CN1229214C - Process for preparing regenerated cellulose films and wires - Google Patents
Process for preparing regenerated cellulose films and wires Download PDFInfo
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- CN1229214C CN1229214C CN 200310111566 CN200310111566A CN1229214C CN 1229214 C CN1229214 C CN 1229214C CN 200310111566 CN200310111566 CN 200310111566 CN 200310111566 A CN200310111566 A CN 200310111566A CN 1229214 C CN1229214 C CN 1229214C
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Abstract
The present invention discloses a method for making a cellulose membrane and a thread. Cellulose is dissolved in mixing water solution containing 5 to 12 wt% of sodium hydroxide and 8 to 20 wt% of carbamide to prepare cellulose solution, membrane scraping or thread spraying of the cellulose solution is carried out, and the regenerated cellulose membrane and the thread are obtained by being washed and dried after the cellulose solution is coagulated and regenerated in a coagulation bath. The cellulose strong solution prepared by the present invention has good fiber spinnability and membrane shaping performance, the made regenerated cellulose membrane has good transparence and mechanical properties, and the made regenerated cellulose thread likewise has good mechanical properties. The method can be used for quickly dissolving the cellulose (2 to 10 minutes) at room temperature to obtain the transparent cellulose strong solution, and the method is a green production process without pollution and with low cost. The method is yearned for replacing the current process for producing glass paper, artificial threads and non-woven fabric with serious pollution, and the method has obvious application prospects.
Description
Technical field
The present invention relates to a kind of method for preparing regenerated cellulose film and silk, belong to the natural polymer field, also belong to chemistry, agricultural, field of environment engineering.
Background technology
Plant cellulose is the abundantest renewable resources of the earth, belongs to the environmental friendliness macromolecular material, 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 at present, and is main because the cellulose dissolution process is numerous and diverse in the existing technology, cost is high and pollution is arranged.Present regenerated cellulose product more than 90% still adopts traditional viscose process production, and Mierocrystalline cellulose is (naoh concentration 18%) and CS under the highly basic effect
2Reaction generates cellulose xanthate, and it is dissolved in alkaline solution and becomes viscose.The Mierocrystalline cellulose viscose is regenerated in dilute acid soln after spray silk or curtain coating, makes viscose fiber or glassine paper.This method discharges a large amount of poisonous CS in process of production
2And H
2S gas not only damages HUMAN HEALTH, and serious environment pollution (J.Macromol.Sci.-Rev.Macromol.Chem., 1980, C18 (1), 1).Producing the cuprammonium regenerated fiber with cuprammonium process exists environmental pollution and solution to reclaim problem.Other organic or inorganic solvents, for example: methyl-sulphoxide-oxynitride (U.S.patent 3236669,1966), 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
2The aqueous solution (U.S.Patent 5290349,1994), trichoro-aldehyde-methyl-sulphoxide-pyridine mixed solution (Polym.J1980,12,521), LiCl/DMAc (U.S.Patent 4302252,1981) is difficult to industrialization for various reasons.In recent years novel solvent N-methyl morpholine oxide (MMNO) (J.Polym.Sci.:Polym.Lett.Ed.1979,17,219) occurs, and be 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 cellulosic fibre of being made by these class methods " Lyocell ".After this, the small amount of fibers cellulose fiber product with its preparation comes into the market in the world, but owing to it costs an arm and a leg, spinning temperature is higher, the suitability for industrialized production slower development.In addition, reported that Mierocrystalline cellulose and urea at high temperature react the generation cellulose carbamate, directly be dissolved in then and obtain spinning solution (Finnish Patent 61003 in the sig water; Finnish Patent 62318; U.S.Patent4404369), but the amount of urea height, and also have by product, be difficult to industrialization.People such as Kamide have reported that Mierocrystalline cellulose is at 2.5molL
-1Dissolving in the NaOH aqueous solution, but this solvent must use the wood pulp cellulose of handling through steam explosion (polymerization degree is lower than 250), and it is dissolvable in water (Japan Patent 1777283,1983 in the NaOH aqueous solution when 4 ℃ of left and right sides; U.S.Patent 4634470; Polymer J., 1984,12,857; Polymer J., 1988,20,447), and obtained fiber yarn intensity is extremely low.We have used the 6wt%NaOH/4wt% aqueous solution of urea as Mierocrystalline cellulose novel solvent (ZL 00114486.3), and successfully prepare the regenerated cellulose film (ZL 00114485.5) of good strength.But under freezing conditions 3-5 hour ability dissolving cellulos of this solvent system prepares transparent Mierocrystalline cellulose strong solution, therefore is difficult to realize industrialization.In addition, the applicant is at room temperature directly dissolved molecular weight and is lower than 10.1 * 10 with the sodium hydroxide of 5-12wt% and the urea mixed aqueous solution of 8-20wt% after cooling
4Natural cellulose and molecular weight be lower than 12 * 10
4Regenerated cellulose (application number: 03128386.1), obtain the Mierocrystalline cellulose strong solution of spinning property and good film-forming property, this method is easy to industrialization.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing regenerated cellulose film and silk, the regenerated cellulose film and the silk of this method preparation have the good mechanical performance, and cost is lower, is easy to suitability for industrialized production.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of method for preparing cellulose membrane in solvent, fully stirs cellulose dissolution, makes cellulose solution, again with cellulose solution curtain coating knifing on flat board, solidifies the regeneration afterwash and be drying to obtain regenerated cellulose film in precipitation bath.Used solvent be 5-12wt% sodium hydroxide and greater than 8wt% to equaling 20wt% urea mixed aqueous solution.Content of cellulose is 2-10wt% in the cellulose solution.
A kind of method for preparing cellulose silk in solvent, fully stirs cellulose dissolution, makes cellulose solution, again with cellulose solution spray silk, solidifies the regeneration afterwash and be drying to obtain regenerated cellulose fiber in precipitation bath.Used solvent be 5-12wt% sodium hydroxide and greater than 8wt% to equaling 20wt% urea mixed aqueous solution.Content of cellulose is 2-10wt% in the cellulose solution.
The present invention adopts 5-12wt% sodium hydroxide and is solvent greater than 8wt% to equaling 20wt% urea mixed aqueous solution, by directly fast (2～10 minutes) dissolving cellulos make the transparent Mierocrystalline cellulose strong solution of high-dissolvability (solubleness can reach 100%).This method is with low price and free of contamination sodium hydroxide and urea [(CO (NH
2)
2)] be the aqueous solution of feedstock production as solvent, the solvent polymerization degree is up to 500 natural cellulose.The Mierocrystalline cellulose strong solution that makes thus has the formability of good fiber spinnability and film, and the regenerated cellulose film of preparation has good light transmittance and mechanical property, and the regenerated cellulose fiber of preparation has the good mechanical performance equally.The present invention is a raw material with the natural cellulose, has that raw material consumption is few, inexpensive, with short production cycle, the simple advantage of technical process; Whole process does not have chemical reaction, with viscose process and cellulose carbamate method in essence different is arranged, and has reduced technologies such as alkalization, experienced, sulfonated and maturation than traditional viscose fiber technology; Technologies such as alkalization, experienced, neutralization, synthetic and purifying have been reduced than cellulose carbamate technology.In addition, used urea is nontoxic and recyclable to be recycled, free from environmental pollution, is a kind of green production process therefore.Compare with Lyocell technology, the new technical process of the present invention has the easy similarity of technology with it, but therefore obvious inexpensive advantage has tangible application prospect.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further: perhaps earlier sodium hydroxide and urea are made into the aqueous solution respectively, mix obtaining required solvent then.
Embodiment 1
Get cotton linters cellulose slurry (polymerization degree 500) 4.1g, add 200g and be chilled in advance in-8 ℃ the 7.8wt%NaOH/10wt% urea mixed aqueous solution, at room temperature stirred 2 minutes, Mierocrystalline cellulose dissolves fully.At 10,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.There is the glass-tube of copper wire (diameter 0.5mm) behind knifing on the sheet glass, to put into 1～3wt%HCl aqueous solution (or 1～2mol/L HAc aqueous solution, or 3～6wt%H immediately with two ends systems
2SO
4The aqueous solution, or 5wt%H
2SO
4/ 5～20 wt%Na
2SO
4The aqueous solution) took out after solidifying in, regenerate 2～5 minutes, water is rinsed well.Be attached at last to dry naturally on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.
Embodiment 2
Get short rayon fiber (polymerization degree 300) 20g, add 180g and be chilled in advance in-8 ℃ the 5.5wt%NaOH/8wt% urea mixed aqueous solution, at room temperature stirred 10 minutes, Mierocrystalline cellulose dissolves fully.At 10,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 1～3wt%HCl aqueous solution (or 1～2mol/L HAc aqueous solution, or 3～6wt%H by syringe needle (diameter 0.3mm) spray silk
2SO
4The aqueous solution, or 5wt%H
2SO
4/ 5～20wt%Na
2SO
4The aqueous solution) solidify in, regenerate and afterwards take out, water is rinsed back drying naturally well and is obtained regenerated cellulose fiber.
Embodiment 3
Get cotton linters cellulose slurry (polymerization degree 500) 8.4g, add 200g and be chilled in advance in-8 ℃ the 7.5wt%NaOH/12wt% urea mixed aqueous solution, at room temperature stirred 2 minutes, Mierocrystalline cellulose dissolves fully.At 10,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.There is the glass-tube of copper wire (diameter 0.5mm) behind knifing on the sheet glass, to put into 1～3wt%HCl aqueous solution (or 1～2mol/L HAc aqueous solution, or 3～6wt%H immediately with two ends systems
2SO
4The aqueous solution, or 5wt%H
2SO
4/ 5～20wt%Na
2SO
4The aqueous solution) took out after solidifying in, regenerate 2～5 minutes, water is rinsed well.Be attached at last to dry naturally on the poly (methyl methacrylate) plate and obtain regenerated cellulose film.With the 3wt%HCl aqueous solution, the 2mol/L HAc aqueous solution, 5wt%H
2SO
4The aqueous solution and 5wt%H
2SO
4/ 10wt%Na
2SO
4The aqueous solution is followed successively by RCM-4Cl, RCM-4HA, RCM-4S and RCM-4Na as the numbering of peptizer gained film.Record the tensile strength (σ of regenerated cellulose film under dry state and hygrometric state by electronic tension tester
b), elongation at break (ε
b) and Young's modulus (E ') come together in subordinate list 1.
Embodiment 4
Get cotton linters cellulose slurry (polymerization degree 500) 8.4g, add 200g and be chilled in advance in-8 ℃ the 7.5wt%NaOH/12wt% urea mixed aqueous solution, at room temperature stirred 2 minutes, Mierocrystalline cellulose dissolves fully.At 10,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 1～3wt%HCl aqueous solution (or 1～2mol/LHAc aqueous solution, or 3～6wt%H by syringe needle (diameter 0.3mm) spray silk
2SO
4The aqueous solution, or 5wt%H
2SO
4/ 5～20wt%Na
2SO
4The aqueous solution) solidify in, regenerate and afterwards take out, water is rinsed back drying naturally well and is obtained regenerated cellulose fiber.With the 3wt%HCl aqueous solution, the 2mol/L HAc aqueous solution, 5wt%H
2SO
4The aqueous solution and 5wt%H
2SO
4/ 10wt%Na
2SO
4The aqueous solution is followed successively by RCF-4Cl, RCF-4HA, RCF-4S and RCF-4Na as the numbering of peptizer gained silk.Record the breaking tenacity (σ of regenerated cellulose fiber under dry state by electronic tension tester
b) and elongation at break (ε
b) come together in subordinate list 2.
Tensile strength (the σ of subordinate list 1. regenerated cellulose films
b), elongation at break (ε
b) and the experimental result of Young's modulus (E ')
| The film numbering | σ b(MPa) | ε b(％) | E’(MPa) | Transmittance (800nm) | |||
| Dry state | Hygrometric state | Dry state | Hygrometric state | Dry state | Hygrometric state | ||
| RCM-4Cl | 66.1 | 1.0 | 10.2 | 62.2 | 3325 | 1.8 | 78％ |
| RCM-4HA | 91.6 | 0.5 | 6.3 | 48.7 | 5054 | 1.4 | 80％ |
| RCM-4S | 86.3 | 0.9 | 6.4 | 55.4 | 4992 | 1.6 | 83％ |
| RCM-4Na | 113.3 | 1.6 | 11.3 | 78.3 | 5614 | 1.9 | 87％ |
Breaking tenacity (σ under the subordinate list 2. regenerated cellulose fiber dry states
b), elongation at break (ε
b) experimental result
| The silk numbering | σ b(cN/tex) | ε b(％) |
| RCF-4Cl | 6.5 | 6.7 |
| RCF-4HA | 8.8 | 8.7 |
| RCF-4S | 7.2 | 7.3 |
| RCF-4Na | 9.2 | 10.9 |
Claims (4)
1. method for preparing cellulose membrane, with cellulose dissolution in solvent, fully stir, make cellulose solution, again with cellulose solution curtain coating knifing on flat board, in precipitation bath, solidify regeneration afterwash be drying to obtain regenerated cellulose film, it is characterized in that: used solvent be 5-12wt% sodium hydroxide and greater than 8wt% to equaling 20wt% urea mixed aqueous solution, content of cellulose is 2-10wt% in the cellulose solution.
2. method according to claim 1 is characterized in that: described peptizer is 1～3wt%HCl aqueous solution, or 1～2mol/L HAc aqueous solution, or 3～6wt%H
2SO
4The aqueous solution, or 5wt%H
2SO
4/ 5～20wt%Na
2SO
4The aqueous solution.
3. method for preparing cellulose silk, with cellulose dissolution in solvent, fully stir, make cellulose solution, again with cellulose solution spray silk, in precipitation bath, solidify regeneration afterwash be drying to obtain regenerated cellulose fiber, it is characterized in that: used solvent be 5-12wt% sodium hydroxide and greater than 8wt% to equaling 20wt% urea mixed aqueous solution, content of cellulose is 2-10wt% in the cellulose solution.
4. method according to claim 3 is characterized in that: described peptizer is 1～3wt%HCl aqueous solution, or 1～2mol/L HAc aqueous solution, or 3～6wt%H
2SO
4The aqueous solution, or 5wt%H
2SO
4/ 5～20wt%Na
2SO
4The aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310111566 CN1229214C (en) | 2003-12-12 | 2003-12-12 | Process for preparing regenerated cellulose films and wires |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310111566 CN1229214C (en) | 2003-12-12 | 2003-12-12 | Process for preparing regenerated cellulose films and wires |
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| Publication Number | Publication Date |
|---|---|
| CN1546298A CN1546298A (en) | 2004-11-17 |
| CN1229214C true CN1229214C (en) | 2005-11-30 |
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ID=34336193
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310111566 Expired - Fee Related CN1229214C (en) | 2003-12-12 | 2003-12-12 | Process for preparing regenerated cellulose films and wires |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282773C (en) | 2005-05-30 | 2006-11-01 | 武汉大学 | Method for preparing regenerative cellulose fiber by two-step coagulating bath process |
| CN1300227C (en) * | 2005-05-30 | 2007-02-14 | 武汉大学 | Microporous membrane and its preparing process and use thereof |
| SE534211C2 (en) * | 2009-10-09 | 2011-05-31 | Stora Enso Oyj | Process for making a substrate containing regenerated cellulose and a substrate made according to the process |
| CN103103663B (en) * | 2012-11-29 | 2016-03-30 | 宁波双盾纺织帆布实业有限公司 | A kind of gas spinning method of fibre and soya |
| CN105136892B (en) * | 2015-09-06 | 2017-12-12 | 广东南海普锐斯科技有限公司 | A kind of electrochemical sensor cellulose heteropoly acid PEM and its preparation method |
| CN107632149A (en) * | 2017-09-18 | 2018-01-26 | 南京工业大学 | Transparent paper base detection and analysis equipment based on zinc oxide nano wire |
| CN109267322A (en) * | 2018-09-19 | 2019-01-25 | 西南大学 | Cotton ready-made clothes anti-bacterial finish technique |
| CN109180978A (en) * | 2018-10-10 | 2019-01-11 | 华南理工大学 | A kind of polyaniline/cellulose conductive composite film and its preparation method and application |
| CN111718495A (en) * | 2020-07-07 | 2020-09-29 | 湖北工业大学 | Cellulose solution and method for dissolving cellulose |
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