CN102146165B - Protic ionic liquid, preparation method and application of protic ionic liquid in cellulose dissolution and regeneration - Google Patents
Protic ionic liquid, preparation method and application of protic ionic liquid in cellulose dissolution and regeneration Download PDFInfo
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- CN102146165B CN102146165B CN 201010616531 CN201010616531A CN102146165B CN 102146165 B CN102146165 B CN 102146165B CN 201010616531 CN201010616531 CN 201010616531 CN 201010616531 A CN201010616531 A CN 201010616531A CN 102146165 B CN102146165 B CN 102146165B
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- mierocrystalline cellulose
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Abstract
The invention discloses protic ionic liquid used for dissolving cellulose. The components of the protic ionic liquid are shown in a formula of HB+A-, wherein B is sulfur-containing organic or inorganic compound, and A is 98 mass percent concentrated sulfuric acid. The preparation method comprises the following steps of: slowly dripping sulfuric acid into a sulfur-containing compound, and stirring to obtain the protic ionic liquid. The system is used for cellulose dissolution and regeneration and has high capacity of dissolving the cellulose, and after the system is fully stirred at room temperature, the cellulose dissolubility is 10 to 30 percent. The dissolved cellulose is subjected to a wet spinning technology, ethanol is used as setting liquid, drawing molding is carried out, and a solvent is recovered. The cellulose is directly dissolved in the prepared protic ionic liquid, and the cellulose dissolubility is obviously improved. Flows such as alkalization and sulfonation in the production process are simplified, and the problem of environmental pollution due to fiber processing is solved; moreover, the fiber production cost can be reduced and the quality stability of the fiber is improved.
Description
Technical field
The present invention relates to a kind of proton type ionic liquid and the application in cellulose dissolution thereof, belong to cellulose regenerated technical field.
Background technology
Cellulosic fibre is the regenerated fibre that becomes textile fibres the earliest, has advantages such as comfortable and easy to wear, that permeability is good, therefore in fields such as weaving, clothes purposes is widely arranged.Mierocrystalline cellulose (C
6H
10O
5) n connects the linear macromolecule form with β-1,4 glycoside bond each other by D2 Glucopyranose acid anhydride, structural unit is a glucone, and adjacent two glucone positions each other are 180 ° to be reversed, and makes 1, and the 4-carbon potential is connected firmly.This structure makes the complex construction of cellulose macromolecule in the hydrogen bond of intramolecularly and intermolecular formation mortise and crystalline region and non-crystalline region coexistence, thereby makes Mierocrystalline cellulose be difficult to be dissolved in common solvent and form true solution.Therefore seek technology simply, Mierocrystalline cellulose novel solvent safely and effectively, be that numerous scientific workers pay close attention to and the important subject of being engaged in always.Nearly 30; The various countries scientist is devoted to study the little cellosolve system of environmental pollution; As: Paraformaldehyde 96/DMSO 99.8MIN. (PF/DMSO) system, nitrogen tetroxide/N (N2O4/DMF) system, lithium chloride/N,N-DIMETHYLACETAMIDE (LiCl/DMAc) system, DMSO 99.8MIN./TEA chloride (DMSO/TEAC) system, ammonia/ammonium thiocyanide (NH3/NH4SCN) system and amine oxide equal solvent system all have certain solubleness to fiber; But there is difficult solvent recovery, the fibrous texture defectiveness of generation, the first-class shortcoming of streaking.
Recent years, people begin to attempt making the dissolution with solvents Mierocrystalline cellulose with ionic liquid.Ionic liquid is called ionic liquid at room temperature, room temperature fused salt, organic ion liquid etc., the ionic compound that under room temperature or low temperature, is in a liquid state again.Since ion liquid designability, the positive fast-developing growth of more than ten years ionic liquid family recently.Except common glyoxaline ion liquid, eutectic solvent, coordination ion liquid etc. have also appearred.The proton type ionic liquid combines to form through B acid and B alkali, and in cohesive process, proton is transferred to alkali from acid, forms proton contribution body and proton acceptor, further forms the hydrogen bond network structure then.Because the proton ionic liquid leans on hydrogen bonded to arrive together, cellulose macromolecule also is to lean on hydrogen bonded together, as long as positively charged ion and the hydroxyl hydrogen bond bonding force in object and the Mierocrystalline cellulose in the ionic liquid are strong; Just can destroy the hydrogen bond between cellulosic molecule; Then destroy cellulosic aggregated structure, finally make cellulose dissolution, reach the purpose of dissolving cellulos; And the hydrogen bond that forms is many more, and intensity is high more big more to cellulosic solubleness.The dissolved Mierocrystalline cellulose adopts the wet-spinning technology in the proton type ionic liquid, does solid solution with ethanol, and wire-drawing shape makes ethanol evaporation through the mode that heats, and reclaims solvent.
Summary of the invention
The purpose of this invention is to provide a kind of proton type ionic liquid.
Another object of the present invention provides above-mentioned preparation method of ionic liquid.
The present invention also aims to provide the application of above-mentioned ionic liquid in cellulose dissolution.
Design of the present invention is such.Because the proton type ionic liquid leans on hydrogen bonded to arrive together, cellulose macromolecule also is to lean on hydrogen bonded together, as long as positively charged ion and the hydroxyl hydrogen bond bonding force in object and the Mierocrystalline cellulose in the ionic liquid are strong; Just can destroy the hydrogen bond between cellulosic molecule; Then destroy cellulosic aggregated structure, finally make cellulose dissolution, reach the purpose of dissolving cellulos; And the hydrogen bond that forms is many more, and intensity is high more big more to cellulosic solubleness.In sulfuric acid/sulfocompound system, sulphur combines with the hydrogen proton, makes the carbon ribbon positive charge, then with Mierocrystalline cellulose in hydroxyl form the C-O-Cell key, destroy the hydrogen bond in the cellulosic molecule.Possible mechanism is shown in following reaction formula:
For this reason, the ion liquid composition of proton type that provides of the present invention is as shown in the formula expression:
HB
+A
-, in the formula, B is the inorganic or organic cpds of sulfur-bearing, A is that massfraction is 98% the vitriol oil.
The mineral compound of sulfur-bearing is: wherein a kind of such as ammonium thiocyanide, Sodium Thiocyanate 99, Rhocya;
The organic cpds of sulfur-bearing is: wherein a kind of such as thiocarbamide, thioacetamide, thiophene, Gelucystine.
The said proton type preparation method of ionic liquid of the present invention is following:
Ratio by amount of substance takes by weighing the sulfocompound and the vitriol oil respectively for (1: 1)～(1: 5); The vitriol oil is placed ice-water bath, join sulfocompound slowly in the vitriol oil then, slowly stir; Dissolve fully up to sulfocompound, can obtain the proton type ionic liquid.
The application method of the said proton type ionic liquid of the present invention in cellulose dissolution and regeneration may further comprise the steps:
(1) earlier ionic liquid is heated to 30～60 ℃;
(2) by being 5%～30% to take by weighing Mierocrystalline cellulose, and it is slowly joined in the ionic liquid gradually, stir, dissolve fully up to Mierocrystalline cellulose with the ionic liquid mass ratio;
(3) dissolved Mierocrystalline cellulose employing wet-spinning technology is regenerated through the spinning machinery spinning and in alcohol solidification is bathed and is solidified.
Among the present invention, the application of proton type ionic liquid in cellulose dissolution and regeneration, said Mierocrystalline cellulose is a kind of in cotton fibre, xylon, bamboo fibers, the straw fiber.
The beneficial effect that the present invention obtains is following:
(1) cost of material that adopts of the present invention cheap, be easy to get, and the preparation method is simple, the ionic liquid that obtains need not be purified.
(2) Mierocrystalline cellulose directly is dissolved in the prepared proton type ionic liquid, the cellulose dissolution degree is significantly improved.
(3) the present invention has not only simplified flow processs such as alkalization, sulfonation in the production technique, has solved the fiber process problem of environmental pollution, and can reduce the fiber production cost, has improved quality of fiber stability.
(4) Mierocrystalline cellulose can be regenerated in ethanol in wire drawing, and solvent recuperation is easy, nontoxicity by product and sewage discharge, and complete processing is simple, ME is reliable.
Embodiment
Following examples are used to explain the present invention.
Embodiment 1
Take by weighing ammonium thiocyanide 7.6 grams, massfraction 98% vitriol oil 9.8～49 grams.Place ice-water bath to sulfuric acid, join ammonium thiocyanide in the sulfuric acid slowly then.After dropwising, slowly stir, dissolve fully up to ammonium thiocyanide.Take by weighing synthetic ionic liquid 10 grams, place heating jacket to be warming up to 30～60 ℃ of insulations.Take by weighing 0.5～3 gram cotton fibre, cotton fibre bit by bit is added in the ionic liquid, be stirred to Mierocrystalline cellulose then and dissolve fully.Dissolved Mierocrystalline cellulose employing wet-spinning technology is regenerated through the spinning machinery spinning and in alcohol solidification is bathed and is solidified.Contain the alcoholic acid solvent and can add heat extraction ethanol, pure ion liquid solvent obtains reclaiming.
Embodiment 2
Take by weighing thiocarbamide 7.6 grams, massfraction 98% vitriol oil 9.8～49 grams.Be added drop-wise to sulfuric acid in the thiocarbamide slowly.After dropwising, slowly stir, dissolve fully up to thiocarbamide.Take by weighing synthetic ionic liquid 10 grams, place heating jacket to be warming up to 30～60 ℃ of insulations.Take by weighing 3 gram cotton fibre, cotton fibre bit by bit is added in the ionic liquid, be stirred to Mierocrystalline cellulose then and dissolve fully.Contain the alcoholic acid solvent and can add heat extraction ethanol, pure ion liquid solvent obtains reclaiming.
Embodiment 3
Take by weighing thioacetamide 7.3 grams, massfraction 98% vitriol oil 9.8～49 grams.Be added drop-wise to sulfuric acid in the thioacetamide slowly.After dropwising, slowly stir, dissolve fully up to thioacetamide.Take by weighing synthetic ionic liquid 10 grams, place heating jacket to be warming up to 30～60 ℃ of insulations.Take by weighing 0.5～3 gram cotton fibre, cotton fibre bit by bit is added in the ionic liquid, be stirred to Mierocrystalline cellulose then and dissolve fully.Contain the alcoholic acid solvent through adding heat extraction ethanol, pure ion liquid solvent obtains reclaiming.
Embodiment 4
Take by weighing Gelucystine 24.0 grams, massfraction 98% vitriol oil 9.8～49 grams.Be added drop-wise to sulfuric acid in the Gelucystine slowly.After dropwising, slowly stir, dissolve fully up to Gelucystine.Take by weighing synthetic ionic liquid 8 grams, place heating jacket to be warming up to 30～60 ℃ of insulations.Take by weighing 0.4～2.4 gram cotton fibre, cotton fibre bit by bit is added in the ionic liquid, be stirred to Mierocrystalline cellulose then and dissolve fully.Contain the alcoholic acid solvent through adding heat extraction ethanol, pure ion liquid solvent obtains reclaiming.
Embodiment 5
Take by weighing thiophene 8.4 grams, massfraction 98% vitriol oil 9.8～49 grams.Be added drop-wise to sulfuric acid in the thiophene slowly.After dropwising, slowly stir, dissolve fully up to thiophene.Take by weighing synthetic ionic liquid 8 grams, place heating jacket to be warming up to 30～60 ℃ of insulations.Take by weighing 0.4～2.4 gram cotton fibre, cotton fibre bit by bit is added in the ionic liquid, be stirred to Mierocrystalline cellulose then and dissolve fully.With solution wire drawing in ethanol of dissolving cellulos, can obtain the Mierocrystalline cellulose of white.Contain the alcoholic acid solvent through adding heat extraction ethanol, pure ion liquid solvent obtains reclaiming.
Embodiment 6
Take by weighing KSCN 9.7 grams, massfraction 98% vitriol oil 9.8～49 grams.Be added drop-wise to sulfuric acid among the KSCN slowly.After dropwising, slowly stir, dissolve fully up to KSCN.Take by weighing synthetic ionic liquid 8 grams, place heating jacket to be warming up to 30～60 ℃ of insulations.Take by weighing 0.4～2.4 gram cotton fibre, cotton fibre bit by bit is added in the ionic liquid, be stirred to Mierocrystalline cellulose then and dissolve fully.With solution wire drawing in ethanol of dissolving cellulos, can obtain the Mierocrystalline cellulose of white.Contain the alcoholic acid solvent through adding heat extraction ethanol, pure ion liquid solvent obtains reclaiming.
Embodiment 7
Take by weighing NaSCN 8.1 grams, massfraction 98% vitriol oil 9.8～49 grams.Be added drop-wise to sulfuric acid among the NaSCN slowly.After dropwising, slowly stir, dissolve fully up to NaSCN.Take by weighing synthetic ionic liquid 8 grams, place heating jacket to be warming up to 30～60 ℃ of insulations.Take by weighing 0.4～2.4 gram cotton fibre, cotton fibre bit by bit is added in the ionic liquid, be stirred to Mierocrystalline cellulose then and dissolve fully.With solution wire drawing in ethanol of dissolving cellulos, can obtain the Mierocrystalline cellulose of white.Contain the alcoholic acid solvent through adding heat extraction ethanol, pure ion liquid solvent obtains reclaiming.
Claims (4)
1. proton type ionic liquid, it is characterized in that: its general formula is HB
+A
-, in the formula, A is that massfraction is 98% the vitriol oil; B is the inorganic or organic cpds of sulfur-bearing, is wherein a kind of of following material: thiocyanate-, thiocarbamide, thioacetamide, thiophene, Gelucystine.
2. proton type preparation method of ionic liquid as claimed in claim 1; It is characterized in that: the mineral compound or the organic cpds and the vitriol oil that take by weighing sulfur-bearing by the ratio of amount of substance for (1: 1)～(1: 5) respectively; The vitriol oil is placed ice-water bath, join the mineral compound of sulfur-bearing or organic cpds slowly in the vitriol oil then, slowly stir; Mineral compound or organic cpds up to sulfur-bearing dissolve fully, can obtain the proton type ionic liquid.
3. the application of proton type ionic liquid as claimed in claim 1 in cellulose dissolution and regeneration is characterized in that may further comprise the steps:
(1) earlier ionic liquid is heated to 30～60 ℃;
(2) by being 5%～30% to take by weighing Mierocrystalline cellulose, and it is slowly joined in the ionic liquid gradually, stir, dissolve fully up to Mierocrystalline cellulose with the ionic liquid mass ratio;
(3) dissolved Mierocrystalline cellulose employing wet-spinning technology is regenerated through the spinning machinery spinning and in alcohol solidification is bathed and is solidified.
4. the application of proton type ionic liquid as claimed in claim 3 in cellulose dissolution and regeneration is characterized in that, said Mierocrystalline cellulose is a kind of in following: cotton fibre, xylon, bamboo fibers, leather fiber.
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| EP2981641B1 (en) * | 2013-04-04 | 2024-05-15 | Aalto University Foundation sr | Process for the production of shaped cellulose articles |
| WO2017011232A1 (en) | 2015-07-10 | 2017-01-19 | Uop Llc | Synthesis of non-cyclic amide and thioamide based ionic liquids |
| WO2017011222A1 (en) | 2015-07-10 | 2017-01-19 | Uop Llc | Hydrocarbon conversion processes using non-cyclic amide and thioamide based ionic liquids |
| CN106702800B (en) * | 2016-12-30 | 2019-02-26 | 中国科学院过程工程研究所 | A method of straw lignin and hemicellulose are removed with proton type ionic liquid |
| CN115961368B (en) * | 2022-11-30 | 2023-09-12 | 新乡化纤股份有限公司 | Ionic liquid method fungus grass regenerated cellulose fiber and preparation method thereof |
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