in example 5 had a concentration of 29wt%;
aqueous ethanol solution: the concentration is 30wt%;
(2) Adding 80g of a substance containing cellulose fibers into 100g of a solvent at 35 ℃ and 0.1MPa, stirring at 1500rpm, and filtering to remove insoluble substances after the cellulose fibers reach a saturated state in the solvent after 5min to obtain a cellulose fiber solution;
(3) Adding cellulose fiber solution into ethanol water solution, dissolving ionic liquid in coagulating bath under magnetic stirring, and separating out dissolved cellulose to realize cellulose fiber regeneration;
(4) Distilling the mixed solution of water and the ionic liquid after separating out cellulose fibers under reduced pressure, drying the mixed solution in a vacuum dryer for 48 hours to remove the water, and recovering to obtain the ionic liquid;
(5) Repeating the operations of the steps (1) - (4) for 30 times; wherein the ionic liquid in the solvent in the step (1) from the second operation is the ionic liquid recovered in the step (4) in the previous operation.
Tests show that the recovery rate of the ionic liquid is 99%.
Example 18
A method of regenerating cellulose fibers substantially as herein described with reference to example 17, but with the exception of: the solvent prepared in the step (1) was an aqueous solution of the ionic liquid prepared in example 6, at a concentration of 22wt%;
the test shows that the recovery rate of the ionic liquid is 97%.
Claims (10)
1. An ionic liquid is characterized by having the following structural formula:
；
wherein R is 1 、R 2 Each independently selected from chloro, bromo or iodo; r is R 3 Is methyl, ethyl, n-butylPropyl or n-butyl; x is Cl or Br.
2. A process for preparing an ionic liquid as claimed in claim 1, wherein the ionic liquid is prepared by reacting a mixture of the components mentioned in the above under nitrogen or inert gas in a solventAnd R is 3 X reacts, and is post-treated to obtain the ionic liquid, wherein R 3 X is represented by the formula R 3 And X.
3. The method according to claim 2, wherein the solvent is one or more of diethyl ether, isopropyl ether, tetrahydrofuran, and 1, 4-dioxane;the molar ratio of the solvent to the solvent is 1:100-500->And R is 3 The molar ratio of X is 1:1.1-1.5; the reaction temperature is 20-30 ℃ and the reaction time is 24-72 h.
4. Use of an ionic liquid according to claim 1, wherein cellulose fibres are added to a solvent at a temperature not lower than 20 ℃ to obtain a cellulose fibre solution, wherein the solvent is an ionic liquid or an aqueous solution of an ionic liquid.
5. The use according to claim 4, wherein the cellulose fiber is MCC, MC, CMC or EC and has a degree of polymerization of 15 to 375.
6. The use according to claim 4, wherein the concentration of the aqueous solution of the ionic liquid is more than 15 wt%.
7. The use according to claim 4, wherein the temperature is 20-35 ℃.
8. The use according to claim 7, characterized in that the cellulose fibres are further stirred after addition to the solvent at a rotational speed of 500 to 1500rpm.
9. Use according to claim 8, characterized in that the cellulose fibres reach a saturation state in the solvent for 2-5 min and a solubility of 15.19-28.46 wt%.
10. The use according to claim 4, wherein after the cellulose fiber solution is obtained, the cellulose fiber solution is further added to an aqueous solution of ethanol, such that the cellulose fibers are precipitated.
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