CN103360619A - Method for regulating and controlling crystallinity of crystals on cellulose surface - Google Patents
Method for regulating and controlling crystallinity of crystals on cellulose surface Download PDFInfo
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- CN103360619A CN103360619A CN2013102480210A CN201310248021A CN103360619A CN 103360619 A CN103360619 A CN 103360619A CN 2013102480210 A CN2013102480210 A CN 2013102480210A CN 201310248021 A CN201310248021 A CN 201310248021A CN 103360619 A CN103360619 A CN 103360619A
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- cellulose
- ionic liquid
- solvent
- mierocrystalline cellulose
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- 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 a method for regulating and controlling crystallinity of crystals on a cellulose surface, which relates to the field of application of biomass resource, in particular to the technical field of application of organic high molecular cellulose. According to the method for regulating and controlling the crystallinity of crystals on the cellulose surface, ionic liquid aqueous solution with concentration of 60-95 percent is used as a solvent; the cellulose and the solvent are mixed according to the mass ratio of the cellulose to the solvent of 1:100-1:8 and react at the temperature of 80-170 DEG C for 0.5-10 hours; the ionic liquid is at least one ionic liquid compound with a general formula of A<+>B<->; A<+> is cation with a general formula I; and B is halogen. The method has the advantages of simple production process, low production cost and no environmental pollution caused by wastewater and waste gas.
Description
Technical field
The present invention relates to a kind of method of regulating and control cellulose surface crystal structure degree, relate to the biomass resource Application Areas, particularly organic polymer Mierocrystalline cellulose applied technical field.
Background technology
Along with day by day serious oil crisis and environmental pollution, country is more and more stricter to the requirement of industrial chemicals production process, more and more payes attention to the development and utilization of renewable biomass resource.Mierocrystalline cellulose is that (accounting for 40～50%Wt), is renewable biomass resource the abundantest on the earth for the main component of farm crop and forestry waste.China is a large agricultural country, and about 600,000,000 ton/years of national agricultural crop straw output wherein can be collected about 300,000,000 ton/years of the Mierocrystalline cellulose of utilization.Being important industrial chemicals with cellulose conversion, is the good method of the development and protection environment of renewable biomass resource, has great importance for alleviating day by day serious environmental pollution and improving the Future in China resource structures.
Cellulose surface is made of jointly crystal and amorphous area, natural cellulose has higher degree of crystallinity, different sites shows different accessibilities to same chemical reagent or catalyzer simultaneously, crystal block section is because the more noncrystal part of the tight reagent accessibility of compound with regular structure is low, and this causes cellulose surface low to the selectivity of chemical reagent.Simultaneously, because cellulosic molecule is interior and the effect of intermolecular hydrogen bonding, its heterogeneous reaction must experience successively reaction process from outward appearance to inner essence.Therefore, may change by a kind of method the crystal structure degree on cellulosic surface, and excessively do not destroy cellulosic internal structure, make it keep as far as possible mechanical property originally, the fiber of processing rear surface degree of crystallinity raising can have better stability to chemical reagent, heat, radiation etc., process the fiber that rear surface degree of crystallinity reduces and then have higher accessibility, the processing such as the easier modification of carrying out the surface, dyeing.
But because cellulosic structure is stable fine and close, be difficult to it is processed, one of cellulosic method of present eco-friendly processing is the ionic liquid method, Mierocrystalline cellulose is under the effect of pure ionic liquid, cellulose crystallity obviously descends, can form homogeneous solution behind the certain hour, wherein degree of crystallinity decline and cellulose dissolution carry out simultaneously.And the applicant finds Mierocrystalline cellulose is joined in the certain density ionic liquid aqueous solution, the aqueous solution of ionic liquid can only dissolve a small amount of amorphous fibres element, can destroy simultaneously the crystalline structure in the Mierocrystalline cellulose under certain condition, its degree of crystallinity is descended, and can not directly dissolve the Mierocrystalline cellulose of crystal, and because solvent destroys the process of the crystalline structure in the Mierocrystalline cellulose, it is the process that solvent penetrates into cellulose crystals inside, its speed also is subject to solvent in the control of fibrous inside mass transfer, thereby, if at a certain temperature, a certain amount of Mierocrystalline cellulose is placed certain density ionic liquid aqueous solution, and then cellulosic degree of crystallinity has the situation that rises and descend and alternately occur.Based on this, the applicant further studies discovery under certain condition (such as raising temperature, ionic liquid concentration), can make within a certain period of time the speed of dissolving amorphous fibres element greater than the speed of the crystalline structure in the solvent destruction Mierocrystalline cellulose, by can dissolve surperficial amorphous fibres element with ionic liquid aqueous solution, surface crystallinity is raise; Perhaps make solvent destroy the speed of the crystalline structure in the Mierocrystalline cellulose greater than the speed of dissolving amorphous fibres element, surface crystallinity is reduced.
Thereby the method for this change cellulose surface crystal structure degree based on ion liquid solvent may promote to develop new efficient Mierocrystalline cellulose utilisation technology, also can promote the renewable biomass efficient utilization of resource.
Reference
[1] Zhang Ruiqin.The fuel of biomass derived and chemical substance..Zhengzhou: press of Zhengzhou University, 2004.
[2] Zhu Qingshi, Yan Lifeng, Guo Qingxiang..The biomass clean energy..Beijing: Chemical Industry Press, 2002.
[3]Swatloski?P?R,Spear?S?K,Holbery?J?D,Rogers?R?D.J.Am.Chem.Soc.,2002,124:4974-4975。
[4]Wu?J,Zhang?J,Zhang?H,He?S,Ren?Q,Guo?M.L.Biomacromolecules,2004,5:266-268。
[5]Fukaya?Y,Sugimoto?A,Ohno?H.Biomacromolecules,2006,7:3295-3297。
Summary of the invention
The purpose of this invention is to provide that a kind of technique is simple, the method for low production cost, change cellulose surface crystal structure degree that productive rate is high.
A kind of method of regulating and control cellulose surface crystal structure degree, ionic liquid aqueous solution take concentration as 60～95wt% is solvent, is Mierocrystalline cellulose: solvent=1:100～1:8 by the mass ratio of Mierocrystalline cellulose and solvent, with Mierocrystalline cellulose and solvent, 80～170 ℃ of lower reactions 0.5～10 hour
Wherein, described Mierocrystalline cellulose is gossypin or Microcrystalline Cellulose;
Described ionic liquid is at least a general formula A that has
+B
-Ion liquid compound, wherein, A
+For having the positively charged ion of general formula I, B is halogen,
Wherein, in the general formula I, R
1Be methyl, R
2For carbonatoms is that 1～5 alkyl or carbonatoms are 1～5 olefin group.
The method of regulation and control cellulose surface crystal structure degree of the present invention, be preferable in the reflux and carry out, specific as follows: as Mierocrystalline cellulose, ion liquid solvent to be joined in the flask of intensification, stirring, reflux and mix into reaction solution, 80～170 ℃ of lower reactions 0.5～10 hour, behind the cooling reaction solution, direct filtration reaction solution, and washing leaching cake, 30 ℃ lower dry that cellulosic surface crystal degree of crystallinity changes product, and solvent recovery cycle is used.
Ionic liquid of the present invention is the synthetic ionic liquid of glyoxaline compound and halogenated alkane, and it is: A
+B
-, wherein, B is halogen, A
+For having the positively charged ion of general formula I, wherein the general formula I positively charged ion is alkyl imidazolium cation.
Wherein, in the general formula I, R
1Be methyl, R
2For carbonatoms is that 1～5 alkyl or carbonatoms are 1～5 olefin group.
Unless otherwise indicated, term used herein has following implication.
Term used herein " alkyl " comprises straight chained alkyl and branched-chain alkyl.As mention single alkyl such as " propyl group ", and then only refer in particular to straight chained alkyl, as mention single branched-chain alkyl such as " sec.-propyl ", then only refer in particular to branched-chain alkyl.
Term used herein " halogen " comprises fluorine, chlorine, bromine and iodine.
The preferred described ionic liquid of method of regulation and control cellulose surface crystal structure degree of the present invention is the halo imidazole type ion liquid, such as following cation A
+Ion liquid compound with general formula I:
1-butyl-3-Methylimidazole villaumite ionic liquid ([Bmim] [Cl]), R
1=methyl, R
2=butyl, B=chlorine;
1-allyl group-3-Methylimidazole villaumite ionic liquid ([Amim] [Cl]), R
1=methyl, R
2=allyl group, B=chlorine;
1-ethyl-3-methylimidazole villaumite ionic liquid ([Emim] [Cl]), R
1=methyl, R
2=ethyl, B=chlorine;
1-butyl-3-Methylimidazole bromine salt ion liquid ([Bmim] [Br]), R
1=methyl, R
2=butyl, B=bromine;
1-ethyl-3-methylimidazole bromine salt ion liquid ([Emim] [Br]), R
1=methyl, R
2=ethyl, B=bromine.
The mechanism of ion liquid solvent dissolving cellulos: have stronger interaction between ion liquid solvent and cellulose macromolecule, destroyed a large amount of hydrogen bonds that exist in cellulosic molecule interchain and the molecular chain, thereby made cellulose dissolution.Take [Bmim] [Cl] ionic liquid as example: under heating condition, the ion in the ionic liquid dissociates, and forms free positively charged ion [Bmim]
+And negatively charged ion [Cl]
-, negatively charged ion [Cl]
-Form hydrogen bond action with the hydrogen atom on the hydroxyl in the cellulose macromolecule chain, and free positively charged ion [Bmim]
+With the Sauerstoffatom effect on the hydroxyl in the cellulose macromolecule chain, thereby destroy original hydrogen bond in the Mierocrystalline cellulose, caused the dissolving of Mierocrystalline cellulose in ionic liquid.
The mechanism of ionic liquid aqueous solution dissolving cellulos is identical with above ion liquid dissolving Mierocrystalline cellulose mechanism, just owing to moisture in the ionic liquid aqueous solution, has reduced the polarity of ionic liquid, causes dissolving a small amount of non-crystal Mierocrystalline cellulose.
Beneficial effect of the present invention is:
1. ionic liquid steam forces down, Heat stability is good;
2. ion liquid solvent can recycle;
3. simple, the low production cost of production technique pollutes without waste water, exhaust environment;
4. the product Mierocrystalline cellulose has very strong prospects for commercial application, as being used for the linen-cotton fibrid dyeing in textile printing and dyeing field.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Used Microcrystalline Cellulose is available from Chemical Reagent Co., Ltd., Sinopharm Group among the following embodiment, model specification: column chromatography (Shanghai examination).
Measure degree of crystallinity by X-ray diffraction method
X-ray crystalline indice=(I
002-I
Am)/I
002* 100%
In the formula:
I
002-002 maximum diffraction intensity;
I
AmDiffracted intensity, the i.e. diffracted intensity of pars amorpha during-2 θ=18 °.
(" Plant Fiber Chemistry " author of China Light Industry Press: the refined favour ISBN:7501929696 of poplar)
Embodiment 1～20
Raw material, implementation condition and product degree of crystallinity that embodiment 1～20 adopts see Table 1.Put down in writing " product cellulose crystallity " in the table 1 and be relative crystallinity, the degree of crystallinity of the product cellulose crystallity=treated Microcrystalline Cellulose of putting down in writing/Microcrystalline Cellulose * 100% is untreated.The material crystal degree is 100%, and greater than 100%, low then less than 100%, concrete operations are as follows than Gao Ze for product degree of crystallinity:
Embodiment 1: at first the 1g Microcrystalline Cellulose is joined 100g[Amim is housed] in the 250ml flask of [Cl] aqueous solution, ionic liquid concentration 60wt%, place oil bath to heat, the control temperature is at 100 ℃, behind the reaction 0.5h, behind the cooling reaction solution, the direct filtration reaction solution, and washing leaching cake, 30 ℃ are lower dry that cellulosic surface crystal degree of crystallinity changes product, and cellulose crystallity and raw cellulose are in a ratio of 105%.
Embodiment 2～20 is identical with embodiment 1 working method, and the concrete operations condition sees Table 1.
Table 1
Claims (2)
1. method of regulating and control cellulose surface crystal structure degree, ionic liquid aqueous solution take concentration as 60～95wt% is solvent, is Mierocrystalline cellulose: solvent=1:100～1:8 by the mass ratio of Mierocrystalline cellulose and solvent, with Mierocrystalline cellulose and solvent, 80～170 ℃ of lower reactions 0.5～10 hour
Wherein, described Mierocrystalline cellulose is gossypin or Microcrystalline Cellulose;
Described ionic liquid is at least a general formula A that has
+B
-Ion liquid compound, wherein, A
+For having the positively charged ion of general formula I, B is halogen,
Wherein, in the general formula I, R
1Be methyl, R
2For carbonatoms is that 1～5 alkyl or carbonatoms are 1～5 olefin group.
2. method according to claim 1, it is characterized in that: described ionic liquid is 1-butyl-3-Methylimidazole villaumite ionic liquid, 1-allyl group-3-Methylimidazole villaumite ionic liquid, 1-ethyl-3-methylimidazole villaumite ionic liquid, 1-butyl-3-Methylimidazole bromine salt ion liquid or 1-ethyl-3-methylimidazole bromine salt ion liquid.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103966878A (en) * | 2014-01-02 | 2014-08-06 | 大连工业大学 | Method for preparing microcrystalline cellulose by ionic liquid |
| EP3072923A1 (en) * | 2015-03-27 | 2016-09-28 | Seiko Epson Corporation | Composition, shaped article production method, and shaped article |
| EP3075746A1 (en) * | 2015-03-30 | 2016-10-05 | Seiko Epson Corporation | Composition set, shaped article production method, and shaped article |
| CN108779310A (en) * | 2016-03-31 | 2018-11-09 | 古河电气工业株式会社 | Thermoplastic resin composition, the manufacturing method of thermoplastic resin composition, cellulose reinforced resin molded product and cellulose reinforced resin molded product manufacturing method |
| CN108774288A (en) * | 2018-06-22 | 2018-11-09 | 齐鲁工业大学 | It is a kind of to utilize BminHSO4The method that system prepares Cellulose nanocrystal body |
| US11597817B2 (en) | 2016-03-31 | 2023-03-07 | Furukawa Electric Co., Ltd | Thermoplastic resin composition, method of producing thermoplastic resin composition, molded article of cellulose-reinforced resin, and method of producing molded article of cellulose-reinforced resin |
| US11629244B2 (en) | 2016-03-31 | 2023-04-18 | Furukawa Electric Co., Ltd. | Thermoplastic resin composition, cellulose-reinforced thermoplastic resin composition, method of producing cellulose-reinforced thermoplastic resin composition, molded article of cellulose-reinforced resin, and method of producing molded article of cellulose-reinforced resin |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103966878A (en) * | 2014-01-02 | 2014-08-06 | 大连工业大学 | Method for preparing microcrystalline cellulose by ionic liquid |
| CN103966878B (en) * | 2014-01-02 | 2016-05-11 | 大连工业大学 | Ionic liquid is prepared the method for microcrystalline cellulose |
| EP3072923A1 (en) * | 2015-03-27 | 2016-09-28 | Seiko Epson Corporation | Composition, shaped article production method, and shaped article |
| US10519335B2 (en) | 2015-03-27 | 2019-12-31 | Seiko Epson Corporation | Composition, shaped article production method, and shaped article |
| EP3075746A1 (en) * | 2015-03-30 | 2016-10-05 | Seiko Epson Corporation | Composition set, shaped article production method, and shaped article |
| US10533107B2 (en) | 2015-03-30 | 2020-01-14 | Seiko Epson Corporation | Composition set, shaped article production method, and shaped article |
| CN108779310A (en) * | 2016-03-31 | 2018-11-09 | 古河电气工业株式会社 | Thermoplastic resin composition, the manufacturing method of thermoplastic resin composition, cellulose reinforced resin molded product and cellulose reinforced resin molded product manufacturing method |
| US11466140B2 (en) | 2016-03-31 | 2022-10-11 | Furukawa Electric Co., Ltd. | Thermoplastic resin composition, method of producing thermoplastic resin composition, molded article of cellulose-reinforced resin, and method of producing molded article of cellulose-reinforced resin |
| US11597817B2 (en) | 2016-03-31 | 2023-03-07 | Furukawa Electric Co., Ltd | Thermoplastic resin composition, method of producing thermoplastic resin composition, molded article of cellulose-reinforced resin, and method of producing molded article of cellulose-reinforced resin |
| US11629244B2 (en) | 2016-03-31 | 2023-04-18 | Furukawa Electric Co., Ltd. | Thermoplastic resin composition, cellulose-reinforced thermoplastic resin composition, method of producing cellulose-reinforced thermoplastic resin composition, molded article of cellulose-reinforced resin, and method of producing molded article of cellulose-reinforced resin |
| CN108774288A (en) * | 2018-06-22 | 2018-11-09 | 齐鲁工业大学 | It is a kind of to utilize BminHSO4The method that system prepares Cellulose nanocrystal body |
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