CN1285644C - Solvent for dissolving cellulose and its preparation method and use - Google Patents
Solvent for dissolving cellulose and its preparation method and use Download PDFInfo
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- CN1285644C CN1285644C CN 200510027217 CN200510027217A CN1285644C CN 1285644 C CN1285644 C CN 1285644C CN 200510027217 CN200510027217 CN 200510027217 CN 200510027217 A CN200510027217 A CN 200510027217A CN 1285644 C CN1285644 C CN 1285644C
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Abstract
The present invention provides a solvent for quickly and directly dissolving cellulose, which is prepared from a quaternary system of sodium hydroxide, thiourea, urea and water. The solvent has a great dissolving capacity when the temperature of the solvent is from-12 to 5DEG C. The present invention also provides a method for quickly dissolving cellulose and preparing cellulose fibers or a cellulose membrane by utilizing the solvent. The solvent system has the advantages of great dissolving capacity for cellulose, solvent nontoxicity, environmental friendliness and low price, and in addition, waste liquid can be directly used for producing chemical fertilizers or recycled with a recrystallization method, and consequently, the solvent system has greater advantages as compared with other solvents.
Description
Technical field
The present invention relates to solvent of a kind of dissolving cellulos and its production and use, relate in particular to a kind of solvent that contains sodium hydroxide, thiocarbamide and urea and preparation method thereof and the application in preparation cellulose fiber peacekeeping film.
Technical background
Mierocrystalline cellulose is a kind of natural renewable resources, and the source is abundant, and is biodegradable, has good biocompatibility, therefore utilizes Mierocrystalline cellulose to be raw material, both can reduce the consumption of oil, and can protect environment.Owing to contain a large amount of hydroxyls in the cellulosic molecule, can form very strong intramolecularly and intermolecular hydrogen bond, degree of crystallinity is higher, and the molecule chain rigidity is stronger relatively, is difficult to dissolve with general solvent; On the other hand, because cellulosic decomposition temperature than its melt temperature height, is difficult to carry out melt-processed.Therefore, cellulosic application is subjected to limiting greatly.At present, had been found that many solvents can dissolving cellulos, but existed environmental pollution, and the problem of aspect such as cost height.The technology of traditional mode of production regenerated cellulose fibre and film is viscose process and cuprammonium process.In the viscose process production process, when the dissolving soda cellulose, need to add a large amount of CS
2, and emit H
2S, SO
2, simultaneously solidify with regenerative process in need to add Zn
2SO
4, serious environment pollution influences HUMAN HEALTH, and complex process; When cuprammonium process is produced the cuprammonium regenerated fiber, also there are environmental pollution and solvent recuperation problem.And some novel solvents are [as N
2O
4/ DMF (dimethyl formamide), N
2O
4/ DMSO (methyl-sulphoxide), Paraformaldehyde 96/DMSO, strong phosphoric acid, Ca (SCN)
2Or Na (SCN)
2The aqueous solution, NH
3/ NH
4Cl etc.] all exist environmental pollution, the solvent recuperation difficulty perhaps to problems such as equipment requirements height, is difficult to carry out suitability for industrialized production.At present, relatively successful novel solvent is N-methylmorpholine-N-oxide compound (NMMO) and sodium hydroxide.NMMO is a strongest present cellosolve, but because the solvent costliness is not a totally nontoxic, also there is certain problem in recovery, and the spinning temperature height, and blast has influenced its suitability for industrialized production easily; The NaOH aqueous solution is the most cheap solvent of dissolving cellulos, but it can only dissolve and dodge quick-fried the mistake through flash distillation and handle, and the polymerization degree is lower than 250 wood pulp celluloses, and can not dissolve the cotton pulp dregs of rice.Recently, professor Zhang Lina of Wuhan University has invented NaOH/ thiourea solution and NaOH/ aqueous solution of urea solvent system (CN200310111447.8; Macromol.Biosci.2004,4,1105-1112; Macromol.RapidCommun.2004,25,1558-1562), wherein the NaOH/ thiourea solution is stronger to cellulosic dissolving power, can be in 5～15 minutes dissolving cellulos fast, (to the polymerization degree is 600 gossypin, and its solid content is about 5%, and solid content was above 5% o'clock but the solid content of gained solution is lower, be difficult to carry out deaeration with general method, the spinning property of solution is poor, even can not dissolve fully), relatively poor to the polymerization degree greater than the dissolving power of 600 gossypin.
Summary of the invention
Solvent that provides a kind of dissolving cellulos and its production and use is provided technical problem to be solved by this invention, and solvent in the prior art is big for environment pollution to solve, the ability of dissolving cellulos, be not suitable for shortcoming such as suitability for industrialized production.
The purpose of this invention is to provide a kind of solvent of quick dissolving cellulos, and it is stable to use this solvent preparation property, the cellulose solution of good spinning property, and with the method for this formulations prepared from solutions regenerated cellulose fibre or film.
The present invention at first provides a kind of solvent of dissolving cellulos, and this solvent comprises the component of following weight percent content:
Sodium hydroxide 6～12
Thiocarbamide 3～8
Urea 1～15
Water surplus.
Preferred scheme is the component that comprises following weight percent content:
Sodium hydroxide 7～10
Thiocarbamide 4.5～7
Urea 1～10
Water surplus.
Above-mentioned solvent can be prepared by following method: sodium hydroxide, thiocarbamide, urea and water are mixed in proportion.Can be earlier with one or both or three kinds of medicine wiring solution-formings (addition sequence in no particular order) in three kinds of solid medicines, and then add other two kinds or a kind of medicine (addition sequence is in no particular order), make its dissolving.Recommend earlier thiocarbamide and urea to be made into the aqueous solution, and then add sodium hydroxide, stir and make its dissolving.The solution that makes be stored in 10 ℃ standby.
A kind of cellulosic method of above-mentioned dissolution with solvents of utilizing: the 100g solvent is chilled to-12～5 ℃ and keep this temperature in advance, natural cellulose or the regenerated cellulose of 4-12g are scattered in the solvent, the powerful stirring 5～10 minutes can make solid content and be 2～12% cellulose solution.
A kind of method of utilizing above-mentioned cellulose solution to prepare cellulose membrane or fiber: with above-mentioned solution through filtration, deaeration, casting film-forming after, film is placed in the precipitation bath regenerates, carry out then making regenerated cellulose film behind the washing and drying; Above-mentioned solution through filtration, deaeration, after orifice is extruded, through precipitation bath regeneration, is made regenerated cellulose fibre after the drying.
Above-mentioned precipitation bath is: one or both in 3～25% acetic acid, 3～25% sulfuric acid, 5～25% ammonium acetate salt brine solution, 5～25% aqueous sodium persulfate solution or 5～25% the aqueous ammonium chloride solution.
Compared with prior art, the present invention has obvious improvement, and the solvent that makes can dissolve natural or regenerated cellulose rapidly at-12～5 ℃, is suitable for the various regenerated cellulose fibres of suitability for industrialized production, film, non-woven fabrics and chromatographic column protruded packing.
Main innovation of the present invention is as follows: the present invention adopts sodium hydroxide/thiocarbamide/urea/water quaternary compound system dissolution with solvents Mierocrystalline cellulose first, and Mierocrystalline cellulose is had very strong dissolving power, and energy is dissolving cellulos fast, and the solution that makes has good stability.Solvent is to various natural celluloses (cotton linter dissolving pulp, absorbent cotton, wood pulp cellulose etc.), quick-fried Mierocrystalline cellulose is dodged in flash distillation and various regenerated cellulose (non-woven fabrics, viscose fiber, lyocell fiber) can directly dissolve fast, and higher solubleness is arranged, particularly the cotton fibre to high-crystallinity has very strong dissolving power; Sodium hydroxide, thiocarbamide, water ternary system solvent and sodium hydroxide, urea, the water ternary system solvent of inventions such as this professor Zhang Lina of solvent ratio Wuhan University have stronger dissolving power, the solvent of professor Zhang Lina invention can only solvent polymerization degree lower (DP=600) the cotton pulp dregs of rice, the polymerization degree there is not dissolving power greater than 1400 the cotton pulp dregs of rice, and the solvent that the present invention makes still has stronger dissolving power to the polymerization degree greater than 1400 the cotton pulp dregs of rice, for the preparation high strength fibre provides the foundation.Under the same conditions, the solution that the solvent that the solution that this solvent makes is taught than Zhang Lina makes is more stable, the time lengthening that gelation point occurs, when the solution solid content less than 6% the time, but standing and defoaming or vacuumizing and defoaming, spinning property is better, therefore more helps suitability for industrialized production.With the Mierocrystalline cellulose strong solution that this method makes, the formability of fine spinning property and film is arranged, can be used for spinning and system film.
The used naoh concentration of the present invention is 6～12%, and the concentration (15～18%) that is equipped with soda cellulose than viscose glue legal system is low, and the concentration of acid is also low in the required precipitation bath, has not only reduced original materials, has reduced cost, has also reduced the corrosion to container; Because dissolution time significantly shortens, and has improved production efficiency;
Solvent for use of the present invention is the aqueous solution of sodium hydroxide, thiocarbamide and urea, and wherein various drug prices are cheap, and pollution-free; The present invention is raw material with the natural cellulose, direct dissolving cellulos, the whole process of preparation stoste does not have chemical reaction and takes place, and with derivatize dissolution process such as viscose process and cellulose carbamate methods the different of essence is arranged, and has lacked technologies such as alkalization, experienced and maturation than traditional adhering process; Raw material consumption is few, and is with short production cycle, and technical process is simple.
The present invention adopts the direct dissolving cellulos of solvent, and condition is wide in range, control easily, and the stability of solution height, technology is simple, can utilize existing viscose process technology to do repacking slightly and can produce.The waste liquid that produces in the production can directly be used for producing chemical fertilizer, or separates with the method for recrystallization, utilizes environmentally safe again.Therefore, can replace adhering process and cuprammonium technology, be with a wide range of applications with this method production regenerated cellulose fibre or film.
Embodiment
Below in conjunction with specific examples this invention is described further
Example 1
Get the cotton pulp dregs of rice (polymerization degree DP=500) 5.8 grams, add in 100 gram 8% sodium hydroxide/6.5% thiocarbamide/8% urea mixed aqueous solutions (solution is chilled to-4 ℃ in advance), then-4 ℃ (by brine bath temperature control) powerful stirring 10 minutes, under 1 normal atmosphere,, obtain clarifying cellulose solution with 200 purpose screen filtrations.This solution can be deposited at 10 ℃ and gelation not take place in 5 days, and leaves standstill natural deaeration in the process.
Example 2
Get the cotton pulp dregs of rice (polymerization degree DP=300) 12 grams, add in 100 gram 9% sodium hydroxide/5.5% thiocarbamide/6% urea mixed aqueous solutions (solution is chilled to-4 ℃ in advance), then-4 ℃ (by brine bath temperature control) powerful stirring 5 minutes, under 1 normal atmosphere,, obtain clarifying cellulose solution with 200 purpose screen filtrations.
Example 3
Get the cotton pulp dregs of rice (polymerization degree DP=1400) 4 grams, add in 100 gram 9% sodium hydroxide/5.5% thiocarbamide/8% urea mixed aqueous solutions (solution is chilled to-2 ℃ in advance), then-2 ℃ (by brine bath temperature control) powerful stirring 8 minutes, under 1 normal atmosphere,, obtain clarifying cellulose solution with 200 purpose screen filtrations.
Example 4
Get the cotton pulp dregs of rice (polymerization degree DP=600) 6 grams, add in 100 gram 9.5% sodium hydroxide/5.5% thiocarbamide/4% urea mixed aqueous solutions (solution is chilled to 0 ℃ in advance), 0 ℃ (by ice-water bath temperature control) powerful stirring 5 minutes, obtain transparent cellulose solution then.At 8000 rev/mins, 10 ℃ were descended centrifugal 30 minutes, and were not changed before cellulose solution is more centrifugal with ultracentrifuge.Pour out cellulose solution, the no micelle precipitation in concentrator bowl bottom, the visible fiber of no naked eyes exists in the gained solution.Regenerated cellulose dissolves fully.
Example 5
Get viscose staple fibre 8 grams, add in 100 gram 8.9% sodium hydroxide/5.5% thiocarbamide/6% urea mixed aqueous solutions (solution is chilled to-4 ℃ in advance) ,-4 ℃ (by ice-water bath temperature control) powerful stirring 5 minutes, obtain transparent cellulose solution then.At 8000 rev/mins, 20 ℃ were descended centrifugal 5 minutes, and were not changed before cellulose solution is more centrifugal with ultracentrifuge.Pour out cellulose solution, the no micelle precipitation in concentrator bowl bottom, the visible fiber of no naked eyes exists in the gained solution, and short rayon fiber dissolves fully.
Example 6
Get the cotton pulp dregs of rice (polymerization degree DP=600) 5.5 grams, add in 100 gram 9% sodium hydroxide/5.5% thiocarbamide/4% urea mixed aqueous solutions (solution is chilled to 0 ℃ in advance), then 0 ℃ (by ice-water bath temperature control) powerful stirring 5 minutes, under 1 normal atmosphere,, obtain settled solution with 200 purpose screen filtrations.Behind knifing on the sheet glass, put into 5% aqueous sulfuric acid, soak after 5 minutes and take out, rinse well with deionized water.Be attached at last to dry naturally on the polyfluortetraethylene plate and obtain regenerated cellulose film.Tensile strength, elongation at break and the Young's modulus of the regenerated cellulose film that is recorded by electronics pulling experiment machine is respectively 92MPa, 13% and 4851MPa, and transmittance is 86% (800nm).
Example 6
Get the cotton pulp dregs of rice (polymerization degree DP=500) 6.5 grams, add in 100 gram 8.5% sodium hydroxide/6.5% thiocarbamide/6% urea mixed aqueous solutions (solution is chilled to 0 ℃ in advance), then 0 ℃ (by ice-water bath temperature control) powerful stirring 5 minutes, under 1 normal atmosphere,, obtain settled solution with 200 purpose screen filtrations.At 15 ℃,, behind knifing on the sheet glass, put into 15% ammonium sulfate solution then, soak after 3-5 minutes and take out, rinse well with deionized water with centrifugation under the rotating speed of 3000r/min 5 minutes.Be attached at last to dry naturally on the polyfluortetraethylene plate and obtain regenerated cellulose film.Tensile strength, elongation at break and the Young's modulus of the regenerated cellulose film that is recorded by electronics pulling experiment machine is respectively 95MPa, 14% and 5112MPa, and transmittance is 86% (800nm).
Example 7
Get the cotton pulp dregs of rice (polymerization degree DP=500) 6.3 grams, add in 100 gram 8.5% sodium hydroxide/6.5% thiocarbamide/6% urea mixed aqueous solutions (solution is chilled to 0 ℃ in advance), then 0 ℃ (by ice-water bath temperature control) powerful stirring 5 minutes, under 1 normal atmosphere,, obtain settled solution with 200 purpose screen filtrations.At 15 ℃,, do not change before Mierocrystalline cellulose is more centrifugal then with centrifugation under the rotating speed of 3000r/min 5 minutes.On the self-control spinning-drawing machine, carry out spinning, orifice directly is 0.1mm, 6 holes, nitrogen pressure are 1.5 normal atmosphere, and spinning temperature is controlled at 10 ℃, 5% sulfuric acid and 15% aqueous sodium persulfate solution are selected in precipitation bath for use, temperature of solidification is 25 ℃, and washing then was 100 ℃ of dryings 15 minutes, intensity, the elongation at break of the regenerated cellulose fibre that is recorded by electronics pulling experiment machine are respectively 1.04CN/dtex, 16%.
Example 8
Get the cotton pulp dregs of rice (polymerization degree DP=600) 5.5 grams, add in 100 gram 8.5% sodium hydroxide/5.5% thiocarbamide/6% urea mixed aqueous solutions (solution is chilled to-6 ℃ in advance), then-6 ℃ (by ice-water bath temperature control) powerful stirring 5 minutes, under 1 normal atmosphere,, obtain settled solution with 200 purpose screen filtrations.At 20 ℃,, do not change before Mierocrystalline cellulose is more centrifugal then with centrifugation under the rotating speed of 3000r/min 5 minutes.On the self-control spinning-drawing machine, carry out spinning, orifice directly is 0.1mm, 6 holes, nitrogen pressure are 1.5 normal atmosphere, and spinning temperature is controlled at 7 ℃, 12% aqueous ammonium chloride solution is selected in precipitation bath for use, temperature of solidification is 20 ℃, and washing then was 100 ℃ of dryings 15 minutes, the intensity, the elongation at break that are recorded the regenerated cellulose fibre that is solidified by aqueous ammonium chloride solution by electronics pulling experiment machine are respectively 0.84CN/drex, 16%.
Claims (5)
1. the solvent of a dissolving cellulos is characterized in that this solvent comprises the component of following weight percent content:
Sodium hydroxide 6～12
Thiocarbamide 3～8
Urea 1～15
Water surplus.
2. the solvent of dissolving cellulos according to claim 1 is characterized in that this solvent comprises the component of following weight percent content:
Sodium hydroxide 7～10
Thiocarbamide 4.5～7
Urea 1～10
Water surplus.
3. a method for preparing the solvent of claim 1 or 2 each described dissolving cellulos is characterized in that sodium hydroxide, thiocarbamide, urea and water are mixed in proportion.
4. one kind according to claim 1 or the cellulosic method of 2 each described dissolution with solvents, it is characterized in that:
The 100g solvent is chilled to-12～5 ℃ and keep this temperature in advance, natural cellulose or the regenerated cellulose of 4-12g is scattered in the solvent, the powerful stirring 5～10 minutes can make solid content and be 2～12% cellulose solution.
5. one kind prepares the method for cellulose membrane or fiber according to claim 4, it is characterized in that cellulose solution regenerating in precipitation bath through filtration, deaeration, casting film-forming or after extruding, after make regenerated cellulose film or fiber after the washing, drying;
Wherein said precipitation bath is one or both in the aqueous ammonium chloride solution of 3～25% acetic acid, 3～25% sulfuric acid, 5～25% ammonium acetate salt brine solution, 5～25% aqueous sodium persulfate solution or 5～25%.
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|---|---|---|---|
| CN 200510027217 CN1285644C (en) | 2005-06-29 | 2005-06-29 | Solvent for dissolving cellulose and its preparation method and use |
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| JP5072846B2 (en) * | 2006-04-21 | 2012-11-14 | ジャングー ロンマ グリーン ファイバーズ カンパニー リミテッド | Use of aqueous sodium hydroxide / thiourea solution in the manufacture of cellulose products on a pilot scale |
| CN103237814B (en) * | 2010-10-27 | 2016-06-01 | 雷纽赛尔卢克斯有限责任公司 | A kind of method for cellulose derivatization |
| CN102787380B (en) * | 2012-08-08 | 2013-11-06 | 张家港市天一纺织有限公司 | Method for preparing straw regenerated cellulose fiber |
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| CN104072622B (en) * | 2014-07-01 | 2016-12-07 | 东华大学 | The preparation of cellulose carbamate and dissolution in low temperature spinning process thereof |
| CN105113236B (en) * | 2015-10-14 | 2017-08-25 | 浙江超凡制衣有限公司 | A kind of low skin irritability flax material and its preparation technology |
| CN106245131A (en) * | 2016-08-09 | 2016-12-21 | 东华大学 | A kind of precursor fiber preparation method of low-temperature alkaline urea method cellulose base carbon fiber |
| CN107299124A (en) * | 2017-08-31 | 2017-10-27 | 齐鲁工业大学 | A kind of preprocess method for improving stalk cellulose saccharification speed |
| CN110297034B (en) * | 2019-06-12 | 2021-08-27 | 重庆工商大学融智学院 | Dynamic change and prediction method for urban ecological environment |
| CN112842965A (en) * | 2021-03-05 | 2021-05-28 | 浙江科技学院 | Regenerated cellulose mask capable of efficiently replenishing water and preparation method thereof |
| CN115772233B (en) * | 2022-11-22 | 2024-02-27 | 宜宾丝丽雅集团有限公司 | Defoaming process and system for producing regenerated cellulose based on low-temperature alkali urea method |
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