CN1285776C - Preparation method for regenerated cellulose fiber - Google Patents
Preparation method for regenerated cellulose fiber Download PDFInfo
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- CN1285776C CN1285776C CN 200410013389 CN200410013389A CN1285776C CN 1285776 C CN1285776 C CN 1285776C CN 200410013389 CN200410013389 CN 200410013389 CN 200410013389 A CN200410013389 A CN 200410013389A CN 1285776 C CN1285776 C CN 1285776C
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- cellulose
- aqueous solution
- solution
- fiber
- regenerated celulose
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Abstract
The present invention discloses a preparation method for a regenerated cellulose fiber. Cellulose is dissolved in a mixed water solution of 5% to 12 wt% of sodium hydroxide and 8% to 20 wt% of urea; the solution is fully stirred and is prepared into a concentrated cellulose solution; a wet spinning method is adopted to carry out spinning on a spinning machine, and carry out regenerated solidification in a coagulation bath; after stretching, orientation and desiccation, a regenerated cellulose fiber is obtained. The present invention has simple method, short technological process, no pollution and low price, and is green production technology. The method has the possibility of replacing the viscose method for producing artificial silk and non-woven fabrics, which has serious pollution at present.
Description
Technical field
The present invention relates to a kind of method for preparing novel regenerated celulose fibre, belong to the natural polymer field, also belong to chemical, agricultural, field of environment engineering.
Background technology
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.Since 100 years, the regenerated cellulose product still adopts traditional viscose process to produce artificial silk and glassine paper.Cellulose is (naoh concentration 18%) and CS under the highly basic effect
2Reaction generates cellulose xanthate, and it is dissolved in aqueous slkali and becomes viscose.The cellulose viscose is regenerated in dilute acid soln after spray silk or curtain coating, makes viscose or glassine paper.This method discharges a large amount of poisonous CS in process of production
2And H
2S gas not only damages health, and serious environment pollution (J.Macromol.Sci.-Rev.Macromol.Chem., 1980, C18 (1), 1).Producing the cuprammonium artificial fibre with cuprammonium process exists environmental pollution and solution to reclaim problem.Other organic or inorganic solvents, for example: methyl-sulfoxide-nitrogen oxide (U.S.patent3236669,1966), 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.Patent5290349,1994), trichloroacetaldehyde-methyl-sulfoxide-adjoin pyridine mixed liquor (Polym.J 1980,12,521), 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 cellulose solvent.1978, German Akzo Nobel company at first obtained its cellulose fibre solvent-spinning method patent, and obtained the production technology patent in 1980.The international artificial silk in Brussels in 1989 and the synthetic fiber Bureau of Standards (BISFA) are the category name of the cellulose 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 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.Patent 4404369), but the amount of urea height, and also have accessory substance, be difficult to industrialization.People such as Kamide have reported that cellulose is at 2.5molL
-1Dissolving in the NaOH aqueous solution, but this solvent must use the wood pulp cellulose of handling through steam blasting (degree of polymerization 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 filament intensity is extremely low.We have used the 6wt%NaOH/4wt% aqueous solution of urea as cellulose novel solvent (ZL 00114486.3), and successfully prepare the regenerated cellulose film (ZL 00114485.5) of good strength.But this dicyandiamide solution thawed and could prepare transparent cellulose concentrated solution by dissolving cellulos under freezing conditions 3-5 hour then, therefore was difficult to realize industrialization.In addition, we at room temperature directly dissolve molecular weight and are lower than 10.1 * 10 with the NaOH of 5-12wt% and the urea mixed aqueous solution of 8-20wt% after cooling
4Native cellulose and molecular weight be lower than 12 * 10
4Regenerated cellulose (application number: 03128386.1), obtain the cellulose concentrated solution of spinnability and good film-forming property, this method is easy to industrialization.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of regenerated celulose fibre, this method is simple and pollution-free, and the regenerated celulose fibre that makes has the good mechanical performance, and cost is low, 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 preparation method of regenerated celulose fibre, with cellulose dissolution in solvent, fully stir, make the cellulose concentrated solution, adopt wet spinning process to solidify spraying silk on the spinning machine and regenerate in coagulating bath, stretched orientation, dry post processing obtain the regenerated celulose fibre of function admirable.Used solvent is 5～12wt% NaOH/8～20wt% urea mixed aqueous solution.Used coagulating bath is 3～25wt%H
2SO
4The aqueous solution, 3～25wt%H
2SO
4/ 5～30wt%Na
2SO
4The aqueous solution, 3～25wt%H
2SO
4/ 5～30wt% (NH
4)
2SO
4The aqueous solution, 3～15wt%HCl aqueous solution or 3～15wt%HCl/5～30wt%NH
4The Cl aqueous solution.
Compared with the prior art, innovation of the present invention is as follows:
NaOH/the aqueous solution of urea that the present invention relates to can reach 800 native cellulose (cotton linter pulp, grass fiber slurry, bagasse pulp, soft wood pulp, hard wood pulp etc.) and regenerated cellulose (nonwoven fabric, glassine paper, short rayon fiber, long filament etc.) by directly quick solvent polymerization degree.The cellulose concentrated solution that makes thus has the mouldability of good fiber spinnability and film.The inventive method and viscose process and cellulose carbamate method have in essence different, have that consumption of raw materials is few, inexpensive, with short production cycle, the simple advantage of technological process, and are a kind of green production processes.The present invention is raw material with the native cellulose, and whole process does not have chemical reaction, has reduced technologies such as alkalization, experienced, axnthation and maturation than traditional viscose technology; Technologies such as alkalization, experienced, neutralization, synthetic and purifying have been reduced than cellulose carbamate technology.Compare with Lyocell technology, the new technological process of the present invention has the easy and obvious inexpensive advantage of technology with it, and the cross section of the cellulose fibre that the present invention makes is circle, and similar natural silk is obviously different with existing viscose.And have higher degree of crystallinity and molecular weight, have the advantage of structure and performance.Therefore this product has good, easily manufactured, the high in technological content characteristics of quality.It has made marked progress than conventional art, thereby application prospect is arranged.
Description of drawings
The section morphology figure of the regenerated celulose fibre (b) that Fig. 1 makes for industrial viscose (a) in the prior art of observation by light microscope and the present invention;
The external form and the sectional view of the regenerated cellulose that Fig. 2 makes for the present invention of sem observation; Wherein Fig. 2 (a) is fibre bundle external form figure; Fig. 2 (b) is filament external form figure; Fig. 2 (c) is an exterior view; Fig. 2 (d) is the filament sectional view.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
Embodiment 1
200g 5wt%NaOH/20wt% urea mixed aqueous solution is chilled to-10 ℃ in advance, adds short rayon fiber (degree of polymerization 250) 12g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 3wt%H by spinning machine spinning head (30 holes, diameter 0.10mm) spray silk
2SO
4Solidify in the aqueous solution, regenerate, stretched orientation back water is rinsed well, and oven dry obtains regenerated celulose fibre.This fiber is a white, and is soft glossy, has higher intensity.
Embodiment 2
200g 12wt%NaOH/8wt% urea mixed aqueous solution is chilled to-4 ℃ in advance, adds cotton linters cellulose slurry (degree of polymerization 800) 6.4g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 25wt%H by spinning machine spinning head (30 holes, diameter 0.10mm) spray silk
2SO
4Solidify in the aqueous solution, regenerate, stretched orientation back water is rinsed well, and oven dry obtains regenerated celulose fibre.This fiber is a white, and is soft glossy, has higher intensity.
Embodiment 3
200g 12wt%NaOH/8wt% urea mixed aqueous solution is chilled to-8 ℃ in advance, adds nonwoven fabric (degree of polymerization 600) 8.4g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 25wt%H by spinning machine spinning head (30 holes, diameter 0.10mm) spray silk
2SO
4/ 5wt%Na
2SO
4Solidify in the aqueous solution, regenerate, stretched orientation back water is rinsed well, and oven dry obtains regenerated celulose fibre.This fiber is a white, and is soft glossy, has higher intensity.
Embodiment 4
200g 12wt%NaOH/8wt% urea mixed aqueous solution is chilled to-8 ℃ in advance, adds bagasse pulp (degree of polymerization 400) 9g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 3wt%H by spinning machine spinning head (30 holes, diameter 0.12mm) spray silk
2SO
4/ 30wt%Na
2SO
4Solidify in the aqueous solution, regenerate, stretched orientation back water is rinsed well, and oven dry obtains regenerated celulose fibre.This fiber is a white, and is soft glossy, has higher intensity.
Embodiment 5
200g 12wt%NaOH/8wt% urea mixed aqueous solution is chilled to-8 ℃ in advance, adds cotton linters cellulose slurry (degree of polymerization 500) 8.4g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 25wt%H by spinning machine spinning head (30 holes, diameter 0.14mm) spray silk
2SO
4/ 5wt% (NH
4)
2SO
4Solidify, regenerate in the aqueous solution aqueous solution, stretched orientation back water is rinsed well, and oven dry obtains regenerated celulose fibre.This fiber is a white, and is soft glossy, has higher intensity.
Embodiment 6
200g 12wt%NaOH/8wt% urea mixed aqueous solution is chilled to-8 ℃ in advance, adds cotton linters cellulose slurry (degree of polymerization 500) 8.4g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 3wt%H by spinning machine spinning head (30 holes, diameter 0.12mm) spray silk
2SO
4/ 30wt% (NH
4)
2SO
4Solidify, regenerate in the aqueous solution aqueous solution, stretched orientation back water is rinsed well, and oven dry obtains regenerated celulose fibre.This fiber is a white, and is soft glossy, has higher intensity.
Embodiment 7
200g 7.5wt%NaOH/10wt% urea mixed aqueous solution is chilled to-8 ℃ in advance, adds cotton linters cellulose slurry (degree of polymerization 500) 8.4g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter in the 3wt%HCl aqueous solution by spinning machine spinning head (30 holes, diameter 0.12mm) spray silk and to solidify, regenerate, stretched orientation afterwards water is rinsed well, dries and obtains regenerated celulose fibre.This fiber is a white, and is soft glossy, has higher intensity.
Embodiment 8
200g 7.5wt%NaOH/10wt% urea mixed aqueous solution is chilled to-8 ℃ in advance, adds cotton linters cellulose slurry (degree of polymerization 500) 8.4g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter in the 15wt%HCl aqueous solution by spinning machine spinning head (30 holes, diameter 0.1mm) spray silk and to solidify, regenerate, stretched orientation afterwards water is rinsed well, dries and obtains regenerated celulose fibre.This fiber is a white, and is soft glossy, has higher intensity.
Embodiment 9
200g 7.5wt%NaOH/10wt% urea mixed aqueous solution is chilled to-8 ℃ in advance, adds cotton linters cellulose slurry (degree of polymerization 500) 8.4g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 15wt%HCl/5wt%NH by spinning machine spinning head (30 holes, diameter 0.12mm) spray silk
4Solidify, regenerate in the Cl aqueous solution, stretched orientation back water is rinsed well, and oven dry obtains regenerated celulose fibre.This fiber is a white, and is soft glossy, has higher intensity.
Embodiment 10
200g 7.5wt%NaOH/10wt% urea mixed aqueous solution is chilled to-8 ℃ in advance, adds cotton linters cellulose slurry (degree of polymerization 500) 8.4g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 3wt%HCl/30wt%NH by spinning machine spinning head (30 holes, diameter 0.12mm) spray silk
4Solidify, regenerate in the Cl aqueous solution, stretched orientation back water is rinsed well, and oven dry obtains regenerated celulose fibre.This fiber is a white, and is soft glossy, has higher intensity.
Embodiment 11
200g 7.5wt%NaOH/10wt% urea mixed aqueous solution is chilled to-8 ℃ in advance, adds cotton linters cellulose slurry (degree of polymerization 500) 8.4g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 10wt%H by spinning machine spinning head (30 holes, diameter 0.10mm) spray silk
2SO
4Solidify in the aqueous solution, regenerate, stretched orientation back water is rinsed well, and oven dry obtains regenerated celulose fibre, is numbered F1.This fiber is a white, and is soft glossy, has higher intensity.Record the fracture strength (σ of regenerated celulose fibre under dry state by XQ-1 isodromicing elongation property fibre strength instrument
b) and elongation at break (ε
b), record the degree of crystallinity (χ of regenerated celulose fibre by X-ray diffractometer
c) come together in subordinate list 1.This fiber of data declaration has mechanical property and high degree of crystallinity preferably in the table.
Embodiment 12
200g 7.5wt%NaOH/10wt% urea mixed aqueous solution is chilled to-8 ℃ in advance, adds cotton linters cellulose slurry (degree of polymerization 500) 8.4g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 10wt%H by spinning machine spinning head (30 holes, diameter 0.12mm) spray silk
2SO
4/ 15wt%Na
2SO
4Solidify in the aqueous solution, regenerate, stretched orientation back water is rinsed well, and oven dry obtains regenerated celulose fibre, numbering F2.This fiber is a white, and is soft glossy, has higher intensity.Record the fracture strength (σ of regenerated celulose fibre under dry state by XQ-1 isodromicing elongation property fibre strength instrument
b) and elongation at break (ε
b), record the degree of crystallinity (χ of regenerated celulose fibre by X-ray diffractometer
c) come together in subordinate list 1.This fiber of data declaration has mechanical property and high degree of crystallinity preferably in the table.The section morphology that is recorded regenerated celulose fibre by light microscope is seen Fig. 1 (b).The surface and the section morphology that are recorded the regenerated celulose fibre of process simple extension by flying-spot microscope are seen Fig. 2.Fig. 1 shows that fiber (Fig. 1 b) that the present invention makes has and is different from existing viscose (Fig. 1 irregular structure a), its cross section illustrates that for uniformly circular (seeing Fig. 1 b) physical property of the fiber that the present invention makes is different from viscose.Fig. 2 illustrates that the fiber that the present invention makes has certain degree of orientation, makes fiber have good mechanical property, and its structure is similar to natural silk, has good compliance.
Embodiment 13
200g 7.5wt%NaOH/10wt% urea mixed aqueous solution is chilled to-8 ℃ in advance, adds cotton linters cellulose slurry (degree of polymerization 500) 8.4g then immediately, at room temperature stirs 2 minutes, and cellulose dissolves fully.At 8,000 rev/mins, 15 ℃ made it the degassing down in centrifugal 30 minutes, obtain transparent cellulose solution with ultracentrifuge.Enter 10wt%H by spinning machine spinning head (30 holes, diameter 0.12mm) spray silk
2SO
4/ 15wt% (NH
4)
2SO
4Solidify in the aqueous solution, regenerate, stretched orientation back water is rinsed well, and oven dry obtains regenerated celulose fibre, numbering F3.This fiber is a white, and is soft glossy, has higher intensity.Record regenerated celulose fibre by XQ-1 isodromicing elongation property fibre strength instrument and be fracture strength (σ under the attitude
b) and elongation at break (ε
b), record the degree of crystallinity (χ of regenerated celulose fibre by X-ray diffractometer
c) come together in subordinate list 1.This fiber of data declaration has mechanical property and high degree of crystallinity preferably in the table.
Fracture strength (the σ of subordinate list 1. regenerated celulose fibres
b), elongation at break (ε
b) and degree of crystallinity (χ
c) experimental result
| The fiber numbering | σ b(cN/tex) | ε b(％) | χ c(％) |
| F1 F2 F3 | 12.5 20.0 15.7 | 19.3 21.2 19.3 | 48 53 54 |
Claims (1)
1. the preparation method of a regenerated celulose fibre, it is characterized in that: with cellulose dissolution in 5～12wt% NaOH and 8～20wt% urea mixed aqueous solution, fully stir, make the cellulose concentrated solution, adopt wet spinning process to solidify spraying silk on the spinning machine and in coagulating bath, regenerate, stretched orientation, be drying to obtain regenerated celulose fibre; Described coagulating bath is 3～25wt%H
2SO
4The aqueous solution, 3～25wt%H
2SO
4/ 5～30wt%Na
2SO
4The aqueous solution, 3～25wt%H
2SO
4/ 5～30wt% (NH
4)
2SO
4The aqueous solution, 3～15wt%HCl aqueous solution or 3～15wt%HCl/5～30wt%NH
4The Cl aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410013389 CN1285776C (en) | 2004-06-29 | 2004-06-29 | Preparation method for regenerated cellulose fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410013389 CN1285776C (en) | 2004-06-29 | 2004-06-29 | Preparation method for regenerated cellulose fiber |
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| Publication Number | Publication Date |
|---|---|
| CN1594680A CN1594680A (en) | 2005-03-16 |
| CN1285776C true CN1285776C (en) | 2006-11-22 |
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|---|---|---|---|
| CN 200410013389 Expired - Fee Related CN1285776C (en) | 2004-06-29 | 2004-06-29 | Preparation method for regenerated cellulose fiber |
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Families Citing this family (10)
| 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 |
| CN101037479B (en) * | 2007-04-13 | 2010-05-19 | 武汉大学 | Method for dissolving cellulos |
| CN102443868B (en) * | 2010-09-30 | 2014-10-15 | 中国纺织科学研究院 | Method for manufacturing regenerated cellulose fibers |
| CN102443869B (en) * | 2011-09-22 | 2014-05-14 | 中国纺织科学研究院 | Cellulose solution coagulation forming method |
| CN102691125B (en) * | 2012-06-19 | 2014-01-01 | 武汉大学 | Method for preparing regenerated cellulose fibers with cellulose carbamate |
| CN103668518A (en) * | 2012-09-21 | 2014-03-26 | 江苏蓝品纤维科技发展有限公司 | Aramid fiber and functional fiber prepared therefrom |
| 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 |
| CN104894669A (en) * | 2015-05-22 | 2015-09-09 | 江苏龙马绿色纤维有限公司 | Wet spinning method for solvent method cellulosic fibers |
| CN109112657B (en) * | 2018-08-21 | 2021-04-20 | 桐庐雷泰生物科技有限公司 | Self-heating cellulose fiber and preparation method and application thereof |
| CN113737390B (en) * | 2021-08-27 | 2023-03-28 | 武汉南望环保技术研究有限责任公司 | Production process and production system of regenerated cellulose fiber short fiber spunlace non-woven fabric |
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