CN1358769A - Cellulose dissolved thiourea alkaline liquod solvent and method for preparing regenerated fibrous membrane - Google Patents
Cellulose dissolved thiourea alkaline liquod solvent and method for preparing regenerated fibrous membrane Download PDFInfo
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- CN1358769A CN1358769A CN 00128162 CN00128162A CN1358769A CN 1358769 A CN1358769 A CN 1358769A CN 00128162 CN00128162 CN 00128162 CN 00128162 A CN00128162 A CN 00128162A CN 1358769 A CN1358769 A CN 1358769A
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- CN
- China
- Prior art keywords
- cellulose
- aqueous solution
- solvent
- thiourea
- solution
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Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 36
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000001913 cellulose Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 title claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000012528 membrane Substances 0.000 title description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000004627 regenerated cellulose Substances 0.000 claims abstract description 11
- 229920000875 Dissolving pulp Polymers 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920001131 Pulp (paper) Polymers 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims 2
- 238000005345 coagulation Methods 0.000 claims 2
- 239000003125 aqueous solvent Substances 0.000 claims 1
- 229920000297 Rayon Polymers 0.000 abstract description 6
- 238000005266 casting Methods 0.000 abstract description 3
- 239000004745 nonwoven fabric Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229920000298 Cellophane Polymers 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000004202 carbamide Substances 0.000 abstract 1
- 239000002964 rayon Substances 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000005357 flat glass Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002955 Art silk Polymers 0.000 description 2
- 108010088842 Fibrinolysin Proteins 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229940001501 fibrinolysin Drugs 0.000 description 2
- 239000011086 glassine Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000008104 plant cellulose Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明公开了一种溶解纤维素的硫脲碱水溶剂以及用此溶剂制备再生纤维素膜的方法。该溶剂是以氢氧化钠和硫脲为原料配成水溶液,用该溶剂溶解纤维素,其溶解能力比氢氧化钠和尿素水溶液液更强。该溶液经流延法刮膜后,经稀酸水溶液凝固再生制得透明的再生纤维素膜。该膜具有良好的力学性能及生物可降解性,而且价格便宜、生产过程简单、方便、无毒、无害、无污染。本法可望取代目前污染严重的粘胶法生产玻璃纸、人造丝及无纺布工艺。由此带来较大的经济效益和社会效益。The invention discloses a thiourea alkali water solvent for dissolving cellulose and a method for preparing a regenerated cellulose film with the solvent. The solvent uses sodium hydroxide and thiourea as raw materials to form an aqueous solution, and the solvent is used to dissolve cellulose, and its dissolving ability is stronger than that of sodium hydroxide and urea aqueous solution. After the solution is scraped by a casting method, it is coagulated and regenerated by a dilute acid aqueous solution to obtain a transparent regenerated cellulose film. The film has good mechanical properties and biodegradability, and is cheap, simple and convenient to produce, non-toxic, harmless and pollution-free. This method is expected to replace the currently polluting viscose method to produce cellophane, rayon and non-woven fabrics. This brings greater economic and social benefits.
Description
The present invention relates to a kind of novel solvent of dissolving cellulos and prepare the novel method of regenerated cellulose film, belong to the natural polymer field, also belong to chemistry, agricultural, field of environment engineering with this solvent.
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.Because Mierocrystalline cellulose has very strong intramolecularly and intermolecular hydrogen bonding, thus indissoluble separate can not fusion, thereby limited its widespread use greatly.The industrialized so far viscose process that is still is produced artificial silk and glassine paper, but produces a large amount of CS in the production process
2And serious environment pollution.Therefore, the novel solvent and the new technology of development dissolving cellulos are extremely urgent.Recent two decades comes, and various free of contamination organic or inorganic novel solvents have been obtained bigger progress, methyl-sulphoxide (DMF)-oxynitride (U.S.pattent 3236669,1966) are wherein arranged, NH
3/ NH
3The SCN aqueous solution (J.Polym.Sci.Polym.Chem.Ed.1980,18,3469), Ca (SCN)
2With the NaSCN aqueous solution (Polymer J.1998,30,43; 30,49), ZnCl
2(U.S.Patent 5290349 for the aqueous solution, 1994), trichoro-aldehyde-methyl-sulphoxide (DMF)-pyridine mixed solution (Polym.J 1980,12,521), (U.S.Patent 4302252 for LiCl/DMAc, 1981), N-methyl-N-morpholine oxide (NMMO) (J.Polym.Sci.:Polym.Lett.Ed.1979,17,219) and the NaOH aqueous solution (Japan Patent 1777283,1983) etc.N-methyl-N-morpholine oxide is the strongest up to now cellosolve, comes into the market with the plain product of the small amount of fibers of its preparation.But owing to it costs an arm and a leg, spinning temperature is higher, the suitability for industrialized production slower development.The NaOH aqueous solution is the most cheap solvent of dissolving cellulos, when natural cellulosic hydrogen bond is corrupted to a certain degree, may be dissolved in during 4 ℃ of left and right sides in the NaOH aqueous solution of 7-9wt%.But this solvent only can be lower than 250 cellulosic molecule by the solvent polymerization degree, and obtained fiber yarn intensity is lower, is not suitable for industrialization spinning or system film.
The purpose of this invention is to provide a kind of novel solvent of dissolving cellulos and prepare the novel method of cellulose membrane with its.This method will be with low price and free of contamination sodium hydroxide and thiocarbamide [(CS (NH
2)
2)] be solvent, by the dissolution in low temperature Mierocrystalline cellulose.Behind curtain coating legal system film, with aqueous sulfuric acid, aqueous acetic acid, CaCl
2The aqueous solution or the HCl aqueous solution be that solidification liquid regeneration makes regenerated cellulose film.It is raw material that present method adopts Mierocrystalline cellulose, utilizes simple casting technique, and to adopt cheap inorganic salt and organic aqueous solution be solvent, is a kind of low cost, the novel method of high production.This method is expected to replace the with serious pollution technology that present viscose process is produced glassine paper and artificial silk, will bring economic benefit and social benefit thus.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of thiocarbamide buck solvent of dissolving cellulos is mixed with the aqueous solution with sodium hydroxide and thiocarbamide in 6-8wt%/2-8wt% ratio, and it is standby to be stored in refrigerator (below 10 ℃) after preparing.
The method of dissolving cellulos: with 10 gram natural cellulose molecular weight (M
η＜10.2 * 10
4) or II fiber type element (M
η＜12 * 10
4) be dispersed in 190 gram 6-8wt%NaOH/2-8wt% thiocarbamide mixed aqueous solutions, in ice-water bath, stirred 5 minutes, be placed in the refrigerator (0 ℃) then freezing 3 to 5 hours.Take out the back and under room temperature, fully stir, promptly make transparent cellulose solution.
The above-mentioned solvent of a kind of usefulness prepares the method for cellulose membrane: use casting method knifing on sheet glass after above-mentioned transparent cellulose solution is filtered, outgases.This film was handled 2-5 minute with the 2-5wt% aqueous sulfuric acid, and clean drying promptly gets regenerated cellulose film.System as peptizer can also be 1-2mol/L aqueous acetic acid, 5wt%CaCl
2/ 1～2wt%HCl mixed aqueous solution or 1～2wt%HCl aqueous solution etc.
Sodium hydroxide/thiourea solution of the present invention can be used for industrial dissolving cellulos, and it has stronger dissolving cellulos ability than sodium hydroxide/quiet plain aqueous solution.Can be used for preparing 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 growing seedlings in the fields such as agricultural, chemical industry, food, environment, covers, packing and parting material.
Compared with the prior art, innovation of the present invention is as follows:
Novel solvent-the sodium hydroxide of dissolving cellulos provided by the present invention and thiocarbamide mixed aqueous solution, its concentration is lower, is respectively 4-8% and 2-8% (weight ratio), and wherein the caustic dip concentration (15-18%) of NaOH concentration ratio viscose process is low 3 times.And various Mierocrystalline celluloses (cotton linter pulp, straw fiber slurry, bagasse pulp, wood pulp and cellulosic nonwoven fabric and steam quick-fried cellulose slurry etc.) there is bigger solubleness, especially for the natural cotton short flannel of high-crystallinity, by adding a small amount of thiocarbamide, just can effectively dissolve natural cellulose (M
η＜10.2 * 10
4).Existing NaOH water solution system (9-10%), wood pulp cellulose and regenerated cellulose after can only the dissolved vapor explosion, especially for the natural cotton short flannel, even through steaming quick-fried processing, its solubleness is still less than 9% (Br.Polym.J 1990,22,73).Its reason mainly is to quicken its dissolving because thiocarbamide can destroy hydrogen bond between poly-polysaccharide molecule effectively.
The present invention makes solvent with sodium hydroxide/thiocarbamide mixed aqueous solution, low price, and solvency power is strong, and is simple to operation, environmentally safe.
The used solidification liquid of the present invention is aqueous sulfuric acid, aqueous acetic acid, the HCl aqueous solution, low price, and production process is simple, convenient, nontoxic, harmless, pollution-free, safe.Regenerated cellulose film by present method preparation has excellent mechanical property, light transmission and biodegradability.Be expected to replace industrial viscose process and cuprammonium process, thereby be with a wide range of applications.
Below in conjunction with concrete example technical scheme of the present invention is described further:
Embodiment 1
Extracting cellulose slurry (viscosity-average molecular weight M
η=10.2 * 10
4) 10 grams, add 190 gram 6wt%NaOH/5wt% thiocarbamide mixed aqueous solutions, in ice-water bath below 6 ℃, stirred 5 minutes, be placed in the refrigerator (0 ℃) then freezing 3 hours, take out fully and stir, obtain colourless transparent solution.Remove by filter on a small quantity not behind the fibrinolysin knifing on sheet glass, put into the 5wt% aqueous sulfuric acid immediately, soak after 2-5 minute and take out, water is rinsed well.Be 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 100MPa, 15% and 4679MPa.Transmittance is 85% (400-800nm)
Embodiment 2
Extracting cellulose slurry (viscosity-average molecular weight M
η=10.2 * 10
4) 10 grams, add 190 gram 6wt%NaOH/5wt% thiocarbamide mixed aqueous solutions, in ice-water bath below 4 ℃, stirred 5 minutes, be placed in the refrigerator (0 ℃) then freezing 4 hours, take out fully and stir, obtain colourless transparent solution.Remove by filter on a small quantity not behind the fibrinolysin knifing on sheet glass, put into the 2mol/L aqueous acetic acid immediately, soak after 3-4 minute and take out, water is rinsed well.Be 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 83MPa, 9.5% and 3923MPa.Transmittance is 84% (400-800nm).
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00128162 CN1126760C (en) | 2000-12-28 | 2000-12-28 | Cellulose dissolved thiourea alkaline liquod solvent and method for preparing regenerated fibrous membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00128162 CN1126760C (en) | 2000-12-28 | 2000-12-28 | Cellulose dissolved thiourea alkaline liquod solvent and method for preparing regenerated fibrous membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1358769A true CN1358769A (en) | 2002-07-17 |
| CN1126760C CN1126760C (en) | 2003-11-05 |
Family
ID=4593014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00128162 Expired - Fee Related CN1126760C (en) | 2000-12-28 | 2000-12-28 | Cellulose dissolved thiourea alkaline liquod solvent and method for preparing regenerated fibrous membrane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7981337B2 (en) | 2006-04-21 | 2011-07-19 | Wuhan University | Use of aqueous NaOH/thiourea solution in pilot-scale production of cellulose products |
| US8492125B2 (en) | 2008-05-06 | 2013-07-23 | Tty Saatio | Method for dissolving cellulose and a cellulosic product obtained from a solution comprising dissolved 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 |
| CN106012667A (en) * | 2016-05-20 | 2016-10-12 | 广州纽楷美新材料科技有限公司 | Hollocellulose transparent paper and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300227C (en) * | 2005-05-30 | 2007-02-14 | 武汉大学 | Microporous membrane and its preparing process and use thereof |
-
2000
- 2000-12-28 CN CN 00128162 patent/CN1126760C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7981337B2 (en) | 2006-04-21 | 2011-07-19 | Wuhan University | Use of aqueous NaOH/thiourea solution in pilot-scale production of cellulose products |
| US8492125B2 (en) | 2008-05-06 | 2013-07-23 | Tty Saatio | Method for dissolving cellulose and a cellulosic product obtained from a solution comprising dissolved cellulose |
| CN102037019B (en) * | 2008-05-06 | 2014-04-02 | 坦佩雷理工大学 | A method for dissolving cellulose and a cellulosic product obtained from a solution comprising dissolved 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 |
| CN106012667A (en) * | 2016-05-20 | 2016-10-12 | 广州纽楷美新材料科技有限公司 | Hollocellulose transparent paper and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1126760C (en) | 2003-11-05 |
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