CN101580549A - Method for preparing cellulose acetate propionate or cellulose acetate butyrate - Google Patents
Method for preparing cellulose acetate propionate or cellulose acetate butyrate Download PDFInfo
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- CN101580549A CN101580549A CNA200810106426XA CN200810106426A CN101580549A CN 101580549 A CN101580549 A CN 101580549A CN A200810106426X A CNA200810106426X A CN A200810106426XA CN 200810106426 A CN200810106426 A CN 200810106426A CN 101580549 A CN101580549 A CN 101580549A
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Abstract
The invention provides a method for preparing cellulose acetate propionate or cellulose acetate butyrate. The method comprises the following steps: a. mixing fibrin and ionic liquid capable of dissolving the fibrin to obtain an ionic liquid solution containing the fibrin; b. adding acetylate and propionyl reagent (1) or acetylate and reagent (2) into the ionic liquid solution containing the fibrin, reacting for 1-24h at 40-120 DEG C, preferably 1-12h, and obtaining reaction mixture; c. adding lower fatty alcohol from C1 to C3 into the reaction mixture and filtering the reaction mixture containing the lower fatty alcohol; and d. drying a solid obtained by filtering to obtain the cellulose acetate propionate or cellulose acetate butyrate. The invention utilizes the ionic liquid as a solvent without any catalyst and has the advantages of simple process and no pollution.
Description
Technical field
The present invention relates to a kind of method for preparing cellulose acetate propionate or cellulose acetate butyrate, particularly a kind of in ionic liquid homogeneous phase prepare the method for cellulose acetate propionate or cellulose acetate butyrate mixed ester.
Background technology
Derivatived cellulose is a human development natural macromolecular material the earliest.Though since the fifties, along with the rise of petrochemical complex, succeeding in developing and large-scale commercial production of various new synthesized polymer materials makes plastics of derivatived cellulose and resin reduce year by year in the shared ratio of polymeric material field.But since the seventies in 20th century, consider from the finiteness of the energy and petroleum resources, adding the fiber material material products has characteristic that other synthesized polymer materials do not replace etc., therefore in field of polymer technology again research and the utilization to natural polymer paid attention to.Cellulose ester is cellulosic important derivatives.The output of cellulose esters is about annual 600000 tons in the world according to statistics.The cellulose acetate of output maximum is widely used in makes plastics, film, coating, fiber etc.Though cellulose acetate at some in nature, all very good as aspects such as flame resistivity, fusing point, toughness and sharpness, water resisting property and solvability are good not enough, and this is restricted with regard to the application that makes it.The cellulose mixed esters class that thereupon grows up not only has the characteristic of cellulose acetate, and all improving a lot aspect solvability, water resisting property, snappiness, weathering resistance, the mouldability, because they have good resin compatible, photostabilization and winter hardiness, be widely used in high-grade car paint and printing-ink simultaneously.Be in the mid-1930s in the world the earliest, at first push cellulose mixed esters to industrial application, owing to its excellent properties has obtained swift and violent development by U.S. Yi Siman Kodak.We can say that making of cellulose mixed esters set up the possibility that further changes cellulose ester character widely.Along with cellulose mixed esters is also constantly enlarging and the continuous discovery of new purposes and its wearing quality in industrial application, advantages such as toxicological harmless and easy handling also more and more cause the concern of more Application Areass.At present with practical value and formed industrial cellulose acetate propionate and the cellulose acetate butyrate of comprising of scale.
The operational path of production of cellulose mixed ester all carries out in nonhomogeneous system at present: utilize the refined cotton linter or the wooden oar dregs of rice to be raw material, with sulfuric acid is catalyst, two kinds of acid anhydrides and Mierocrystalline cellulose make the cellulose ester of full replacement earlier under the acidic solution condition, pass through hydrolysis again, neutralization, filter, operations such as washing are made different acid anhydrides esters, the cellulose mixed esters of different viscosity.But this method often causes cellulosic severely degrade and to environment damage.In recent years along with the continuous discovery of a large amount of Mierocrystalline cellulose novel dissolvents, a kind of method of new single stage method homogeneous phase synthetic cellulose ester causes the concern of researcher gradually.This homogeneous phase synthetic method technology is simple, and speed of reaction is fast and controlled, the product property homogeneous that obtains, and range of application is also corresponding extended.Publication number be CN02147004.9 patent disclosure 1-allyl group-3-methyl chloride imidazole salts (AmimCl) ionic liquid, this ionic liquid can dissolving cellulos, forms cellulose solution.Compare with other cellosolves, 1-allyl group-3-methyl chloride imidazole salts has nontoxic, non-volatile, the advantage of easy recovery etc.Disclose in " high chemical journal " the 27th 3 phases of volume and to be entitled as " homogeneous phase acetylize and the selectivity thereof of Mierocrystalline cellulose in ionic liquid " literary composition; Mierocrystalline cellulose homogeneous acetylization reaction in 1-allyl group-3-methyl chloride imidazole ion liquid is disclosed in the literary composition; this reaction adopts diacetyl oxide or Acetyl Chloride 98Min. as acetylation reagent; at catalyst-free or pyridine is under the condition of catalyzer, has obtained cellulose acetate.The method that adopts ionic liquid to prepare cellulose acetate propionate or cellulose acetate butyrate yet there are no open.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of method for preparing cellulose acetate propionate or cellulose acetate butyrate.
The invention provides a kind of method for preparing cellulose acetate propionate or cellulose acetate butyrate, this method may further comprise the steps:
A. Mierocrystalline cellulose is mixed with ionic liquid that can dissolving cellulos, obtain containing cellulosic ionic liquid solution;
B. with 1) acetylation reagent and propionyl reagent or 2) acetylation reagent and Butyrylation reagent adds and contains in the cellulosic ionic liquid solution, 40-120 ℃ of reaction 1-24 hour, obtains reaction mixture;
C. in described reaction mixture, add C
1-C
3Lower aliphatic alcohols, filter the reaction mixture contain lower aliphatic alcohols;
D. behind the solid drying that filtration is obtained, obtain cellulose acetate propionate or cellulose acetate butyrate.Ionic liquid that can dissolving cellulos is 200610026709.4 Chinese patent application referring to application number.
Preferably, in step b with 1) acetylation reagent and propionyl reagent or 2) acetylation reagent and Butyrylation reagent adds and contains in the cellulosic ionic liquid solution, 40-120 ℃ of reaction 1-12 hour, obtains reaction mixture.
Preferably, step a comprise with Mierocrystalline cellulose 40-120 ℃ with ionic liquid mixing that can dissolving cellulos 1-12 hour, obtain containing cellulosic ionic liquid solution.
Preferably, the temperature of reaction of step b is 60-120 ℃.
Preferably, the temperature of reaction of step b is 80-100 ℃.
Preferably, described C
1-C
3Lower aliphatic alcohols and ion liquid volume ratio be 3: 1-10: 1.
Preferably, C
1-C
3Lower aliphatic alcohols be methyl alcohol or ethanol.
Preferably; in described step b; with 1) acetylation reagent and propionyl reagent or 2) acetylation reagent and Butyrylation reagent adds at the same time or separately and contains in the cellulosic ionic liquid solution; when with 1) acetylation reagent and propionyl reagent or 2) acetylation reagent and Butyrylation reagent adds respectively when containing cellulosic ionic liquid solution, and the joining day of two kinds of acylating reagents is spaced apart 0.5-12 hour.
Preferably, the timed interval of two kinds of acylating reagent addings is 1-5 hour.
Preferably, described acetylation reagent is diacetyl oxide or Acetyl Chloride 98Min., and described propionyl reagent is propionic anhydride or propionyl chloride, and described Butyrylation reagent is butyryl oxide or butyryl chloride.
Preferably, describedly contain that Mierocrystalline cellulose quality concentration is 1-30% in the cellulosic ionic liquid solution.
Preferably, describedly contain that Mierocrystalline cellulose quality concentration is 4-10% in the cellulosic ionic liquid.
Preferably, the mol ratio of glucose unit is 1 in described acetylation reagent, propionyl reagent or Butyrylation reagent and the described Mierocrystalline cellulose: 1-10: 1.
Preferably, the mol ratio of glucose unit is 3 in described acetylation reagent, propionyl reagent or Butyrylation reagent and the described Mierocrystalline cellulose: 1-5: 1.
Preferably, described ionic liquid that can dissolving cellulos is the C of imidazoles halogen or imidazoles
1-C
6Carboxylate salt.
More preferably, described imidazoles halogen is the imidazoles villaumite, the C of described imidazoles
1-C
6Carboxylate salt is an imidazoles acetate.
Preferably, the C of described imidazoles halogen or imidazoles
1-C
6The positively charged ion of carboxylate salt has following formula (I) structure:
In this structural formula, R
1And R
2Be C
1-C
20Alkyl or alkenyl, R
3, R
4, R
5Be independently selected from hydrogen, C
1-C
20Alkyl, alkoxyl group and thiazolinyl.
More preferably, the C of described imidazoles halogen or imidazoles
1-C
6The positively charged ion of carboxylate salt has formula (II) structure:
R
1And R
2Be C
1-C
20Alkyl or alkenyl.
Most preferably, the C of described imidazoles halogen or imidazoles
1-C
6The positively charged ion of carboxylate salt has formula (III) structure:
The present invention is the homogeneous reaction medium with the ionic liquid, has obtained cellulose acetate propionate or cellulose acetate butyrate with single stage method.Compare with the method for existing production of cellulose mixed ester, the present invention uses ionic liquid to be solvent, without any need for catalyzer, has simple, the free of contamination advantage of technology.Cellulose acetate propionate or the cellulose acetate butyrate for preparing with the inventive method has identical character with cellulose acetate propionate or the cellulose acetate butyrate that other art methods obtains simultaneously.Comparing different with the method that prior art is produced cellulose acetate is that the present invention has finished cellulosic two kinds of esterifications in 1-24 hour, obtained the blending in of fibers ester of wanting.And the acidylate among the present invention does not need to adopt any catalyzer, only adopts acid anhydrides or acyl chlorides just can finish cellulosic acylation reaction.Acetyl substitution value in the cellulose acetate propionate that employing the inventive method obtains is 0.1-2.5, and the propionyl substitution value is 0.1-2.5, and the acetyl substitution value in the cellulose acetate butyrate that obtains is 0.1-2.5, and the butyryl substitution value is 0.1-2.5.Meanwhile; by in reaction process, controlling the amount of every kind of acylating reagent effectively; thereby can control 1 in the gained cellulose mixed esters) ethanoyl and propionyl or 2) the ratio of hydroxyl on ethanoyl and the butyryl radicals substituted cellulose, obtain the cellulose mixed esters of required physicochemical property.
Embodiment
Below be used to further specify the method that the present invention describes by concrete embodiment, but do not limit the present invention.
Embodiment 1
Take by weighing the about 0.6g of Mierocrystalline cellulose, ionic liquid 1-allyl group-3-Methylimidazole villaumite (AMIMCl) 59.4g is put into round-bottomed flask, and oil bath is heated to 60 ℃, and the sealing intense mechanical stirred 1 hour.Obtain the cellulose solution of clear, the concentration of cellulose solution is 1% (mass percent).Oil bath temperature is increased to 80 ℃, in solution, add simultaneously diacetyl oxide (about 1.05ml) and propionic anhydride (about 4.75ml), the mol ratio that makes diacetyl oxide and Mierocrystalline cellulose glucose unit is 3: 1, and the mol ratio of propionic anhydride and Mierocrystalline cellulose glucose unit is 10: 1, reaction 1h.Reaction finishes, the methyl alcohol of 3 times of ionic liquid volumes is added in the reaction mixture, with the ionic liquid in the washing reaction mixed solution, filtration contains the reaction mixture of methyl alcohol, solid matter that dry filter obtains and the washings that contains methyl alcohol, then this solids is put into vacuum drying oven, 60 ℃ of oven dry, 23h; The methyl alcohol of removing in the washings by rotary evaporation is realized ion liquid recovery simultaneously, after testing, obtains the degree of substitution with acetyl group DS of product
A=1.14; The substitution value of propionyl is DS
P=0.63.
Embodiment 2
Take by weighing the about 0.6g of Mierocrystalline cellulose, ionic liquid 1-ethyl-3-Methylimidazole acetate (EMIMAc) 9.4g is put into round-bottomed flask, and oil bath is heated to 80 ℃, and the sealing intense mechanical stirs 4h.Obtain the cellulose solution of clear, the concentration of cellulose solution is 6% (mass percent).Oil bath temperature is risen to 100 ℃, add diacetyl oxide (about 1.74ml) earlier in solution, the mol ratio that makes diacetyl oxide and Mierocrystalline cellulose glucose unit is 5: 1; Add propionic anhydride (about 3.80ml) again behind the reaction 1h, the mol ratio that makes propionic anhydride and Mierocrystalline cellulose glucose unit is 8: 1, continues reaction 3h.After reaction finished, the mode that the aftertreatment of reacting the back mixture and ionic liquid are reclaimed was substantially with embodiment 1, and different is adds the ethanol of 5 times of ionic liquid volumes in the reaction mixture, and after testing, the degree of substitution with acetyl group that obtains product is DS
A=2.50; The substitution value of propionyl is DS
P=0.32.
Embodiment 3
Take by weighing the about 3g of Mierocrystalline cellulose, ionic liquid 1-butyl-3-Methylimidazole villaumite (BMIMCl) 12g is put into round-bottomed flask, and oil bath is heated to 100 ℃, and the sealing intense mechanical stirs 10h.Obtain the cellulose solution of clear, the concentration of cellulose solution is 20% (mass percent).Oil bath temperature is risen to 120 ℃, add propionic anhydride (about 14.25ml) earlier in solution, the mol ratio that makes propionic anhydride and Mierocrystalline cellulose glucose unit is 6: 1; Behind the reaction 2h, add diacetyl oxide (about 12.25ml) again, the mol ratio that makes diacetyl oxide and Mierocrystalline cellulose glucose unit is 7: 1, continues reaction 5h.After reaction finished, the mode that the aftertreatment of reacting the back mixture and ionic liquid are reclaimed was substantially with embodiment 1, and different is adds the propyl alcohol of 7 times of ionic liquid volumes in the reaction mixture, and after testing, the degree of substitution with acetyl group that obtains product is DS
A=0.90; The substitution value of propionyl is DS
P=1.60.
Embodiment 4
Take by weighing the about 0.3g of Mierocrystalline cellulose, ionic liquid 1-allyl group-3-Methylimidazole villaumite (AMIMCl) 14.7g is put into round-bottomed flask, and oil bath is heated to 80 ℃, and the sealing intense mechanical stirs 1h.Obtain the cellulose solution of clear, the concentration of cellulose solution is 2% (mass percent).Simultaneously add diacetyl oxide (about 1.05ml) and butyryl oxide (about 2.74ml) in solution, the mol ratio that makes diacetyl oxide and Mierocrystalline cellulose glucose unit is 6: 1, and the mol ratio of butyryl oxide and Mierocrystalline cellulose glucose unit is 9: 1, reaction 4h.
After reaction finished, the mode that the aftertreatment of reacting the back mixture and ionic liquid are reclaimed was substantially with embodiment 1, and different is adds the ethanol of 10 times of ionic liquid volumes in the reaction mixture, and after testing, the degree of substitution with acetyl group that obtains product is DS
A=1.60; The substitution value of butyryl radicals is DS
B=0.70.
Embodiment 5
Take by weighing the about 1g of Mierocrystalline cellulose, ionic liquid 1-propyl group-3-Methylimidazole villaumite (PMIMCl) 11.5g is put into round-bottomed flask, and oil bath is heated to 100 ℃, sealing, and intense mechanical stirs 4h.Obtain the cellulose solution of clear, the concentration of cellulose solution is 8% (mass percent).Earlier add diacetyl oxide (about 4.66ml) in solution, the mol ratio that makes diacetyl oxide and Mierocrystalline cellulose glucose unit is 8: 1; Add butyryl oxide (about 4.06ml) again behind the reaction 1h, the mol ratio that makes butyryl oxide and Mierocrystalline cellulose glucose unit is 4: 1, continues reaction 6h.
After reaction finished, the mode that the aftertreatment of reacting the back mixture and ionic liquid are reclaimed was with embodiment 1, and after testing, the substitution value that obtains the ethanoyl of product is DS
A=2.36; The substitution value of butyryl radicals is DS
B=0.27.
Embodiment 6
Take by weighing the about 3g of Mierocrystalline cellulose, ionic liquid 1-propyl group-3-Methylimidazole acetate (PMIMAc) 9g is put into round-bottomed flask, and oil bath is heated to 120 ℃, sealing, and intense mechanical stirs 12h.Obtain the cellulose solution of clear, the concentration of cellulose solution is 25% (mass percent).Earlier add butyryl oxide (about 3.04ml) in solution, the mol ratio that makes butyryl oxide and Mierocrystalline cellulose glucose unit is 1: 1; Add diacetyl oxide (about 17.39ml) again behind the reaction 1h, the mol ratio that makes diacetyl oxide and Mierocrystalline cellulose glucose unit is 10: 1, continues reaction 18h.
After reaction finished, the mode that the aftertreatment of reacting the back mixture and ionic liquid are reclaimed was with embodiment 2, and after testing, the substitution value that obtains the ethanoyl of product is DS
A=1.85; The substitution value of butyryl radicals is DS
B=0.40.
Embodiment 7
Take by weighing the about 0.6g of Mierocrystalline cellulose, ionic liquid 1-butyl-3-Methylimidazole villaumite (BMIMCl) 14.4g is put into round-bottomed flask, and oil bath is heated to 80 ℃, and the sealing intense mechanical stirs 2h.Obtain the cellulose solution of clear, the concentration of cellulose solution is 4% (mass percent).Oil bath temperature is reduced to 40 ℃, in solution, add simultaneously Acetyl Chloride 98Min. (about 1.32ml) and propionyl chloride (about 2.59ml), making the mol ratio of Acetyl Chloride 98Min. and Mierocrystalline cellulose glucose unit is 5: 1, and the mol ratio that makes propionyl chloride and Mierocrystalline cellulose glucose unit is 8: 1, reaction 8h.
After reaction finished, the mode that the aftertreatment of reacting the back mixture and ionic liquid are reclaimed was with embodiment 3, and after testing, the degree of substitution with acetyl group of reaction product is DS
A=1.68; The propionyl substitution value is DS
P=1.12.
Embodiment 8
Take by weighing the about 1g of Mierocrystalline cellulose, ionic liquid 1-allyl group-3-Methylimidazole acetate (AMIMAc) 9g is put into round-bottomed flask, is heated to 100 ℃, and the sealing intense mechanical stirs 6h.Obtain the cellulose solution of clear, the concentration of cellulose solution is 10% (mass percent).Oil bath temperature is reduced to 60 ℃, in solution, add earlier Acetyl Chloride 98Min. (about 0.44ml), the mol ratio that makes Acetyl Chloride 98Min. and Mierocrystalline cellulose glucose unit is 1: 1, add propionyl chloride (about 5.39ml) again behind the reaction 10h, the mol ratio that makes propionyl chloride and Mierocrystalline cellulose glucose unit is 10: 1, continues reaction 12h.
After reaction finished, the mode that the aftertreatment of reacting the back mixture and ionic liquid are reclaimed was with embodiment 4, and after testing, the substitution value that obtains the ethanoyl of product is DS
A=0.75; The substitution value of propionyl is DS
P=1.34.
Embodiment 9
Take by weighing the about 3g of Mierocrystalline cellulose, ionic liquid (BMIMCl) 7g puts into round-bottomed flask, and oil bath is heated to 120 ℃, and the sealing intense mechanical stirs 12h, obtains the cellulose solution of clear, and the concentration of cellulose solution is 30% (mass percent).Oil bath temperature is reduced to 80 ℃, earlier add propionyl chloride (about 9.70ml) in solution, the mol ratio that makes propionyl chloride and Mierocrystalline cellulose glucose unit is 6: 1, adds Acetyl Chloride 98Min. (about 9.25ml) again behind the reaction 3h, the mol ratio that makes Acetyl Chloride 98Min. and Mierocrystalline cellulose glucose unit is 7: 1, continues reaction 2h.
After reaction finished, the mode that the aftertreatment of reacting the back mixture and ionic liquid are reclaimed was with embodiment 1, and after testing, the substitution value that obtains the ethanoyl of product is DS
A=0.29; The substitution value of propionyl is DS
P=2.15.
Embodiment 10
Take by weighing the about 0.6g of Mierocrystalline cellulose, ionic liquid (BMIMCl) 14.4g puts into round-bottomed flask, and oil bath is heated to 80 ℃, and the sealing intense mechanical stirs 2h, obtains the cellulose solution of clear, and the concentration of cellulose solution is 4% (mass percent).Oil bath temperature is reduced to 40 ℃, in solution, add earlier Acetyl Chloride 98Min. (about 1.59ml) and butyryl chloride (about 3.49ml) simultaneously, making the mol ratio of Acetyl Chloride 98Min. and Mierocrystalline cellulose glucose unit is 6: 1, and the mol ratio that makes butyryl chloride and Mierocrystalline cellulose glucose unit is 9: 1, reaction 4h.
After reaction finished, the mode that the aftertreatment of reacting the back mixture and ionic liquid are reclaimed was with embodiment 1, and after testing, the degree of substitution with acetyl group of product is DS
A=1.45; The butyryl radicals substitution value is DS
B=0.98.
Embodiment 11
Take by weighing the about 3g of Mierocrystalline cellulose, ionic liquid (BMIMCl) 17g puts into round-bottomed flask, and oil bath is heated to 100 ℃, and the sealing intense mechanical stirs 8h, obtains the cellulose solution of clear, and the concentration of cellulose solution is 15% (mass percent).Oil bath temperature is reduced to 60 ℃, add Acetyl Chloride 98Min. (about 10.57ml) earlier in solution, the mol ratio that makes Acetyl Chloride 98Min. and Mierocrystalline cellulose glucose unit is 8: 1; Add butyryl chloride (about 7.75ml) again behind the reaction 1h, the mol ratio that makes butyryl chloride and Mierocrystalline cellulose glucose unit is 4: 1, continues reaction 5h.
After reaction finished, the mode that the aftertreatment of reacting the back mixture and ionic liquid are reclaimed was with embodiment 1, and after testing, the degree of substitution with acetyl group that obtains product is DS
A=2.00; The butyryl radicals substitution value is DS
B=0.86.
Embodiment 12
Take by weighing the about 0.6g of Mierocrystalline cellulose, ionic liquid (BMIMCl) 9.4g puts into round-bottomed flask, and oil bath is heated to 80 ℃, and the sealing intense mechanical stirs 4h, obtains the cellulose solution of clear, and the concentration of cellulose solution is 6% (mass percent).In solution, add earlier butyryl chloride (about 0.39ml), the mol ratio that makes butyryl chloride and Mierocrystalline cellulose glucose unit is 1: 1, add Acetyl Chloride 98Min. (about 2.64ml) again behind the reaction 12h, the mol ratio that makes Acetyl Chloride 98Min. and Mierocrystalline cellulose glucose unit is 10: 1, continues reaction 0.5h.
After reaction finished, the mode that the aftertreatment of reacting the back mixture and ionic liquid are reclaimed was with embodiment 1, and after testing, the degree of substitution with acetyl group that obtains product is DS
A=1.47, the butyryl radicals substitution value is DS
B=0.75.
Claims (10)
1. method for preparing cellulose acetate propionate or cellulose acetate butyrate, this method may further comprise the steps:
A. Mierocrystalline cellulose is mixed with ionic liquid that can dissolving cellulos, obtain containing cellulosic ionic liquid solution;
B. with 1) acetylation reagent and propionyl reagent or 2) acetylation reagent and Butyrylation reagent adds described containing in the cellulosic ionic liquid solution, 40-120 ℃ of reaction 1-24 hour, preferred 1-12 hour, obtains reaction mixture;
C. in described reaction mixture, add C
1-C
3Lower aliphatic alcohols, filter the reaction mixture contain lower aliphatic alcohols;
D. behind the solid drying that filtration is obtained, obtain cellulose acetate propionate or cellulose acetate butyrate.
2. method according to claim 1, wherein step a comprise with described Mierocrystalline cellulose 40-120 ℃ with ionic liquid mixing that can dissolving cellulos 1-12 hour, obtain containing cellulosic ionic liquid solution.
3. method according to claim 1 and 2, wherein the temperature of reaction of step b is 60-120 ℃, preferred 80-100 ℃.
4. according to each described method among the claim 1-3, wherein said C
1-C
3Lower aliphatic alcohols and ion liquid volume ratio be 3: 1-10: 1, preferably, described lower aliphatic alcohols is methyl alcohol or ethanol.
5. according to each described method among the claim 1-4; wherein in described step b; with 1) acetylation reagent and propionyl reagent or 2) acetylation reagent and Butyrylation reagent adds at the same time or separately and contains in the cellulosic ionic liquid solution; when with 1) acetylation reagent and propionyl reagent or 2) acetylation reagent and Butyrylation reagent adds respectively when containing cellulosic ionic liquid solution; the joining day of two kinds of acylating reagents is spaced apart 0.5-12 hour, preferred 1-5 hour.
6. according to each described method among the claim 1-5, wherein said acetylation reagent is diacetyl oxide or Acetyl Chloride 98Min., and described propionyl reagent is propionic anhydride or propionyl chloride, and described Butyrylation reagent is butyryl oxide or butyryl chloride.
7. according to each described method among the claim 1-6, wherein saidly contain that Mierocrystalline cellulose quality concentration is 1-30% in the cellulosic ionic liquid solution, preferred 4-10%.
8. according to each described method among the claim 1-7, the mol ratio of glucose unit is 1 in wherein said acetylation reagent, propionyl reagent or Butyrylation reagent and the described Mierocrystalline cellulose: 1-10: 1, preferred 3: 1-5: 1.
9. according to each described method among the claim 1-8, wherein said ionic liquid that can dissolving cellulos is the C of imidazoles halogen or imidazoles
1-C
6Carboxylate salt, preferably, described imidazoles halogen is the imidazoles villaumite, the C of described imidazoles
1-C
6Carboxylate salt is an imidazoles acetate.
10. method according to claim 9, the C of wherein said imidazoles halogen or imidazoles
1-C
6The positively charged ion of carboxylate salt has following formula (I) structure:
In this structural formula, R
1And R
2Be C
1-C
20Alkyl or alkenyl, R
3, R
4, R
5Be independently selected from hydrogen, C
1-C
20Alkyl, alkoxyl group and thiazolinyl;
Preferably, the C of described imidazoles halogen or imidazoles
1-C
6The positively charged ion of carboxylate salt has formula (II) structure:
R
1And R
2Be C
1-C
20Alkyl or alkenyl;
More preferably, the C of described imidazoles halogen or imidazoles
1-C
6The positively charged ion of carboxylate salt has formula (III) structure:
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