CN1289587C - Cellosolve and its use - Google Patents
Cellosolve and its use Download PDFInfo
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- CN1289587C CN1289587C CN 200410012682 CN200410012682A CN1289587C CN 1289587 C CN1289587 C CN 1289587C CN 200410012682 CN200410012682 CN 200410012682 CN 200410012682 A CN200410012682 A CN 200410012682A CN 1289587 C CN1289587 C CN 1289587C
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- cellulose
- lithium hydroxide
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- thiocarbamide
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Abstract
The present invention relates to a new cellulose solvent prepared from 3.0 to 7.0 wt% of lithium hydroxide, 3.0 to 6.0 wt% of thiourea, and water as the rest. The mixed water solution of the lithium hydroxide and the thiourea can dissolve natural cellulose and regenerated cellulose with the method that the mixed water solution is frozen and then unfrozen after being mixed with the cellulose, and alternatively, the mixed water solution can be cooled to-10DEG C to 0DEG C in advance, and then the temperature is maintained between-8DEG C and 0DEG C more or less to directly dissolve the natural cellulose and the regenerated cellulose. The solubility of the new cellulose solvent for dissolving the cellulose can reach 100%, and a transparent cellulose concentrated solution is prepared. The molecular weight of the natural cellulose in use can reach 2*10<5>. The new solvent can be used for preparing a regenerated cellulose membrane, a blending membrane, a cellulose/nanometer particle functional membrane and a non-woven fabric and can also be used as a reaction medium for cellulose derivatization.
Description
Technical field
The present invention relates to novel solvent of a kind of dissolving cellulos and uses thereof.Content of the present invention belongs to chemistry and materialogy field.
Background technology
Because the nondegradation plastic refuse causes environmental pollution serious day by day, and petroleum resources will be progressively exhausted after 50 years, and the research and development of renewable plant resources are noticeable day by day.Plant cellulose is the abundantest renewable resources of the earth, belongs to the environmental friendliness macromolecular material.Mierocrystalline cellulose more and more comes into one's own with its significant reproduction speed (1,000 hundred million tons/year), and is expected one of main industrial chemicals that becomes 21 century.Yet Mierocrystalline cellulose is far from reaching and makes full use of in chemical industry, and is main because the cellulose dissolution process is numerous and diverse in the existing technology, cost is high and pollution (J.Macromol.Sci.-Rev.Macromol.Chem., 1980, C18 (1), 1) is arranged.Present cellulose prods more than 90% still adopts traditional viscose process production.Mierocrystalline cellulose is (naoh concentration 18%) and CS under the highly basic effect
2Reaction generates cellulose xanthate, and it is soluble in alkaline solution and becomes viscose.Viscose is regenerated in dilute acid soln behind wire drawing or system film, makes viscose fiber or glassine paper.Because this method discharges a large amount of deleterious CS in process of production
2And H
2S gas has caused huge injury to HUMAN HEALTH, simultaneously also environment is caused severe contamination, and it is extremely urgent therefore to research and develop new cellosolve system.In recent years, various organic or inorganic novel solvents have been obtained bigger progress, methyl-sulphoxide-oxynitride (U.S.patent 3236669,1966) are wherein arranged, NH
3/ NH
4The SCN aqueous solution (J.Polym.Sci.Polym.Chem.Ed., 1980,18,3469), Ca (SCN)
2/ NaSCN the aqueous solution (Polymer J., 1998,30,43; 30,49), ZnCl
2(U.S.Patent 5290349 for the aqueous solution, 1994), trichoro-aldehyde-methyl-sulphoxide-pyridine mixed solution (Polym.J 1980,12,521), (U.S.Patent 4302252 for LiCl/DMAc, 1981), N-methylmorpholine oxynitride (MMNO) (J.Polym.Sci.:Polym.Lett.Ed.1979,17,219) and the NaOH aqueous solution (Japan Patent 1777283,1983) etc.MMNO is acknowledged as the most promising cellosolve.1978, German Akzo Nobel company at first obtained its cellulosic fibre solvent-spinning method patent, and obtained the production technique patent in 1980.The international artificial silk in Brussels in 1989 and the synthon Bureau of Standards (BISFA) are the category name of the cellulose silk of being made by these class methods " Lyocell ".In addition, reported that Mierocrystalline cellulose and urea at high temperature react the generation cellulose carbamate, cellulose carbamate can directly be dissolved in and obtain spinning solution (Finnish Patent 61003 in the sig water; FinnishPatent 62318; U.S.Patent 4404369), but amount of urea is big, and also have by product.People such as Kamide have reported that Mierocrystalline cellulose is at 2.5molL
-1Dissolving in the NaOH aqueous solution, but must adopt the wood pulp cellulose of handling through steam explosion (polymerization degree＜250), it may be dissolved in the NaOH aqueous solution when 4 ℃ of left and right sides, and prepared regenerated fibre intensity is very low, and (U.S.Patent 4634470; Polymer J., 1984,12,857; Polymer J., 1988,20,447).We have used the 6%NaOH/5% thiourea solution as the Mierocrystalline cellulose novel solvent, and dissolving cellulos is also successfully prepared the regenerated cellulose film (Chinese patent: ZL00128162.3) of good strength.But this system deficiency is to be difficult to dissolve more high-molecular weight Mierocrystalline cellulose, thereby can not obtain high-molecular weight Mierocrystalline cellulose strong solution.
Summary of the invention
Problem to be solved by this invention provides a kind of Mierocrystalline cellulose novel solvent, and this solvent can dissolve the high molecular weight fibers element by freeze-thaw method or direct dissolving method, and obtains the transparent Mierocrystalline cellulose strong solution of high-dissolvability.
Technical scheme provided by the invention is: a kind of cellosolve, and it consists of: the lithium hydroxide of 3.0～7.0wt%, the thiocarbamide of 3.0～6.0wt%, all the other are water.
A kind of method of dissolving cellulos, natural cellulose or regenerated cellulose are scattered in the mixed aqueous solution of 3.0～7.0wt% lithium hydroxide and 3.0～6.0wt% thiocarbamide, freezing 3～5 hours at-25 ℃～-15 ℃, and the transparent Mierocrystalline cellulose strong solution of back formation of at room temperature thawing, wherein content of cellulose is 2～10wt%.
A kind of method of dissolving cellulos, natural cellulose or regenerated cellulose are scattered in the mixed aqueous solution of 3.0～7.0wt% lithium hydroxide of being cooled to-10 ℃～0 ℃ and 3.0～6.0wt% thiocarbamide, stirred 5～15 minutes at-8 ℃～0 ℃ then, obtain transparent Mierocrystalline cellulose strong solution, wherein content of cellulose is 2-10wt%.
Lithium hydroxide of the present invention and thiocarbamide mixed aqueous solution can be used for directly dissolving natural cellulose and regenerated cellulose fast, obtain preparing the Mierocrystalline cellulose strong solution of multiple cellulosics (cellulose silk, film, non-woven fabrics, chromatographic column protruded packing, medical biomimetic material, derivatived cellulose etc.) thus.Especially, (molecular weight of natural cellulose can reach 2 * 10 for lithium hydroxide of the present invention and thiourea solution solubilized high-molecular weight natural cellulose
5) and regenerated cellulose.Therefore have obvious innovation and purposes widely.
Compared with the prior art, innovation of the present invention is as follows:
The lithium hydroxide of the high molecular weight fibers of invention solubilized first element and thiourea solution solvent compositions and preparation method thereof.Lithium hydroxide that the present invention relates to and thiourea solution can dissolve natural cellulose (cotton linter pulp, straw fiber slurry, bagasse pulp, soft wood pulp, hard wood pulp etc.) and regenerated cellulose (non-woven fabrics, glassine paper, viscose yarn etc.) by freeze-thaw method or direct method, and can obtain the plain strong solution of transparent high molecular weight fibers of high-dissolvability (solubleness can reach 100%).Its characteristics are to pass through the direct method dissolving cellulos, and are with short production cycle, and technical process is short, is beneficial to suitability for industrialized production.Therefore compare with the patent of having applied for, the invention solves the problems of dissolution of high molecular weight fibers element in aqueous systems, tangible technical progress and application prospect are widely arranged.Resultant transparent Mierocrystalline cellulose strong solution has kept the formability of good fiber spinnability and film, can be used for spinning or system film.This novel solvent can be used for preparing regenerated cellulose film, blend film, cellulose/nanometer particle functional membrane, fiber, non-woven fabrics.The reaction medium that also can be used as cellulose-derivedization.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
Cellosolve among the following embodiment is pressed the method preparation: after lithium hydroxide and thiocarbamide mixing, add water and obtain required ratio of components as cellosolve; Perhaps earlier lithium hydroxide is made into the aqueous solution, adds thiocarbamide then and obtain required ratio of components; Also lithium hydroxide and thiocarbamide can be made into the aqueous solution respectively, mix obtaining required solvent then.It consists of: the lithium hydroxide of 3.0～7.0wt%, and the thiocarbamide of 3.0～6.0wt%, all the other are water.
Embodiment 1
200 gram 3.0wt%LiOH/6.0wt% thiocarbamide mixed aqueous solutions add 20 gram regenerated celluloses (short rayon fiber, the polymerization degree 300) and stir and be placed in the refrigerator (-20 ℃ approximately) freezing 3～5 hours.At room temperature thaw then, obtain transparent cellulose solution after the stirring.With ultracentrifuge at 10,000 rev/mins, 15 ℃ of following centrifugal 30 minutes de-bubbled, the no micelle in concentrator bowl bottom precipitates.
Embodiment 2
200 gram 7.0wt%LiOH/3.0wt% thiocarbamide mixed aqueous solutions add 8.4 gram wood pulp celluloses (polymerization degree 460) and stir and be placed in the refrigerator (-20 ℃ approximately) freezing 3～5 hours.At room temperature thaw then, obtain transparent cellulose solution after the stirring.With ultracentrifuge at 10,000 rev/mins, 15 ℃ of following centrifugal 30 minutes de-bubbled, the no micelle in concentrator bowl bottom precipitates.
Embodiment 3
200 gram 4.5wt%LiOH/5.0wt% thiocarbamide mixed aqueous solutions add 8.4 gram cotton linter pulps (polymerization degree 800) then and stir and be placed in the refrigerator (-20 ℃ approximately) freezing 3～5 hours.At room temperature thaw then, obtain transparent cellulose solution after the stirring.With ultracentrifuge at 10,000 rev/mins, 15 ℃ of following centrifugal 30 minutes de-bubbled, the no micelle in concentrator bowl bottom precipitates.
Embodiment 4
200 gram 5.0wt%LiOH/5.0wt% thiocarbamide mixed aqueous solutions add 4.5 gram absorbent cotton (polymerization degree 2300) and stir and be placed in the refrigerator (-20 ℃ approximately) freezing 3～5 hours.At room temperature thaw then, obtain transparent cellulose solution after the stirring.With ultracentrifuge at 10,000 rev/mins, 15 ℃ of following centrifugal 30 minutes de-bubbled, the no micelle in concentrator bowl bottom precipitates.
Embodiment 5
200 gram 5.0wt%LiOH/5.0wt% thiocarbamide mixed aqueous solutions are cooled to about-8 ℃, add 10.5 gram cotton linter pulps (polymerization degree 500) then and stir fast and kept 5～15 minutes at-8 ℃～0 ℃, obtain transparent cellulose solution.With ultracentrifuge at 10,000 rev/mins, 15 ℃ of following centrifugal 30 minutes de-bubbled, the no micelle in concentrator bowl bottom precipitates.
Claims (3)
1. cellosolve, it consists of: the lithium hydroxide of 3.0～7.0wt%, the thiocarbamide of 3.0～6.0wt%, all the other are water.
2. one kind is utilized the cellulosic method of the described dissolution with solvents of claim 1, it is characterized in that: natural cellulose or regenerated cellulose are scattered in the mixed aqueous solution of 3.0～7.0wt% lithium hydroxide and 3.0～6.0wt% thiocarbamide, freezing 3～5 hours at-25 ℃～-15 ℃, and the transparent Mierocrystalline cellulose strong solution of back formation of at room temperature thawing, wherein content of cellulose is 2～10wt%.
3. one kind is utilized the cellulosic method of the described dissolution with solvents of claim 1, it is characterized in that: natural cellulose or regenerated cellulose are scattered in the mixed aqueous solution of 3.0～7.0wt% lithium hydroxide of being cooled to-10 ℃～0 ℃ and 3.0～6.0wt% thiocarbamide, stirred 5～15 minutes at-8 ℃～0 ℃ then, obtain transparent Mierocrystalline cellulose strong solution, wherein content of cellulose is 2-10wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012682 CN1289587C (en) | 2004-01-18 | 2004-01-18 | Cellosolve and its use |
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|---|---|---|---|
| CN 200410012682 CN1289587C (en) | 2004-01-18 | 2004-01-18 | Cellosolve and its use |
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| CN1557864A CN1557864A (en) | 2004-12-29 |
| CN1289587C true CN1289587C (en) | 2006-12-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200410012682 Expired - Fee Related CN1289587C (en) | 2004-01-18 | 2004-01-18 | Cellosolve and its use |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2011815B1 (en) * | 2006-04-21 | 2013-02-13 | Jiangsu Long-Ma Green Fibers Co., Ltd. | The use of aqueous solution of sodium-hydroxide and sulfourea in producing cellulose products in pilot-scale |
| CN101074285B (en) * | 2007-06-22 | 2010-05-19 | 武汉大学 | Method for dissolving cellulose |
| CN101328271B (en) * | 2008-07-29 | 2011-06-22 | 中国林业科学研究院林产化学工业研究所 | Preparation of cellulose solution |
| CN101805462B (en) * | 2010-03-16 | 2012-01-11 | 武汉大学 | Aqueous solution of polyaniline and cellulose, preparation method thereof and use thereof |
| WO2012138531A1 (en) | 2011-04-06 | 2012-10-11 | Dow Global Technologies Llc | Process for reducing the amount of water-insoluble fibers in a water-soluble cellulose derivative |
| CN103060937B (en) * | 2013-01-29 | 2015-06-10 | 武汉大学 | Preparation method of cellulose nanofiber |
| CN104480722B (en) * | 2014-12-24 | 2017-02-22 | 东华大学 | Non-slurry self-sizing method for cellulosic fiber containing yarns |
| CN107177040B (en) * | 2017-06-05 | 2019-10-25 | 武汉大学 | A kind of cellulose solution and its dissolving method and application |
| CN108380184A (en) * | 2018-03-01 | 2018-08-10 | 浙江理工大学 | A method of utilizing paper pulp chemical preparation cellulose base material for water treatment |
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