CN103657144B - Method for separating unimolecular cellulose - Google Patents
Method for separating unimolecular cellulose Download PDFInfo
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- CN103657144B CN103657144B CN201310676949.9A CN201310676949A CN103657144B CN 103657144 B CN103657144 B CN 103657144B CN 201310676949 A CN201310676949 A CN 201310676949A CN 103657144 B CN103657144 B CN 103657144B
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Abstract
The invention discloses a method for separating unimolecular cellulose. The method sequentially comprises the following steps: A, mixing and dissolving cellulose and a solvent in a mass ratio of (0.001mg:1g)-(100mg:1g), heating to 90-160 DEG C, and insulating for 1-8 hours; B, cooling the material in the step A to 30-70 DEG C; C, dripping 1-5mu L of the material in the step B on the surface of a siloxane modified mica plate, spinning for 0.5-5 minutes at a speed of 500-3,000 revolutions/minute, insulating for 1-4 minutes at 70-120 DEG C, washing and purifying, and blowing to dry. According to the method for separating the unimolecular cellulose provided by the invention, the prepared unimolecular cellulose is high in yield and high in purity, and a new reference method is provided to researches and development of new cellulose products from the molecular level.
Description
Technical field
The present invention relates to the cellulosic separation method of a kind of unimolecule.
Background technology
Cellulose, as one of the abundantest natural reproducible resource, reaches more than 1,000 hundred million tons by biosynthetic renewable cellulose every year, has inexpensive, degradable and the not advantage such as pollution of ecological environment.The macromolecular polysaccharide that cellulose is made up of glucose is the main component of plant cell wall, water insoluble and common organic solvents.Along with the growing interest of countries in the world environmental pollution, various countries more and more pay attention to biodegradable and the environment compatibility of this natural macromolecular material of cellulose, have stepped up its functional research and development.Along with the development of science and technology, unprecedented height has been reached to cellulosic research and Application and Development, except except weaving, in paper industry, cellulose is utilized with original form, other realizes industrialization in succession as sulfate cellulose, celluloid, cellulose acetate, methylcellulose, ethyl cellulose, light ethyl cellulose, light propyl cellulose and shuttle methylcellulose etc., plays an important role in national economy.In recent years, utilized the cellulose raw raw material that the earth extensively exists to produce clean alcohol fuel, as a kind of high-end clean energy technology, be sent to very high expectation.And higher production cost limits the popularization of the biological alcohol fuel technology of cellulose.If can study from molecular level the reaction mechanism that cellulose transfers biomass fuel and other chemicals to, then will play inestimable impetus to the exploitation of cellulose new product and new technology spread.But there is no the relevant report that unimolecule cellulose is separated at present.
Summary of the invention
The present invention newly provides the cellulosic separation method of a kind of unimolecule.
For solving the problems of the technologies described above, the invention of this reality adopts following technical scheme:
The cellulosic separation method of a kind of unimolecule, comprises the following steps that order connects:
A, be that the cellulose of (0.001mg:1g)-(100mg:1g) and solvent are miscible by mass ratio, and be heated to 90-160 DEG C, insulation 1-8h;
B, steps A gained material is cooled to 30-70 DEG C;
C, get 1-50 μ L step B gains gob be added in siloxanes modify mica sheet surface, with the speed spin coating 0.5-5 minute of 500-3000 rev/min, then at 70-120 DEG C, insulation 1-4 hour, washing purifying, dry up, to obtain final product.
Adopt said method, separablely obtain unimolecule cellulose, for providing new reference method from molecular level research and exploitation cellulose new product.
Applicant finds after deliberation, in step C, the mica sheet using siloxanes to modify can make unimolecule cellulose be attached to the surface of mica sheet securely by the effect of hydrogen bond and covalent bond, does not relatively have modified mica sheet can decrease the cellulosic loss of unimolecule significantly.
The preparation method of mica that siloxanes is modified is: after mica sheet being placed in the siloxanes aqueous solution that volume ratio is (1:100)-(1:1000) after 4-10 minute, taking out, wash, drying up, to obtain final product.Can further improve the cellulosic yield of unimolecule like this.Above-mentioned volume ratio refers to the volume ratio of siloxanes and water.The time that mica sheet leaves standstill in the siloxanes aqueous solution is preferably 4-6 minute, can ensure product quality like this, can enhance productivity again.
After mica sheet takes out, washing, and dry up with nitrogen, to obtain final product.So not only easy and simple to handle, and the purity of product can be ensured.
Mica sheet is preferably Electronic Speculum substrate mica, and surface roughness is less than 0.2 nanometer.Be convenient to clear view unimolecule cellulose like this.The roughness of the mica sheet after the modification of the siloxanes aqueous solution is also less than 0.2 nanometer.Like this can the adhesive force of bonding molecules fibrin on mica sheet, be convenient to again clear view unimolecule cellulose.
Siloxanes is 3-aminopropyl triethoxysilane, isocyanatopropyl triethoxysilane or 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane.Can further improve unimolecule cellulose adhesive force on mica sheet like this, reduce the cellulosic loss of unimolecule further.
In steps A, solvent is ionic liquid, N-methylmorpholine-N-oxide (NMMO) or lithium chloride/dimethylacetylamide (LiCl/DMAc); When solvent is ionic liquid, step B is, steps A gained material is cooled to 30-70 DEG C, adds catalyst, mixing.Can further improve the cellulosic yield of unimolecule like this.
In step B, catalyst is the concentrated sulfuric acid or acidic ion liquid, and catalyst charge is the 0.1%-1% of steps A gained quality of material.The yield of efficiency and the product prepared can be ensured like this.
In steps A, cellulose can be various cellulose, is preferably cotton, flax, microcrystalline cellulose or paper pulp.
In step C, be incubated after 1-4 hour, washing, and dry up with nitrogen, to obtain final product.So not only easy and simple to handle, and the purity of products obtained therefrom can be ensured.
The square of the mica sheet modified of siloxanes to be the length of side be 0.5-1cm.Both save material like this, the yield of product can be ensured simultaneously.
The NM technology of the present invention is prior art.
The invention provides the cellulosic separation method of a kind of unimolecule, the cellulosic yield of gained unimolecule is high, purity is high, for providing new reference method from molecular level research and exploitation cellulose new product.
Figure of description
Fig. 1 is the cellulosic AFM phenogram of the embodiment of the present invention 1 gained unimolecule;
Can know from Fig. 1 and see, isolated unimolecule cellulose is fixed on the mica sheet surface that siloxanes is modified, and the width scale of picture is 1.4 microns, this shows, the cellulosic length of unimolecule is from 100 nanometers to 500 nanometers, and the isolated cellulosic molecule of the method is the longest reaches several microns; In picture, most bright spot is 2 nanometers with most dim spot difference in height, the height of fiber in figure can be measured by Elevation Analysis software and be about 0.5 nanometer, it is corresponding with the height corresponding to single cellulosic molecule that (single cellulosic theoretical level value is 0.4-0.5 nanometer, determine whether that the cellulosic foundation of unimolecule is: confirm whether cellulosic height drops on the interval of 0.4-0.5 nanometer, see Determination of the Structure ofCellulose II, Vol.9, No.2, March-April 1976).
Detailed description of the invention
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
In following embodiment, mica sheet is Electronic Speculum substrate mica, purchased from middle mirror tech, during use, is cut to the square that the length of side is 0.8cm.
Embodiment 1
By absorbent cotton and NMMOH
2o is that 0.001mg:1g is miscible according to mass ratio, and is heated to 90 DEG C, insulation reaction 4h, fully dissolves.Then 70 DEG C are cooled to; Mica sheet is placed in the 3-aminopropyl triethoxysilane aqueous solution 5 minutes that volume ratio is 1:600, and fully after washing, nitrogen dries up, and obtains the mica that 3-aminopropyl triethoxysilane is modified; The cellulose NMMO solution getting 10 μ L drips the mica sheet surface of modifying at 3-aminopropyl triethoxysilane, with the speed spin coating 1 minute of 1000 revs/min, in 100 DEG C of insulations 2 hours, finally use deionized water washing purifying, and dry up with nitrogen, obtain unimolecule cellulose (being highly about 0.5 nanometer) at mica surface.
Embodiment 2
Be that 1mg:1g is miscible by microcrystalline cellulose and ionic liquid chlorination (1-butyl-3-methylimidazole) according to mass ratio, and be heated to 110 DEG C, insulation reaction 6h, fully dissolve; Then be cooled to 70 DEG C, add the concentrated sulfuric acid of liquid quality fraction 0.2%, fully stir; Mica sheet to be placed in 3-(2,3-epoxy third oxygen) the propyl trimethoxy silicane aqueous solution that volume ratio is 1:500 5 minutes, and fully after washing, nitrogen dries up, and obtains the mica sheet that 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane is modified; Cellulose chlorination (1-butyl-3-methylimidazole) solution getting 20 μ L drips at 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane modify mica sheet surface, with the speed spin coating 3 minutes of 2000 revs/min, in 80 DEG C of insulations 3 hours, finally use deionized water washing purifying, and dry up with nitrogen, obtain unimolecule cellulose (be highly about 0.5 nanometer, method of testing is with embodiment 1) at mica surface.
Embodiment 3
Be that 0.5mg:1g is miscible by flax and lithium chloride/dimethylacetylamide (LiCl/DMAc) according to mass ratio, and be heated to 150 DEG C, insulation reaction 3h, fully dissolve, be then cooled to 50 DEG C; Mica sheet is placed in the isocyanatopropyl triethoxysilane aqueous solution 5 minutes that volume ratio is 1:100, and fully after washing, nitrogen dries up, and obtains the mica sheet that isocyanatopropyl triethoxysilane is modified; Cellulose lithium chloride/dimethylacetylamide (LiCl/DMAc) solution getting 30 μ L drips the mica sheet surface of modifying at isocyanatopropyl triethoxysilane, with the speed spin coating 1.5 minutes of 3000 revs/min, in 90 DEG C of insulations 2 hours, finally use deionized water washing purifying, and dry up with nitrogen, unimolecule cellulose (be highly about 0.5 nanometer, method of testing is with embodiment 1) is obtained at mica surface.
Embodiment 4
Be that 0.1mg:1g is miscible by paper pulp and ionic liquid chlorination (1-butyl-3-methylimidazole) according to mass ratio, and be heated to 110 DEG C, insulation reaction 6h, fully dissolve; Then be cooled to 70 DEG C, add acidic ion liquid 4-(3-methyl isophthalic acid-imidazoles)-1-butyl sulfonic acid disulfate of liquid quality fraction 0.5%, fully stir; Mica sheet to be placed in 3-(2,3-epoxy third oxygen) the propyl trimethoxy silicane aqueous solution that volume ratio is 1:500 5 minutes, and fully after washing, nitrogen dries up, and obtains the mica that 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane is modified; Cellulose chlorination (1-butyl-3-methylimidazole) solution getting 20 μ L drips at 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane modify mica sheet surface, with the speed spin coating 3 minutes of 2000 revs/min, in 80 DEG C of insulations 3 hours, finally use deionized water washing purifying, and dry up with nitrogen, obtain unimolecule cellulose (be highly about 0.5 nanometer, method of testing is with embodiment 1) at mica surface.
Claims (8)
1. the cellulosic separation method of unimolecule, is characterized in that: comprise the following steps that order connects:
A, be that the cellulose of (0.001mg:1g)-(100mg:1g) and solvent are miscible by mass ratio, and be heated to 90-160 DEG C, insulation 1-8h;
B, steps A gained material is cooled to 30-70 DEG C;
C, get 1-50 μ L step B gains gob be added in siloxanes modify mica sheet surface, with the speed spin coating 0.5-5 minute of 500-3000 rev/min, then at 70-120 DEG C, insulation 1-4 hour, washing purifying, dry up, to obtain final product;
In steps A, solvent is ionic liquid, N-methylmorpholine-N-oxide or lithium chloride/dimethylacetylamide;
In steps A, cellulose is cotton, flax, microcrystalline cellulose or paper pulp;
Siloxanes in step C is 3-aminopropyl triethoxysilane, isocyanatopropyl triethoxysilane or 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane.
2. the cellulosic separation method of unimolecule as claimed in claim 1, it is characterized in that: the preparation method of the mica that siloxanes is modified is: mica sheet is placed in the siloxanes aqueous solution of volume ratio for (1:100)-(1:1000) after 4-10 minute, take out, washing, dry up after, to obtain final product.
3. the cellulosic separation method of unimolecule as claimed in claim 2, is characterized in that: after mica sheet takes out, washing, and dries up with nitrogen, to obtain final product.
4. the cellulosic separation method of unimolecule as claimed in claim 2 or claim 3, is characterized in that: mica sheet is Electronic Speculum substrate mica, and surface roughness is less than 0.2 nanometer.
5. the cellulosic separation method of the unimolecule as described in claim 1-3 any one, is characterized in that: when solvent is ionic liquid, and step B is, steps A gained material is cooled to 30-70 DEG C, adds catalyst, mixing.
6. the cellulosic separation method of unimolecule as claimed in claim 5, it is characterized in that: in step B, catalyst is the concentrated sulfuric acid or acidic ion liquid, and catalyst charge is the 0.1%-1% of steps A gained quality of material.
7. the cellulosic separation method of the unimolecule as described in claim 1-3 any one, is characterized in that: in step C, is incubated after 1-4 hour, washing, and dries up with nitrogen, to obtain final product.
8. the cellulosic separation method of the unimolecule as described in claim 1-3 any one, is characterized in that: the square of the mica sheet modified of siloxanes to be the length of side be 0.5-1cm.
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| CN104151622B (en) * | 2014-08-08 | 2016-09-07 | 华中科技大学 | A kind of biodegradable cellulose intermingling material and preparation method thereof |
| CN113278166B (en) * | 2021-05-19 | 2023-06-16 | 青岛量子元基环保科技有限公司 | Dissolving regeneration and stable dispersion system of single-molecule cellulose |
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| US4364759A (en) * | 1979-03-28 | 1982-12-21 | Monsanto Company | Methods for preparing anisotropic hollow fiber membranes comprising polymer of acrylonitrile and styrene and hollow fiber membranes produced therefrom |
| US7056455B2 (en) * | 2001-04-06 | 2006-06-06 | Carnegie Mellon University | Process for the preparation of nanostructured materials |
| CN101182686A (en) * | 2007-12-07 | 2008-05-21 | 华南理工大学 | Decrystallizing method of cellulose in ion liquid |
| CN101509209B (en) * | 2009-03-10 | 2011-02-09 | 中国林业科学研究院林产化学工业研究所 | Method of preparing clubbed nano-cellulose |
| CN101503865B (en) * | 2009-03-23 | 2010-08-25 | 江南大学 | Method for preparing mlcrocrystalline cellulose by corps straw |
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