CN101130605A - Solvent composition for solubilizing cellulose - Google Patents
Solvent composition for solubilizing cellulose Download PDFInfo
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- CN101130605A CN101130605A CNA2007100535656A CN200710053565A CN101130605A CN 101130605 A CN101130605 A CN 101130605A CN A2007100535656 A CNA2007100535656 A CN A2007100535656A CN 200710053565 A CN200710053565 A CN 200710053565A CN 101130605 A CN101130605 A CN 101130605A
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Abstract
The invention discloses a solvent to dissolve cellulose, which comprises the following parts: 6-8wt% sodium hydroxide, 0. 5-2wt% sodium zincate, 8-16wt% aquacare and water, wherein the solvent can dissolve cellulose through freezing-thawing method, which can be precooled to -12- -14 deg. c to dissolve the cellulose under 0-5 deg. c; the method can dissolve natural cellulose and regenerative cellulose with molecular weight below 20X104 and solubility at 100%. The solvent can be applied to make regenerative cellulose film, blending film, cellulose/nanometer particle functional film and nonwoven fabrics, which can also be reacting dielectric of the derived cellulose.
Description
Technical field
The present invention relates to a kind of solvent compositions of dissolving cellulos.
Background technology
Plant cellulose is a renewable resources the abundantest on the earth, belongs to environment-friendly material, makes full use of Mierocrystalline cellulose and not only can protect environment, and can save limited petroleum resources.Yet, because Mierocrystalline cellulose contains a large amount of intramolecularly and intermolecular hydrogen bonding, indissoluble separates also that infusibility melts processing, at present the technology of large-scale industrial production regenerated cellulose product remain viscose process, this technology produces a large amount of CS in the process of producing artificial silk and glassine paper
2With heavy metal and serious environment pollution.Other organic or inorganic solvents, for example: methyl-sulphoxide-oxynitride (U.S.patent 3236669,1966), ZnCl
2The aqueous solution (U.S.Patent 5290349,1994), LiCl/DMAc (U.S.Patent 4302252,1981) etc. are difficult to industrialization owing to dissolution process is numerous and diverse with price problem.In recent years (U.S.patent 2179181,1939 novel solvent N-methyl morpholine oxide (NMMO) to have occurred; Brit.1144048,1967; U.S.patent4246221,1981), and be considered to the most promising cellosolve, but owing to it costs an arm and a leg, the temperature of dissolving cellulos is higher, suitability for industrialized production is made slow progress.Equally, ionic liquid also is used for dissolving cellulos, but still exists high-temperature digestion and solvent to need problems such as recovery fully.In addition, Mierocrystalline cellulose and urea at high temperature react the generation cellulose carbamate, directly are 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, by product is arranged, also be difficult to industrialization.Japan reports (Japan Patent 1777283,1983; U.S.Patent4634470) at 2.5molL
-1Dissolving cellulos in the NaOH aqueous solution, but must use the wood pulp cellulose of handling through steam explosion (polymerization degree is lower than 250).The solvent compositions (NaOH/ urea/water) that Chinese patent 200310111566.3 discloses a kind of dissolving cellulos is used for cellulosic dissolving, and this solvent compositions can only dissolve the less relatively Mierocrystalline cellulose of molecular weight and (be lower than 12 * 10
4), and the cellulose solution concentration not high (the high-molecular weight Mierocrystalline cellulose can only reach about 4wt%) of preparation, so industrialization is subjected to certain limitation.
Summary of the invention
The purpose of this invention is to provide a kind of cellosolve, this solvent can be by freeze-thaw or direct dissolving method dissolving high molecular weight fibers element, and the cellulose solution concentration height of preparation is easy to industrialization.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of solvent compositions of dissolving cellulos, it consists of: 6～8wt% sodium hydroxide, 0.5～2wt% sodium zincate, 8～16wt% urea, 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 6～8wt% sodium hydroxide, 0.5～2wt% sodium zincate and 8～16wt% urea, descended freezing 3～5 hours at-20 ℃, at room temperature thawing stirs can make transparent cellulose solution.
A kind of method of dissolving cellulos, natural cellulose or regenerated cellulose are scattered in the mixed aqueous solution of the 6～8wt% sodium hydroxide, 0.5～2wt% sodium zincate and the 8～16wt% urea that are cooled to-12 °～-14 °, under 0～5 ℃, stir then and can make transparent cellulose solution.
The present invention can be used for industrial dissolving cellulos, prepares various cellulose silks, film, non-woven fabrics and chromatographic column protruded packing.Also can be used on the laboratory and carry out the research of molecular weight cellulose and SOLUTION PROPERTIES.Cellulose membrane of the present invention can be used as textiles, plastic sheeting for farm use, packing and the parting material in the fields such as textile industry, agricultural, chemical industry, food, environment.
Compared with the prior art, innovation of the present invention is as follows:
The present invention adopts polycomponent dissolution with solvents Mierocrystalline cellulose, and simple efficient, the dissolved molecular weight cellulose is 20 * 10
4Below, concentration height, and the cellulose solution good stability of preparation can store for a long time.Solubleness to various Mierocrystalline celluloses (cotton linter pulp, straw fiber slurry, bagasse pulp, wood pulp and cellulosic nonwoven fabric and steam quick-fried cellulose slurry etc.) all reaches 100%, can make the high-molecular weight strong solution.Solvent compositions with respect to the NaOH/ urea/water of Chinese patent 200310111566.3 invention can improve 20%～60% to the cellulose solution concentration of preparation.And the dissolving and regeneration all be physical process, chemical reaction does not take place, the easy recycling use of waste liquid.Not high to equipment requirements, help suitability for industrialized production.The present invention is a raw material with sodium hydroxide, urea, sodium zincate, water, and low price is simple to operation, environmentally safe.
Embodiment
Below in conjunction with concrete example technical scheme of the present invention is described further:
Embodiment 1
Get cotton linter pulp (viscosity-average molecular weight M
η=10 * 10
4) 8.4 gram inputs, 200 gram 7wt%NaOH/0.5wt%Na
2ZnO
2In/10wt% urea the mixed water solution, descended freezing 3～5 hours at-20 ℃, at room temperature thawing stirs can make transparent cellulose solution.With the vitreous fibre cellulose solution high speed centrifugation that makes, there is not molten part, the cellulose dissolution degree reaches 100%.
Embodiment 2
Get cotton linter pulp (viscosity-average molecular weight M
η=8 * 10
4) 1 gram input, 200 gram 7wt%NaOH/0.5wt%Na
2ZnO
2In/12wt% urea the mixed water solution, descended freezing 3～5 hours at-20 ℃, at room temperature thawing stirs can make transparent cellulose solution.With the vitreous fibre cellulose solution high speed centrifugation that makes, there is not molten part, the cellulose dissolution degree reaches 100%.
Embodiment 3
200 gram 7wt%NaOH/0.5wt%Na
2ZnO
2/ 14wt% urea mixed water solution is chilled to-14 ℃ in advance, gets cotton linter pulp (viscosity-average molecular weight M immediately
η=20 * 10
4) 6 grams drop into wherein, stir under 0 ℃, make transparent cellulose solution.With the vitreous fibre cellulose solution high speed centrifugation that makes, there is not molten part, the cellulose dissolution degree reaches 100%.
Embodiment 4
200 gram 6wt%NaOH/2wt%Na
2ZnO
2/ 16wt% urea mixed water solution is chilled to-13 ℃ in advance, gets non-woven fabrics (viscosity-average molecular weight M immediately
η=15 * 10
4) 10 grams drop into wherein, stir under 0 ℃, make transparent cellulose solution.With the vitreous fibre cellulose solution high speed centrifugation that makes, there is not molten part, the cellulose dissolution degree reaches 100%.
Embodiment 5
200 gram 8wt%NaOH/1wt%Na
2ZnO
2/ 8wt% urea mixed water solution is chilled to-12 ℃ in advance, gets wood pulp (viscosity-average molecular weight M immediately
η=12 * 10
4) 10 grams drop into wherein, stir under 0 ℃, make transparent cellulose solution.With the vitreous fibre cellulose solution high speed centrifugation that makes, there is not molten part, the cellulose dissolution degree reaches 100%.
Embodiment 6
200 gram 7wt%NaOH/0.5wt%Na
2ZnO
2/ 12wt% urea mixed water solution is chilled to-12 ℃ in advance, gets cotton linter pulp (viscosity-average molecular weight M immediately
η=15 * 10
4) 8.4 grams drop into wherein, stir under 0 ℃, make transparent cellulose solution.With after the transparency cellulose solution centrifugal deaeration that makes on sheet glass casting film-forming, put into the 5wt% aqueous sulfuric acid then, soak after 5 minutes and to take out, water is rinsed well, is attached at last that natural airing obtains regenerated cellulose film on the sheet glass.Record its tensile strength σ by electronics pulling experiment machine
b, elongation at break ε
bAnd Young's modulus is respectively 110MPa, 12% and 4500MPa.Transmittance is 92% (800nm).
The cellulose solution (the cellulose concentration scope is 0.05%～10%) that can prepare different concns with aforesaid method.
Claims (3)
1. the solvent compositions of a dissolving cellulos, it consists of: 6～8wt% sodium hydroxide, 0.5～2wt% sodium zincate, 8～16wt% urea, 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 6～8wt% sodium hydroxide, 0.5～2wt% sodium zincate and 8～16wt% urea, descended freezing 3～5 hours at-20 ℃, at room temperature thawing stirs can make transparent cellulose solution.
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 the 6～8wt% sodium hydroxide, 0.5～2wt% sodium zincate and the 8～16wt% urea that are cooled to-12 °～-14 ℃, under 0～5 ℃, stir then and can make transparent cellulose solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100535656A CN101130605A (en) | 2007-10-16 | 2007-10-16 | Solvent composition for solubilizing cellulose |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100535656A CN101130605A (en) | 2007-10-16 | 2007-10-16 | Solvent composition for solubilizing cellulose |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101130605A true CN101130605A (en) | 2008-02-27 |
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| CNA2007100535656A Pending CN101130605A (en) | 2007-10-16 | 2007-10-16 | Solvent composition for solubilizing cellulose |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432891A (en) * | 2011-09-15 | 2012-05-02 | 喻翠云 | Method for dissolving cellulose |
| CN103668979A (en) * | 2013-12-03 | 2014-03-26 | 苏州爱马仕服饰有限公司 | Preparation process for anti-ultraviolet fabric |
| CN106519306A (en) * | 2016-10-09 | 2017-03-22 | 浙江理工大学 | Cellulose based Ag @ ZnO nano composite hydrogel and preparation method thereof |
| CN108822343A (en) * | 2018-04-25 | 2018-11-16 | 武汉水木弘新材料有限公司 | A kind of preparation method of phase transformation material of regenerated cellulose |
| CN112724394A (en) * | 2020-12-28 | 2021-04-30 | 山东一诺威新材料有限公司 | Preparation method of cellulose polyether polyol |
| CN113564731A (en) * | 2021-06-17 | 2021-10-29 | 武汉纺织大学 | Method for recycling waste denim laser ash and recycled material |
| CN116921417A (en) * | 2023-07-31 | 2023-10-24 | 覃姿颖 | Method for repairing and treating heavy metal contaminated soil |
-
2007
- 2007-10-16 CN CNA2007100535656A patent/CN101130605A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432891A (en) * | 2011-09-15 | 2012-05-02 | 喻翠云 | Method for dissolving cellulose |
| CN102432891B (en) * | 2011-09-15 | 2014-02-12 | 南华大学 | Method for dissolving cellulose |
| CN103668979A (en) * | 2013-12-03 | 2014-03-26 | 苏州爱马仕服饰有限公司 | Preparation process for anti-ultraviolet fabric |
| CN106519306A (en) * | 2016-10-09 | 2017-03-22 | 浙江理工大学 | Cellulose based Ag @ ZnO nano composite hydrogel and preparation method thereof |
| CN108822343A (en) * | 2018-04-25 | 2018-11-16 | 武汉水木弘新材料有限公司 | A kind of preparation method of phase transformation material of regenerated cellulose |
| CN112724394A (en) * | 2020-12-28 | 2021-04-30 | 山东一诺威新材料有限公司 | Preparation method of cellulose polyether polyol |
| CN113564731A (en) * | 2021-06-17 | 2021-10-29 | 武汉纺织大学 | Method for recycling waste denim laser ash and recycled material |
| CN116921417A (en) * | 2023-07-31 | 2023-10-24 | 覃姿颖 | Method for repairing and treating heavy metal contaminated soil |
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