KR20140044624A - Process for depolymerization of cellulose using acidic ionic liquid catalysts - Google Patents
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- MIESUULGXMFVEM-UHFFFAOYSA-N CC[N]1(CCCS(O)(=O)=O)CCCC1 Chemical compound CC[N]1(CCCS(O)(=O)=O)CCCC1 MIESUULGXMFVEM-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
The present invention relates to an acidic ionic liquid catalyst used in the depolymerization of cellulose.
The present invention also relates to a method for depolymerization of cellulose to produce cellulose oligosaccharides by reacting cellulose with an acidic ionic liquid catalyst.
Cellulose is the basic structural component of plant cell walls, accounting for 33% of all plant material, and is the most abundant substance in organic matter produced in nature. In particular, the use of herbal cellulose is a resource that can be supplied indefinitely, and is recognized as a sustainable raw material that can replace the existing fossil fuel, but in order to use it efficiently, some obstacles must be overcome first. One of them must be able to convert a biomass called lignocellulosic material into a fermentable state. The value of fermentable sugars is not only bio-energy, but also the value of infinite raw material which is not exhausted in almost all industries such as pharmaceutical, textile, food and cosmetics. Accordingly, research on fuels and compounds that can be used as renewable feedstocks that can replace fossil fuels by changing sugars is increasing.
The most difficult process in producing biofuels or compounds from biomass is to hydrolyze cellulose into fermentable sugars. Cellulose in biomass can produce cellulosic textiles directly through suitable spinning techniques and is also an endless source of glucose. However, the cellulose chain is composed of beta (1,4) -glycosidic bonds, so there is no solubility in water or organic solvents.
Recently, it has been reported that cellulose dissolves in certain ionic liquids ( J. Am . Chem . Soc. 2002 , 124, 4974 4975). Since then, several researchers have fermented through saccharification using acid catalysts. The method of preparing possible sugars (fermented sugar: glucose or cellobiose, etc.) was studied. However, the fermentable sugar has a problem that the separation process is very difficult because of the high solubility in ionic liquids. This problem can be solved by depolymerization from cellulose to cellulooligosaccharides without the complete depolymerization from cellulose. Accordingly, there is a need for an advanced technology for efficiently separating ionic liquids and depolymerized cellulose oligosaccharides and efficiently regenerating ionic liquids and acid catalysts used in the dissolution process.
It is an object of the present invention to provide an acidic ionic liquid catalyst for cellulose depolymerization.
Another object of the present invention is to provide a cellulose depolymerization method capable of producing cellulose oligosaccharides of high yield by reacting cellulose with an acidic ionic liquid catalyst for cellulose depolymerization. More specifically, an object of the present invention is to prepare a cellulose oligosaccharide in the form of a hydrogel, and to provide a cellulose depolymerization method capable of easily separating the cellulose oligosaccharide from an ionic liquid or an acidic ionic liquid catalyst.
The present invention for achieving the above object relates to an acidic ionic liquid catalyst for cellulose depolymerization comprising any one or two or more compounds selected from the following formula (1).
(Formula 1)
[A +] [X -]
In Formula 1, A + is
The R 1 To R 12 are each independently of the other C 1 -C 6 alkyl group, C 1 -C 6 alkylcarboxyl group, C 1 -C 6 alkylester group, hydroxyC 1 -C 6 alkyl group, dihydroxyC 1 -C 6 An alkyl group, a C 1 -C 6 alkoxyC 1 -C 6 alkyl group, a C 6 -C 20 aryl group or a halogen atom,
The aryl group is C 1 -C 6 alkyl group, halogen group, nitro group, cyano group, hydroxy group, amino group, C 6 -C 20 aryl group, C 2 -C 7 alkenyl group, C 3 -C 20 cycloalkyl group, N, O At least one further selected from a 5 to 7 membered heterocycloalkyl group including at least one element selected from S or a C 4 -C 20 heteroaryl group containing at least one element selected from N, O and S Can be,
N is an integer selected from 1 to 4, X - represents a monovalent anion.
In addition, the present invention is the R 1 To R 12 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, acetyl group, propyl group, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, hydroxymethyl, hydroxy Selected from the group consisting of ethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, 1,2-dihydroxyethyl, dimethoxymethyl, methoxyethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, and phenyl groups Become,
The phenyl may be further substituted with bromo, fluorine, trifluoromethyl, cyano, trifluoromethoxy, tibutyl and benzoyl,
Wherein X - is a halogen, nitrate, sulfate, phosphate, tetrafluoroborate, tetrachloro aluminate, tetrachloro page rate (III), hexa fluoro phosphate, methane hexafluoro to antimonate, carboxylate, trifluoroacetic Sulfonates, hydrogensulfonates, C 1 -C 6 alkylphosphates, C 1 -C 6 alkylsulfates, C 1 -C 6 alkylsulfonates, benzenesulfonates, bis (trifluoro-methylsulfonyl) imides, The present invention relates to an acidic ionic liquid catalyst selected from trifluoromethanesulfonimide or thiocyanate.
In another embodiment of the present invention, a cellulose solution is prepared by dissolving cellulose in an ionic liquid, and the cellulose solution is reacted with one or two or more acidic ionic liquid catalysts selected from the following Chemical Formula 1 to cellulose oligosaccharides. It relates to a depolymerization method of cellulose to prepare a.
(Formula 1)
[A +] [X -]
In Formula 1, A + is
The R 1 To R 12 are each independently of the other C 1 -C 6 alkyl group, C 1 -C 6 alkylcarboxyl group, C 1 -C 6 alkylester group, hydroxyC 1 -C 6 alkyl group, dihydroxyC 1 -C 6 An alkyl group, a C 1 -C 6 alkoxyC 1 -C 6 alkyl group, a C 6 -C 20 aryl group or a halogen atom,
The aryl group is C 1 -C 6 alkyl group, halogen group, nitro group, cyano group, hydroxy group, amino group, C 6 -C 20 aryl group, C 2 -C 7 alkenyl group, C 3 -C 20 cycloalkyl group, N, O At least one further selected from a 5 to 7 membered heterocycloalkyl group including at least one element selected from S or a C 4 -C 20 heteroaryl group containing at least one element selected from N, O and S Can be,
N is an integer selected from 1 to 4, X - represents a monovalent anion.
In addition, the present invention is the R 1 To R 12 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, acetyl group, propyl group, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, hydroxymethyl, hydroxy Selected from the group consisting of ethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, 1,2-dihydroxyethyl, dimethoxymethyl, methoxyethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, and phenyl groups Become,
The phenyl may be further substituted with bromo, fluorine, trifluoromethyl, cyano, trifluoromethoxy, tibutyl and benzoyl,
Wherein X - is a halogen, nitrate, sulfate, phosphate, tetrafluoroborate, tetrachloro aluminate, tetrachloro page rate (III), hexa fluoro phosphate, methane hexafluoro to antimonate, carboxylate, trifluoroacetic Sulfonates, hydrogensulfonates, C 1 -C 6 alkylphosphates, C 1 -C 6 alkylsulfates, C 1 -C 6 alkylsulfonates, benzenesulfonates, bis (trifluoro-methylsulfonyl) imides, It relates to a process for depolymerization of cellulose, which is selected from trifluoromethanesulfonimide or thiocyanate.
The present invention also relates to a depolymerization method of cellulose in which the ionic liquid is any one or two or more selected from the following Chemical Formula 2.
(2)
[B +] [X -]
In Formula 2, B + is
R 14 to R 30 are each independently of each other, a C 1 -C 6 alkyl group, a C 1 -C 6 alkylcarboxyl group, a C 1 -C 6 alkylester group, a hydroxyC 1 -C 6 alkyl group, and dihydroxyC 1 -C 6 alkyl group, C 1 -C 6 alkoxyC 1 -C 6 alkyl group, C 6 -C 20 aryl group or halogen atom,
The alkyl group or aryl group is C 1 -C 6 alkyl group, halogen group, nitro group, cyano group, hydroxy group, amino group, C 6 -C 20 aryl group, C 2 -C 7 alkenyl group, C 3 -C 20 cycloalkyl group, N At least one member selected from a 5 to 7 membered heterocycloalkyl group including at least one element selected from O, S, or a C 4 -C 20 heteroaryl group including at least one element selected from N, O, and S May be further substituted,
N is an integer selected from 1 to 4, X - represents a monovalent anion.
In the present invention, the R 14 To R 30 Is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, acetyl group, propyl group, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate Hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, 1,2-dihydroxyethyl, dimethoxymethyl, methoxyethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, And a phenyl group,
The phenyl may be further substituted with bromo, fluorine, trifluoromethyl, cyano, trifluoromethoxy, tibutyl and benzoyl,
Wherein X - is a halogen, nitrate, sulfate, phosphate, tetrafluoroborate, tetrachloro aluminate, tetrachloro page rate (III), hexa fluoro phosphate, methane hexafluoro to antimonate, carboxylate, trifluoroacetic Sulfonates, hydrogensulfonates, C 1 -C 6 alkylphosphates, C 1 -C 6 alkylsulfates, C 1 -C 6 alkylsulfonates, benzenesulfonates, bis (trifluoro-methylsulfonyl) imides, It relates to a process for depolymerization of cellulose, which is selected from trifluoromethanesulfonimide or thiocyanate.
The present invention also relates to a method for depolymerization of cellulose in which the acidic ionic liquid catalyst is any one or two or more selected from Formula 3 below.
(Formula 3)
The present invention also relates to a method for depolymerization of cellulose in which the melting point of the ionic liquid is -50 to 180 ° C.
The present invention also relates to a method for depolymerization of cellulose in which the acidic ionic liquid catalyst uses 10 to 100 parts by weight based on 100 parts by weight of cellulose.
In addition, the present invention relates to a depolymerization method of cellulose that is reacted for 0.25 to 5 hours at 50 to 130 ° C during depolymerization.
In the present invention, the acidity is high Cellulose is partially formed by any one or two or more acidic ionic liquid catalysts selected from Chemical Formula 1, that is, acidic acidic acidic catalysts having low acidity, rather than solid acidic catalysts that are prepared even in small molecular weight compounds such as glucose. Celluloligosaccharide can be prepared by depolymerization, and after completion of the reaction, an ionic liquid and an acidic ionic liquid catalyst are easily and cleanly separated from the celluligosaccharide, and the present invention relates to a method of depolymerization of cellulose which can increase the yield of celluligosaccharide.
Hereinafter, each configuration of the present invention will be described in detail.
In the present invention, "acidic ionic liquid catalyst" may be synthesized by adding an acid to a specific ionic liquid, preferably alkylated imidazolium, pyrrolidinium, pyridinium,
In addition, the term "celloligosaccharide" in the present invention means a compound having a molecular weight of 500 or more and 3000 or less by depolymerization of cellulose.
The present invention relates to an acidic ionic liquid catalyst for cellulose depolymerization including any one or two or more compounds selected from
(Formula 1)
[A +] [X -]
In
R 1 to R 12 are each independently of each other, a C 1 -C 6 alkyl group, a C 1 -C 6 alkylcarboxyl group, a C 1 -C 6 alkylester group, a hydroxyC 1 -C 6 alkyl group, dihydroxyC 1 -C 6 alkyl group, C 1 -C 6 alkoxyC 1 -C 6 alkyl group, C 6 -C 20 aryl group or halogen atom,
The aryl group is C 1 -C 6 alkyl group, halogen group, nitro group, cyano group, hydroxy group, amino group, C 6 -C 20 aryl group, C 2 -C 7 alkenyl group, C 3 -C 20 cycloalkyl group, N, O At least one further selected from a 5 to 7 membered heterocycloalkyl group including at least one element selected from S or a C 4 -C 20 heteroaryl group containing at least one element selected from N, O and S Can be,
N is an integer selected from 1 to 4, X - represents a monovalent anion.
More specifically R 1 to R 12 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, acetyl group, propyl group, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, Hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, 1,2-dihydroxyethyl, dimethoxymethyl, methoxyethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, and Selected from the group consisting of phenyl groups,
The phenyl may be further substituted with bromo, fluorine, trifluoromethyl, cyano, trifluoromethoxy, tibutyl and benzoyl,
Wherein X - is a halogen, nitrate, sulfate, phosphate, tetrafluoroborate, tetrachloro aluminate, tetrachloro page rate (III), hexa fluoro phosphate, methane hexafluoro to antimonate, carboxylate, trifluoroacetic Sulfonates, hydrogensulfonates, C 1 -C 6 alkylphosphates, C 1 -C 6 alkylsulfates, C 1 -C 6 alkylsulfonates, benzenesulfonates, bis (trifluoro-methylsulfonyl) imides, Trifluoromethanesulfonimide or thiocyanate.
In still another aspect of the present invention, a cellulose solution is prepared by dissolving cellulose in an ionic liquid, and the cellulose solution is reacted with one or two or more acidic ionic liquid catalysts selected from
(Formula 1)
[A +] [X -]
In
The R 1 To R 12 are each independently of the other C 1 -C 6 alkyl group, C 1 -C 6 alkylcarboxyl group, C 1 -C 6 alkylester group, hydroxyC 1 -C 6 alkyl group, dihydroxyC 1 -C 6 An alkyl group, a C 1 -C 6 alkoxyC 1 -C 6 alkyl group, a C 6 -C 20 aryl group or a halogen atom,
The aryl group is C 1 -C 6 alkyl group, halogen group, nitro group, cyano group, hydroxy group, amino group, C 6 -C 20 aryl group, C 2 -C 7 alkenyl group, C 3 -C 20 cycloalkyl group, N, O At least one further selected from a 5 to 7 membered heterocycloalkyl group including at least one element selected from S or a C 4 -C 20 heteroaryl group containing at least one element selected from N, O and S Can be,
N is an integer selected from 1 to 4, X - represents a monovalent anion.
More specifically the R 1 R 12 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, acetyl group, propyl group, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, hydroxymethyl, hydroxy Selected from the group consisting of ethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, 1,2-dihydroxyethyl, dimethoxymethyl, methoxyethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, and phenyl groups Become,
The phenyl may be further substituted with bromo, fluorine, trifluoromethyl, cyano, trifluoromethoxy, tibutyl and benzoyl,
Wherein X - is a halogen, nitrate, sulfate, phosphate, tetrafluoroborate, tetrachloro aluminate, tetrachloro page rate (III), hexa fluoro phosphate, methane hexafluoro to antimonate, carboxylate, trifluoroacetic Sulfonates, hydrogensulfonates, C 1 -C 6 alkylphosphates, C 1 -C 6 alkylsulfates, C 1 -C 6 alkylsulfonates, benzenesulfonates, bis (trifluoro-methylsulfonyl) imides, Trifluoromethanesulfonimide or thiocyanate.
Specifically, the acidic ionic liquid catalyst may include any one or two or more selected from Chemical Formula 3, but is not limited thereto.
(Formula 3)
Using the acidic ionic liquid catalyst in the present invention, it is possible to more easily and cleanly separate the cell oligosaccharides generated after the depolymerization reaction from the ionic liquid and the acidic ionic liquid catalyst, and to increase the yield of the cell oligosaccharides. It is preferable because of that.
As a preferred embodiment of the present invention, the cellulose is preferably a natural cellulose-based material, and the natural cellulose-based material is a water-insoluble fibrous material derived from nature containing cellulose. Its origin may be vegetable or animal, and the flora and fauna which produce it may be, for example, wood, bamboo, straw, straw, cotton, ramie, vargas, kenaf, beets, hoya, bacterial cellulose, and the like. As the raw material, one of these natural cellulose substances may be used alone, or a mixture of two or more kinds thereof may be used.
In a preferred embodiment of the present invention, the depolymerization method of the cellulose will be briefly described. The ionic liquid and the cellulose are introduced into a reactor equipped with a reflux condenser and then stirred at a high temperature. Thereafter, an acidic ionic liquid catalyst may be added to proceed the depolymerization reaction, and after completion of the reaction, the reaction solution may be cooled and an excess amount of water may be added to prepare a hydrogel oligosaccharide in hydrogel form. At this time, the produced hydrogel cellooligosaccharide is washed with a solvent such as water, dichloromethane, methanol, ethanol or acetone and dried.
The addition of the cellulose to the ionic liquid and stirring may transform the crystalline structure of the cellulose strongly bound by hydrogen bonding into an amorphous structure, thereby increasing the yield of cellulose oligosaccharide, and thus, before adding the acidic ionic liquid catalyst. It is preferable to go through the process of adding cellulose to the ionic liquid and stirring. In addition, the cellulose is added to the ionic liquid rather than other solvents and stirred, because the ionic liquid can more effectively transform the crystalline structure of the cellulose into an amorphous structure than the other solvents.
The ionic liquid may be any one or two or more selected from formula (2), can dissolve cellulose, and is not limited as long as it is water-soluble.
(2)
[B +] [X -]
In Formula 2, B + is
The R 14 To R 30 are each independently from each other, a C 1 -C 6 alkyl group, a C 1 -C 6 alkylcarboxyl group, a C 1 -C 6 alkylester group, a hydroxyC 1 -C 6 alkyl group, a dihydroxyC 1 -C 6 An alkyl group, a C 1 -C 6 alkoxyC 1 -C 6 alkyl group, a C 6 -C 20 aryl group or a halogen atom,
The alkyl group or aryl group is C 1 -C 6 alkyl group, halogen group, nitro group, cyano group, hydroxy group, amino group, C 6 -C 20 aryl group, C 2 -C 7 alkenyl group, C 3 -C 20 cycloalkyl group, N At least one member selected from a 5 to 7 membered heterocycloalkyl group including at least one element selected from O, S, or a C 4 -C 20 heteroaryl group including at least one element selected from N, O, and S May be further substituted,
N is an integer selected from 1 to 4, X - represents a monovalent anion.
More specifically, R 14 To R 30 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, acetyl group, propyl group, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, hydroxymethyl, hydroxy Selected from the group consisting of ethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, 1,2-dihydroxyethyl, dimethoxymethyl, methoxyethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, and phenyl groups Become,
The phenyl may be further substituted with bromo, fluorine, trifluoromethyl, cyano, trifluoromethoxy, tibutyl and benzoyl,
Wherein X - is a halogen, nitrate, sulfate, phosphate, tetrafluoroborate, tetrachloro aluminate, tetrachloro page rate (III), hexa fluoro phosphate, methane hexafluoro to antimonate, carboxylate, trifluoroacetic Sulfonates, hydrogensulfonates, C 1 -C 6 alkylphosphates, C 1 -C 6 alkylsulfates, C 1 -C 6 alkylsulfonates, benzenesulfonates, bis (trifluoro-methylsulfonyl) imides, Trifluoromethanesulfonimide or thiocyanate.
As an example of the present invention, the melting point of the ionic liquid is preferably 180 ° C or less, preferably -50 ° C to 180 ° C, and more preferably -20 ° C to 120 ° C.
In addition, as an example of the present invention, the acidic ionic liquid catalyst is preferably used 10 to 100 parts by weight with respect to 100 parts by weight of cellulose, which can increase the depolymerization efficiency of cellulose to increase the yield of cellulose oligosaccharides, acidic ionic This is because the separation of cellooligosaccharides from the liquid catalyst can be made easier.
In addition, as an example of the present invention, it is preferable to react 0.25 to 5 hours at 50 to 130 ℃ during the depolymerization reaction, and if the temperature and the reaction time range is satisfied, the depolymerization reaction is smoothly made to maximize the yield of cellulose oligosaccharides. And the rate of increase in yield is efficient.
In addition, the depolymerization reaction can be carried out in air or an inert gas, that is, helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), radon (Rn) gas, preferably It is preferably performed in air, but is not limited thereto.
The acidic ionic liquid catalyst according to the present invention has a low acidity to partially depolymerize cellulose to produce cell oligosaccharides. The depolymerization method of the cellulose which can raise the yield of this is related.
1 is a 1 H NMR of the acidic ionic liquid catalyst prepared in Example 1 of the present invention,
2 is 1 H NMR of the acidic ionic liquid catalyst prepared in Example 2 of the present invention,
3 is 1 H NMR of the acidic ionic liquid catalyst prepared in Example 3 of the present invention,
4 is 1 H NMR of the acidic ionic liquid catalyst prepared in Example 4 of the present invention.
5 is 13 C NMR of the cellulose oligosaccharide prepared in Example 5 of the present invention,
FIG. 6 is 13 C NMR of cellulose oligosaccharide prepared in Example 6 of the present invention. FIG.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the appended claims. And it is natural that such variations and modifications are included in the appended claims.
<Preparation of acidic ionic liquid catalyst>
Example 1 1-methylimidazolium-3-propanesulfonic acid / hydrogensulfonate (1-methylimidazolim-3-propanesulfonicacid / hydrogensulfonate ) Synthesis of
In a reactor equipped with a reflux capacitor, 3.1 mL (0.039 mol) of methylimidazole was dissolved in 100 mL of acetone, and 3.42 mL (0.039 mol) of 1,3-propanesulfone was dissolved. . At this time, slowly added while stirring at a low temperature of 0 ° C. And a precipitate was obtained by stirring for 72 hours at a temperature of 25 ° C. in a nitrogen stream. It was washed with acetone, vacuum-hot dried (60 ° C), and then 4.5 g (56.5%) colorless solid crystals of 1-methylimidazolium-3-propanesulfonate (1-methylimidazolim-3-propanesulfonate) were added. Got it. This was reacted with 1 equivalent of sulfuric acid (H 2 SO 4 ) to synthesize 1-methylimidazolium-3-propanesulfonic acid / hydrogensulfonate, and 1 H NMR was shown in FIG. 1.
[ Example 2] 1- Methylpyrrolidinium -One- Propanesulfonic acid / Hydrogensulfonate (1- methylpyrrolidinium -One- propanesulfonicacid / hydrogensulfonate ) Synthesis of
3.66 mL (0.03523 mol) of methylpyrrolidine was dissolved in 100 mL of acetone and 3.09 mL (0.03523 mol) of 1,3-propanesulfone in a reactor equipped with a reflux capacitor. At this time, slowly added while stirring at a low temperature of 0 ° C. And a precipitate was obtained by stirring for 72 hours at 25 ° C. temperature in a nitrogen stream. This was washed with acetone, vacuum-hot dried (60 ° C), and then 6.25 g (85.6%) colorless solid crystals of 1-methylpyrrolidinium-1-propanesulfonate (1-methylpyrrolidinium-1-propanesulfonate) were added. Got it. This was reacted with 1 equivalent of sulfuric acid (H 2 SO 4) to synthesize desired 1-methylpyrrolidinium-1-propanesulfonic acid / hydrogensulfonate, and 1H NMR was shown in FIG. 2.
[ Example 3] 1- Methylpyridinium -3- Propanesulfonic acid / Hydrogensulfonate (1- methylpyridinium -3- propanesulfonicacid / hydrogensulfonate ) Synthesis of
In a reactor equipped with a reflux condenser, 3.1 mL (0.0379 mol) of pyridine was dissolved in 100 mL of acetone, and 3.3 mL (0.0379 mol) of 1,3-propanesulfone were dissolved. At this time, slowly added while stirring at a low temperature of 0 ° C. And a precipitate was obtained by stirring for 72 hours at 25 ° C. in a nitrogen stream. This was washed with acetone, vacuum-hot dried (60 ° C.) and then 1.23 g (16%) of colorless solid crystals of 1-methylpyridinium-3-propanesulfonate (1-methylpyridinium-3-propanesulfonate). Got it. This was reacted with 1 equivalent of sulfuric acid (H 2 SO 4) to synthesize desired 1-methylpyridinium-3-propanesulfonic acid / hydrogensulfonate, and 1 H NMR was shown in FIG. 3.
[ Example 4] Triethylammoniumpropanesulfonic acid / Hydrogensulfonate ( triethylammonium propanesulfonicacid / hydrogensulfonate ) Synthesis of
In a reactor equipped with a reflux condenser, 4.1 mL (0.02964 mol) of triethylamine was dissolved in 100 mL of acetone, and 2.6 mL (0.02964 mol) of 1,3-propanesulfone was dissolved. At this time, slowly added while stirring at a low temperature of 0 ° C. And a precipitate was obtained by stirring for 72 hours at 25 ° C. in a nitrogen stream. This was washed with acetone and again vacuum-hot dried (60 ° C.) to give 6.6 g (29%) of colorless solid crystals of triethylammonium propanesulfonate. This was reacted with 1 equivalent of sulfuric acid (H 2 SO 4) to synthesize the desired triethylammoniumpropanesulfonic acid / hydrogensulfonate, and 1 H NMR was shown in FIG. 4.
<Depolymerization of Cellulose>
[Example 5]
5 g of 1-butyl-3-methylimidazolium chloride and 250 mg of microcrystalline cellulose were added to a reactor equipped with a reflux condenser. Stir for 1 hour. Then 0.1 mL distilled water was added and stirred for 15 minutes to prepare a cellulose solution. 125 mg of 1-methylimidazolium-3-propanesulfonic acid / hydrogensulfonate prepared in Example 1 was added to the prepared cellulose solution, stirred for 5 hours, cooled to 25 ° C., and 50 mL of water was added. It was. The hydrogel formed at this time was precipitated using a centrifuge. And it dried at 100 degreeC and produced the cello oligosaccharide. At this time, by measuring the prepared cell oligosaccharides by 13 C NMR is shown in Figure 5 below.
[Example 6]
5 g of 1-butyl-3-methylimidazolium chloride and 250 mg of microcrystalline cellulose were added to a reactor equipped with a reflux condenser. Stir for 1 hour. Then 0.1 mL distilled water was added and stirred for 15 minutes to prepare a cellulose solution. 125 mg of 1-methylpyrrolidinium-1-propanesulfonic acid / hydrogensulfonate prepared in Example 2 was added to the prepared cellulose solution, stirred for 5 hours, cooled to 25 ° C., and 50 mL of water was added thereto. Added. The hydrogel formed at this time is precipitated using a centrifuge. And it dried at 100 degreeC and produced the cello oligosaccharide. At this time, by measuring the prepared cell oligosaccharides by 13 C NMR is shown in Figure 6 below.
[Example 7]
5 g of 1-butyl-3-methylimidazolium chloride and 250 mg of microcrystalline cellulose were added to a reactor equipped with a reflux condenser. Stir for 1 hour. Then 0.1 mL distilled water was added and stirred for 15 minutes to prepare a cellulose solution. 125 mg of 1-methylpyridinium-3-propanesulfonic acid / hydrogensulfonate prepared in Example 3 was added to the prepared cellulose solution, stirred for 5 hours, cooled to 25 ° C., and 50 mL of water was added. It was. The hydrogel formed at this time was precipitated using a centrifuge. And it dried at 100 degreeC and produced the cello oligosaccharide. At this time, by measuring the prepared cell oligosaccharides by 13 C NMR is shown in Figure 7 below.
[Example 8]
5 g of 1-butyl-3-methylimidazolium chloride and 250 mg of microcrystalline cellulose were added to a reactor equipped with a reflux condenser. Stir for 1 hour. Then 0.1 mL distilled water was added and stirred for 15 minutes to prepare a cellulose solution. 250 mg of triethylammoniumpropanesulfonic acid / hydrogensulfonate prepared in Example 4 was added to the prepared cellulose solution, stirred for 5 hours, cooled to 25 ° C., and 50 mL of water was added thereto. The hydrogel formed at this time was precipitated using a centrifuge. And it dried at 100 degreeC and produced the cello oligosaccharide. In this case, the yield and average degree of polymerization of the prepared cellulose oligosaccharides are shown in Table 1 below, and measured by 13 C NMR.
[Comparative Example 1]
5 g of 1-butyl-3-methylimidazolium chloride and 250 mg of microcrystalline cellulose were added to a reactor equipped with a reflux condenser. Stir for 1 hour. Then 0.1 mL distilled water was added and stirred for 15 minutes to prepare a cellulose solution. 12.5 mg of triethylammoniumpropanesulfonic acid / hydrogensulfonate prepared in Example 4 was added to the prepared cellulose solution, stirred for 5 hours, cooled to 25 ° C., and 50 mL of water was added thereto. The hydrogel formed at this time was precipitated using a centrifuge. And it dried at 100 degreeC and produced the cello oligosaccharide.
[Comparative Example 2]
5 g of 1-butyl-3-methylimidazolium chloride and 250 mg of microcrystalline cellulose were added to a reactor equipped with a reflux condenser. Stir for 1 hour. Then 0.1 mL distilled water was added and stirred for 15 minutes to prepare a cellulose solution. 262.5 mg of triethylammoniumpropanesulfonic acid / hydrogensulfonate prepared in Example 4 was added to the prepared cellulose solution, stirred for 5 hours, cooled to 25 ° C., and 50 mL of water was added thereto. The hydrogel formed at this time was precipitated using a centrifuge. And it dried at 100 degreeC and produced the cello oligosaccharide.
Claims (10)
(Formula 1)
[A +] [X -]
(In Formula 1, A + is
The R 1 To R 12 are each independently of the other C 1 -C 6 alkyl group, C 1 -C 6 alkylcarboxyl group, C 1 -C 6 alkylester group, hydroxyC 1 -C 6 alkyl group, dihydroxyC 1 -C 6 An alkyl group, a C 1 -C 6 alkoxyC 1 -C 6 alkyl group, a C 6 -C 20 aryl group or a halogen atom,
The aryl group is C 1 -C 6 alkyl group, halogen group, nitro group, cyano group, hydroxy group, amino group, C 6 -C 20 aryl group, C 2 -C 7 alkenyl group, C 3 -C 20 cycloalkyl group, N, O At least one further selected from a 5 to 7 membered heterocycloalkyl group including at least one element selected from S or a C 4 -C 20 heteroaryl group containing at least one element selected from N, O and S Can be,
N is an integer selected from 1 to 4, X - represents a monovalent anion.)
In Formula 1, R < 1 > R 12 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, acetyl group, propyl group, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, hydroxymethyl, hydroxy Selected from the group consisting of ethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, 1,2-dihydroxyethyl, dimethoxymethyl, methoxyethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, and phenyl groups Become,
The phenyl may be further substituted with bromo, fluorine, trifluoromethyl, cyano, trifluoromethoxy, tibutyl and benzoyl,
Wherein X - is a halogen, nitrate, sulfate, phosphate, tetrafluoroborate, tetrachloro aluminate, tetrachloro page rate (III), hexa fluoro phosphate, methane hexafluoro to antimonate, carboxylate, trifluoroacetic Sulfonates, hydrogensulfonates, C 1 -C 6 alkylphosphates, C 1 -C 6 alkylsulfates, C 1 -C 6 alkylsulfonates, benzenesulfonates, bis (trifluoro-methylsulfonyl) imides, An acidic ionic liquid catalyst selected from trifluoromethanesulfonimide or thiocyanate.
(Formula 1)
[A +] [X -]
(In Formula 1, A + is
It is one kind selected from
The R 1 To R 12 are each independently of the other C 1 -C 6 alkyl group, C 1 -C 6 alkylcarboxyl group, C 1 -C 6 alkylester group, hydroxyC 1 -C 6 alkyl group, dihydroxyC 1 -C 6 An alkyl group, a C 1 -C 6 alkoxyC 1 -C 6 alkyl group, a C 6 -C 20 aryl group or a halogen atom,
The aryl group is C 1 -C 6 alkyl group, halogen group, nitro group, cyano group, hydroxy group, amino group, C 6 -C 20 aryl group, C 2 -C 7 alkenyl group, C 3 -C 20 cycloalkyl group, N, O At least one further selected from a 5 to 7 membered heterocycloalkyl group including at least one element selected from S or a C 4 -C 20 heteroaryl group containing at least one element selected from N, O and S Can be,
N is an integer selected from 1 to 4, X - represents a monovalent anion.)
The ionic liquid is any one or two or more selected from the formula (2) Depolymerization method of cellulose.
(2)
[B +] [X -]
(In Formula 2, B + is
R 14 to R 30 are each independently of each other, a C 1 -C 6 alkyl group, a C 1 -C 6 alkylcarboxyl group, a C 1 -C 6 alkylester group, a hydroxyC 1 -C 6 alkyl group, and dihydroxyC 1 -C 6 alkyl group, C 1 -C 6 alkoxyC 1 -C 6 alkyl group, C 6 -C 20 aryl group or halogen atom,
The alkyl group or aryl group is C 1 -C 6 alkyl group, halogen group, nitro group, cyano group, hydroxy group, amino group, C 6 -C 20 aryl group, C 2 -C 7 alkenyl group, C 3 -C 20 cycloalkyl group, N At least one member selected from a 5 to 7 membered heterocycloalkyl group including at least one element selected from O, S, or a C 4 -C 20 heteroaryl group including at least one element selected from N, O, and S May be further substituted,
N is an integer selected from 1 to 4, X - represents a monovalent anion.)
In Formula 1, R 1 to R 12 are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, acetyl group, propyl group, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, Hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, 1,2-dihydroxyethyl, dimethoxymethyl, methoxyethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, and Selected from the group consisting of phenyl groups,
The phenyl may be further substituted with bromo, fluorine, trifluoromethyl, cyano, trifluoromethoxy, tibutyl and benzoyl,
Wherein X - is a halogen, nitrate, sulfate, phosphate, tetrafluoroborate, tetrachloro aluminate, tetrachloro page rate (III), hexa fluoro phosphate, methane hexafluoro to antimonate, carboxylate, trifluoroacetic Sulfonates, hydrogensulfonates, C 1 -C 6 alkylphosphates, C 1 -C 6 alkylsulfates, C 1 -C 6 alkylsulfonates, benzenesulfonates, bis (trifluoro-methylsulfonyl) imides, Process for depolymerization of cellulose selected from trifluoromethanesulfonimide or thiocyanate.
R 14 of Formula 2 To R 30 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, acetyl group, propyl group, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, hydroxymethyl, hydroxy Selected from the group consisting of ethyl, hydroxypropyl, hydroxybutyl, hydroxyhexyl, 1,2-dihydroxyethyl, dimethoxymethyl, methoxyethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, and phenyl groups Become,
The phenyl may be further substituted with bromo, fluorine, trifluoromethyl, cyano, trifluoromethoxy, tibutyl and benzoyl,
Wherein X - is a halogen, nitrate, sulfate, phosphate, tetrafluoroborate, tetrachloro aluminate, tetrachloro page rate (III), hexa fluoro phosphate, methane hexafluoro to antimonate, carboxylate, trifluoroacetic Sulfonates, hydrogensulfonates, C 1 -C 6 alkylphosphates, C 1 -C 6 alkylsulfates, C 1 -C 6 alkylsulfonates, benzenesulfonates, bis (trifluoro-methylsulfonyl) imides, Process for depolymerization of cellulose selected from trifluoromethanesulfonimide or thiocyanate.
The acidic ionic liquid catalyst is any one or two or more selected from the formula (3) Depolymerization method.
(Formula 3)
Melting point of the ionic liquid is -50 ~ 180 ℃ depolymerization method of cellulose.
The acidic ionic liquid catalyst is 10 to 100 parts by weight based on 100 parts by weight of cellulose is depolymerization method of cellulose.
The depolymerization is a method of depolymerization of cellulose that is reacted at 50 to 130 ℃ for 0.25 to 5 hours.
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