CN1193061C - Solvent composite and preparation method and use thereof - Google Patents
Solvent composite and preparation method and use thereof Download PDFInfo
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- CN1193061C CN1193061C CNB031283861A CN03128386A CN1193061C CN 1193061 C CN1193061 C CN 1193061C CN B031283861 A CNB031283861 A CN B031283861A CN 03128386 A CN03128386 A CN 03128386A CN 1193061 C CN1193061 C CN 1193061C
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- Prior art keywords
- urea
- cellulose
- sodium hydroxide
- solution
- solvent composition
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- 239000002904 solvent Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000002131 composite material Substances 0.000 title 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 94
- 229920002678 cellulose Polymers 0.000 claims abstract description 56
- 239000001913 cellulose Substances 0.000 claims abstract description 52
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004202 carbamide Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004627 regenerated cellulose Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 235000010980 cellulose Nutrition 0.000 description 50
- 239000000243 solution Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 17
- 239000000835 fiber Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 229920000297 Rayon Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 5
- 239000000693 micelle Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229920000433 Lyocell Polymers 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 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
- 230000035800 maturation Effects 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 229920002955 Art silk Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000002977 biomimetic material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000008104 plant cellulose Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to a solvent composition which is basically prepared from 5 to 12 wt% of sodium hydroxide, 8 to 20 wt% of urea and the balance of water. The present invention also provides a preparation method of the solvent composition, which comprises: the sodium hydroxide and the urea are mixed and prepared into the solvent composition within the proportioning range, or firstly, the sodium hydroxide is prepared into a water solution, and secondly, the urea is added to obtain the required solvent composition. The water solution of the sodium hydroxide and the urea of the present invention can be used for directly and quickly dissolving natural cellulose and regenerated cellulose, and a transparent concentrated cellulose solution of high solubility (which can reach 100%) can be obtained.
Description
Technical field
The present invention relates to a kind of solvent compositions and its production and use.
Background technology
Because the nondegradation plastic refuse causes environmental pollution serious day by day, and petroleum resources will be progressively exhausted after 50 years, and the research and development of renewable resources are noticeable day by day.Plant cellulose is the abundantest reproducible organic resource of the earth, belongs to the environmental friendliness macromolecular material.Mierocrystalline cellulose more and more comes into one's own with its distinguished reproduction speed (1,000 hundred million tons/year), and is expected to become the functional materials of 21 century.Yet Mierocrystalline cellulose is far from reaching and makes full use of in chemical industry, and is main because the cellulose dissolution process is numerous and diverse in the existing technology, cost is high and pollution (J.Macromol.Sci.-Rev.Macromol.Chem., 1980, C18 (1), 1) is arranged.Present cellulose prods more than 90% still adopts traditional viscose process production.Mierocrystalline cellulose is (naoh concentration 18%) and CS under the highly basic effect
2Reaction generates cellulose xanthate, and it is soluble in alkaline solution and becomes viscose.But viscose is wire drawing or system film after maturation, regenerates in dilute acid soln then, obtains viscose fiber or glassine paper.Because this method discharges a large amount of poisonous CS in process of production
2And H
2S gas has caused huge injury for human body health, also environment has been caused serious pollution simultaneously, and it is extremely urgent therefore to research and develop new cellosolve system.In recent years, various organic or inorganic novel solvents have been obtained bigger progress, methyl-sulphoxide-oxynitride (U.S.patent 3236669,1966) are wherein arranged, 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
2(U.S.Patent 5290349 for the aqueous solution, 1994), trichoro-aldehyde-methyl-sulphoxide-pyridine mixed solution (Polym.J 1980,12,521), LiCl/DMAc (U.S.Patent4302252,1981), N-methyl morpholine oxide (MMNO) (J.Polym.Sci.:Polym.Lett.Ed.1979,17,219) and the NaOH aqueous solution (Japan Patent 1777283,1983) etc.MMNO is 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, cellulose carbamate can directly be dissolved in and obtain spinning solution (Finnish Patent 61003 in the sig water; Finnish Patent 62318; U.S.Patent 4404369), but must generate cellulose carbamate than reaction under the severe condition, and also have by product, therefore there is not using value yet.People such as Kamide have reported that Mierocrystalline cellulose is at 2.5molL
-1Dissolving in the NaOH aqueous solution, but must adopt the wood pulp cellulose of handling through steam explosion (polymerization degree＜250), it may be dissolved in (U.S.Patent4634470 in the NaOH aqueous solution when 4 ℃ of left and right sides; Polymer J., 1984,12,857; Polymer J., 1988,20,447).But this solvent lacks prospects for commercial application because of being subjected to the restriction of cellulose dissolution degree.Publication number is the patent application of CN1318582A, relates generally to the sodium hydroxide of 4-8% and the urea mixed aqueous solution of 2-8%, adds behind the Mierocrystalline cellulose under the refrigerator freezing conditions, by freezing, thaw cycles process dissolving cellulos.But weak point is that cellulosic solubleness is not high enough, lacks the large-scale application prospect.
Summary of the invention
Problem to be solved by this invention provides a kind of solvent compositions and its production and use, this solvent compositions can be directly dissolving cellulos fast, and obtain the transparent Mierocrystalline cellulose strong solution of high-dissolvability.
Technical scheme provided by the invention is: a kind of solvent compositions, and it consists of: the sodium hydroxide of 5-12wt%, the urea of 8.5-20wt%, all the other are water.
The content of above-mentioned sodium hydroxide is 6.5～10.5wt%, and content of urea is 8.5～15wt%.
The present invention also provides the preparation method of above-mentioned solvent compositions, in the said ratio scope, sodium hydroxide and urea are mixed, add water and be made into solvent compositions, perhaps sodium hydroxide and urea are made into the aqueous solution respectively, mix obtaining required solvent compositions then, perhaps earlier sodium hydroxide is made into the aqueous solution, add urea then and obtain required solvent compositions.
Sodium hydroxide of the present invention and aqueous solution of urea can be used for directly dissolving natural cellulose and regenerated cellulose fast, obtain preparing the cellulose solution of multiple cellulosics (cellulosic fibre, film, non-woven fabrics, chromatographic column protruded packing, medical biomimetic material etc.) thus.
Compared with the prior art, innovation of the present invention is as follows:
Invention first can be directly the sodium hydroxide of dissolving cellulos and aqueous solution of urea solvent compositions and preparation method thereof fast.Sodium hydroxide that the present invention relates to and aqueous solution of urea can directly dissolve natural cellulose (cotton linter pulp, straw fiber slurry, bagasse pulp, soft wood pulp, hard wood pulp etc.) and regenerated cellulose (non-woven fabrics, glassine paper, short rayon fiber, long filament etc.) fast, and can obtain the transparent Mierocrystalline cellulose strong solution of high-dissolvability (solubleness can reach 100%).This method and viscose process and cellulose carbamate method have in essence different, have that raw material consumption is few, inexpensive, with short production cycle, the simple advantage of technical process.The present invention is raw material with the natural cellulose, and whole process does not have chemical reaction, 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:
Embodiment 1
190 gram 6.5wt%NaOH/15wt% urea mixed aqueous solutions (are mixed in proportion sodium hydroxide and urea, add water and be made into this solvent compositions), place-5 ℃ of cryosels to bathe cooling, add 10 gram cotton linter pulps (polymerization degree 500) then and stir fast, obtain transparent cellulose solution.Falling ball method is surveyed this cellulose solution viscosity and is about 60PaS.Filter with 400 order gauzes and poplin cloth under 1～2MPa barometric point, solution can filter fully, and the visible fiber of no naked eyes exists in the gained solution.Mierocrystalline cellulose dissolves fully, obtains solubleness and be 100% Mierocrystalline cellulose clear solution.
Embodiment 2
190 gram 12wt%NaOH/8.5wt% urea mixed aqueous solutions (with sodium hydroxide and urea be made into aqueous solution evenly and must this solvent compositions), place-5 ℃ of cryosels to bathe cooling, add 10 gram cotton linter pulps (polymerization degree 500) then and stir fast, obtain transparent cellulose solution.Falling ball method is surveyed this cellulose solution viscosity and is about 60PaS.At 10,000 rev/mins, 15 ℃ 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.Mierocrystalline cellulose dissolves fully, obtains solubleness and be 100% Mierocrystalline cellulose clear solution.
Embodiment 3
167.2 the gram 9.1wt%NaOH aqueous solution places-5 ℃ of cryosels to bathe cooling, obtains 190 gram 8wt%NaOH/12wt% urea mixed aqueous solutions after the adding 22.8 gram urea dissolvings.Add 10 gram cotton linter pulps (polymerization degree 500) and stir fast, obtain transparent cellulose solution.At 10,000 rev/mins, 15 ℃ 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.Mierocrystalline cellulose dissolves fully, obtains solubleness and be 100% Mierocrystalline cellulose clear solution.
Embodiment 4
Method by embodiment 1 or 2 or 3 is mixed with 192 gram 10.5wt%NaOH/20wt% urea mixed aqueous solutions, is cooled to-10 ℃, adds 8 gram cotton linter pulps (polymerization degree 500) then and stirs fast, obtains transparent cellulose solution.At 10,000 rev/mins, 15 ℃ 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.
Embodiment 5
Method by embodiment 1 or 2 or 3 is mixed with 180 gram 5wt%NaOH/8wt% urea mixed aqueous solutions, adds 20 gram regenerated celluloses (polymerization degree 300) when temperature is+4 ℃ and stirs fast, obtains transparent cellulose solution.At 10,000 rev/mins, 15 ℃ 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, obtains solubleness and be 100% Mierocrystalline cellulose clear solution.
Embodiment 6
Method by embodiment 1 or 2 or 3 is mixed with 190 gram 8wt%NaOH/15wt% urea mixed aqueous solutions, places-5 ℃ of cryosels to bathe cooling, adds 10 gram wood pulps (polymerization degree 460) then and stirs rapidly, obtains transparent cellulose solution.At 10,000 rev/mins, 15 ℃ 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.Mierocrystalline cellulose dissolves fully, obtains solubleness and be 100% Mierocrystalline cellulose clear solution.
Also available other alkali of sodium hydroxide in the solvent compositions of the present invention replace as lithium hydroxide, potassium hydroxide.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031283861A CN1193061C (en) | 2003-07-25 | 2003-07-25 | Solvent composite and preparation method and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031283861A CN1193061C (en) | 2003-07-25 | 2003-07-25 | Solvent composite and preparation method and use thereof |
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|---|---|
| CN1482159A CN1482159A (en) | 2004-03-17 |
| CN1193061C true CN1193061C (en) | 2005-03-16 |
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|---|---|---|---|
| CNB031283861A Expired - Fee Related CN1193061C (en) | 2003-07-25 | 2003-07-25 | Solvent composite and preparation method and use thereof |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296417C (en) * | 2004-09-01 | 2007-01-24 | 武汉大学 | Cellulose and nanometer titania composite material, preparation and use thereof |
| CN1282773C (en) | 2005-05-30 | 2006-11-01 | 武汉大学 | Method for preparing regenerated cellulose fiber by two-step coagulation bath method |
| CN1313495C (en) * | 2005-08-24 | 2007-05-02 | 武汉大学 | Hydroxy ethyl cellulose preparation method |
| CN101037479B (en) * | 2007-04-13 | 2010-05-19 | 武汉大学 | A method for dissolving cellulose |
| CN102191706A (en) * | 2010-03-19 | 2011-09-21 | 上海市七宝中学 | Process for preparing cellulose |
| CN102432891B (en) * | 2011-09-15 | 2014-02-12 | 南华大学 | A kind of dissolving method of cellulose |
| CN102926015B (en) * | 2012-11-20 | 2015-04-08 | 东华大学 | A method for preparing hydroxyethyl cellulose fiber by pregel method |
| CN109258691A (en) * | 2018-10-29 | 2019-01-25 | 广东惠利民有害生物防制工程有限公司 | A kind of paddy bait that efficiently kills mouse |
| CN109438579B (en) * | 2018-11-09 | 2021-03-19 | 陕西科技大学 | Preparation method of hydrophobically modified cellulose polymer micelle |
| CN112591736B (en) * | 2020-12-16 | 2022-12-20 | 四川大学 | A method for cellulose-assisted dispersion of carbon nanotubes |
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2003
- 2003-07-25 CN CNB031283861A patent/CN1193061C/en not_active Expired - Fee Related
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| CN1482159A (en) | 2004-03-17 |
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