CN103657144A - Method for separating unimolecular cellulose - Google Patents
Method for separating unimolecular cellulose Download PDFInfo
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- CN103657144A CN103657144A CN201310676949.9A CN201310676949A CN103657144A CN 103657144 A CN103657144 A CN 103657144A CN 201310676949 A CN201310676949 A CN 201310676949A CN 103657144 A CN103657144 A CN 103657144A
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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 advantage such as pollution of ecological environment not.The macromolecular polysaccharide that cellulose is comprised 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 problem, 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 scientific and technical development, cellulosic research and Application and Development have been reached to unprecedented height, in weaving, 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., in national economy, plays an important role.In recent years, utilize the cellulose raw raw material extensively existing on the earth to produce clean alcohol fuel, as a kind of high-end clean energy technology, be sent to very high expectation.And higher production cost has limited the popularization of the biological alcohol fuel technology of cellulose.If can study the reaction mechanism that cellulose transfers biomass fuel and other chemicals to from molecular level, will play inestimable impetus to the exploitation of cellulose new product and new technology spread.But there is no at present the relevant report of unimolecule cellulose separation.
Summary of the invention
The present invention newly provides a kind of unimolecule cellulosic separation method.
For solving the problems of the technologies described above, the invention of this reality adopts following technical scheme:
The cellulosic separation method of unimolecule, comprises the following steps that order is joined:
A, by mass ratio be the cellulose of (0.001mg:1g)-(100mg:1g) and solvent according to miscible, and be heated to 90-160 ℃, insulation 1-8h;
B, steps A gained material is cooled to 30-70 ℃;
C, get 1-50 μ L step B gains gob and be added in the mica sheet surface that siloxanes is modified, with the speed spin coating 0.5-5 minute of 500-3000 rev/min, then at 70-120 ℃, insulation 1-4 hour, washing purifying, dries up, and obtains.
Adopt said method, the separable unimolecule cellulose that obtains, for providing new reference method from molecular level research and exploitation cellulose new product.
Applicant finds after deliberation, in step C, the mica sheet that uses siloxanes to modify can make unimolecule cellulose by the effect of hydrogen bond and covalent bond, be attached to securely the surface of mica sheet, does not relatively have modified mica sheet can reduce significantly the cellulosic loss of unimolecule.
The preparation method of the mica that siloxanes is modified is: mica sheet is placed in to the siloxanes aqueous solution that volume ratio is (1:100)-(1:1000) and after 4-10 minute, takes out, after washing, drying up, obtain.Can further improve so the cellulosic yield of unimolecule.Above-mentioned volume ratio refers to the volume ratio of siloxanes and water.Mica sheet standing time in the siloxanes aqueous solution is preferably 4-6 minute, can guarantee product quality like this, can enhance productivity again.
After mica sheet takes out, washing, and dry up with nitrogen, obtain.So not only easy and simple to handle, and can guarantee the purity of product.
Mica sheet is preferably Electronic Speculum substrate mica, and surface roughness is less than 0.2 nanometer.Be convenient to like this clear view unimolecule cellulose.The roughness of the mica sheet after the siloxanes aqueous solution is modified is also less than 0.2 nanometer.Like this can the adhesive force of bonding molecule cellulose on mica sheet, be convenient to again clear view unimolecule cellulose.
Siloxanes is 3-aminopropyl triethoxysilane, isocyanic acid propyl-triethoxysilicane or 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane.Can further improve like this unimolecule cellulose adhesive force on mica sheet, further reduce the cellulosic loss of unimolecule.
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 ℃, adds catalyst, mixes.Can further improve so the cellulosic yield of unimolecule.
In step B, catalyst is the concentrated sulfuric acid or acidic ion liquid, and catalyst addition is the 0.1%-1% of steps A gained quality of material.Can guarantee like this efficiency of preparation and the yield of product.
In steps A, cellulose can be various celluloses, is preferably cotton, flax, microcrystalline cellulose or paper pulp.
In step C, be incubated after 1-4 hour, washing, and dry up with nitrogen, obtain.So not only easy and simple to handle, and can guarantee the purity of products obtained therefrom.
The mica sheet that siloxanes is modified is that the length of side is the square of 0.5-1cm.So both save material, and can guarantee the yield of product 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.
Accompanying drawing explanation
Fig. 1 is the cellulosic AFM phenogram of the embodiment of the present invention 1 gained unimolecule;
From Fig. 1, can know 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, bright spot is 2 nanometers with dim spot difference in height, by height analysis software, can measure the height of fiber in figure and be about 0.5 nanometer, it is corresponding with the corresponding height of 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, referring to Determination of the Structure of Cellulose II, Vol.9, No.2, March-April1976).
The specific embodiment
In order to understand better the present invention, below in conjunction with embodiment, further illustrate content of the present invention, 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 ℃, and insulation reaction 4h, fully dissolves.Then be cooled to 70 ℃; 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 of getting 10 μ L drips the mica sheet surface of modifying at 3-aminopropyl triethoxysilane, with the speed spin coatings of 1000 revs/min 1 minute, in 100 ℃ of insulations 2 hours, finally use deionized water washing purifying, and dry up with nitrogen, at mica surface, obtain unimolecule cellulose (being highly about 0.5 nanometer).
Embodiment 2
By microcrystalline cellulose and ionic liquid chlorination (1-butyl-3-methylimidazole), according to mass ratio, be that 1mg:1g is miscible, and be heated to 110 ℃, insulation reaction 6h, fully dissolves; Then be cooled to 70 ℃, add the concentrated sulfuric acid of liquid quality fraction 0.2%, fully stir; Mica sheet is placed in the 3-that volume ratio is 1:500 (2,3-epoxy the third oxygen) the propyl trimethoxy silicane aqueous solution 5 minutes, and fully, after washing, nitrogen dries up, and obtains the mica sheet that 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane is modified; Cellulose chlorination (1-butyl-3-methylimidazole) solution of getting 20 μ L drips at 3-(2,3-epoxy the third oxygen) the mica sheet surface that propyl trimethoxy silicane is modified, with the speed spin coatings of 2000 revs/min 3 minutes, in 80 ℃ of insulations 3 hours, finally use deionized water washing purifying, and dry up with nitrogen, at mica surface, obtain unimolecule cellulose (be highly about 0.5 nanometer, method of testing is with embodiment 1).
Embodiment 3
By flax and lithium chloride/dimethylacetylamide (LiCl/DMAc), according to mass ratio, be that 0.5mg:1g is miscible, and be heated to 150 ℃, insulation reaction 3h, fully dissolves, and is then cooled to 50 ℃; Mica sheet is placed in the isocyanic acid propyl-triethoxysilicane aqueous solution 5 minutes that volume ratio is 1:100, and fully, after washing, nitrogen dries up, and obtains the mica sheet that isocyanic acid propyl-triethoxysilicane is modified; Cellulose lithium chloride/dimethylacetylamide (LiCl/DMAc) solution of getting 30 μ L drips the mica sheet surface of modifying at isocyanic acid propyl-triethoxysilicane, with the speed spin coatings of 3000 revs/min 1.5 minutes, in 90 ℃ of insulations 2 hours, finally use deionized water washing purifying, and dry up with nitrogen, at mica surface, obtain unimolecule cellulose (be highly about 0.5 nanometer, method of testing is with embodiment 1).
Embodiment 4
By paper pulp and ionic liquid chlorination (1-butyl-3-methylimidazole), according to mass ratio, be that 0.1mg:1g is miscible, and be heated to 110 ℃, insulation reaction 6h, fully dissolves; Then be cooled to 70 ℃, add the acidic ion liquid 4-(3-methyl isophthalic acid-imidazoles of liquid quality fraction 0.5%)-1-butyl sulfonic acid disulfate, fully stirs; Mica sheet is placed in the 3-that volume ratio is 1:500 (2,3-epoxy the third oxygen) the propyl trimethoxy silicane aqueous solution 5 minutes, and fully, after washing, nitrogen dries up, and obtains the mica that 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane is modified; Cellulose chlorination (1-butyl-3-methylimidazole) solution of getting 20 μ L drips at 3-(2,3-epoxy the third oxygen) the mica sheet surface that propyl trimethoxy silicane is modified, with the speed spin coatings of 2000 revs/min 3 minutes, in 80 ℃ of insulations 3 hours, finally use deionized water washing purifying, and dry up with nitrogen, at mica surface, obtain unimolecule cellulose (be highly about 0.5 nanometer, method of testing is with embodiment 1).
Claims (10)
1. the cellulosic separation method of unimolecule, is characterized in that: comprise the following steps that order is joined:
A, by mass ratio be the cellulose of (0.001mg:1g)-(100mg:1g) and solvent according to miscible, and be heated to 90-160 ℃, insulation 1-8h;
B, steps A gained material is cooled to 30-70 ℃;
C, get 1-50 μ L step B gains gob and be added in the mica sheet surface that siloxanes is modified, with the speed spin coating 0.5-5 minute of 500-3000 rev/min, then at 70-120 ℃, insulation 1-4 hour, washing purifying, dries up, and obtains.
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 was placed in to the siloxanes aqueous solution that volume ratio is (1:100)-(1:1000) after 4-10 minute, take out, after washing, drying up, obtain.
3. the cellulosic separation method of unimolecule as claimed in claim 2, is characterized in that: after mica sheet takes out, wash, and dry up with nitrogen, obtain.
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 unimolecule as claimed in claim 2 or claim 3, is characterized in that: siloxanes is 3-aminopropyl triethoxysilane, isocyanic acid propyl-triethoxysilicane or 3-(2,3-epoxy the third oxygen) propyl trimethoxy silicane.
6. the cellulosic separation method of unimolecule as described in claim 1-3 any one, is characterized in that: in steps A, solvent is ionic liquid, N-methylmorpholine-N-oxide or lithium chloride/dimethylacetylamide; When solvent is ionic liquid, step B is, steps A gained material is cooled to 30-70 ℃, adds catalyst, mixes.
7. the cellulosic separation method of unimolecule as claimed in claim 6, is characterized in that: in step B, catalyst is the concentrated sulfuric acid or acidic ion liquid, and catalyst addition is the 0.1%-1% of steps A gained quality of material.
8. the cellulosic separation method of unimolecule as described in claim 1-3 any one, is characterized in that: in steps A, cellulose is cotton, flax, microcrystalline cellulose or paper pulp.
9. the cellulosic separation method of unimolecule as described in claim 1-3 any one, is characterized in that: in step C, be incubated after 1-4 hour, wash, and dry up with nitrogen, obtain.
10. the cellulosic separation method of unimolecule as described in claim 1-3 any one, is characterized in that: the mica sheet that siloxanes is modified is that the length of side is the square of 0.5-1cm.
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| CN113278166A (en) * | 2021-05-19 | 2021-08-20 | 青岛量子元基环保科技有限公司 | Dissolution regeneration and stable dispersion system of monomolecular cellulose |
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