CN1491974A - Cellulose solution and its preparing method - Google Patents
Cellulose solution and its preparing method Download PDFInfo
- Publication number
- CN1491974A CN1491974A CNA021470049A CN02147004A CN1491974A CN 1491974 A CN1491974 A CN 1491974A CN A021470049 A CNA021470049 A CN A021470049A CN 02147004 A CN02147004 A CN 02147004A CN 1491974 A CN1491974 A CN 1491974A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- ionic liquid
- solution
- cellulose solution
- mierocrystalline cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The cellulose solution consists of ionic liquid and cellulose in the weight ratio of 3-8 to 100. The ionic liquid is ionic liquid of 1-ethyl 3-methyl imidazol acetate, 1-allyl 3-methyl imidazol chlorate, 1-allyl 3-methyl imidazol acetate or 1-butyl 3-methyl imidazol acetate. The cellulose material is insoluble wood pulp fiber. The preparation process of the cellulose solution is also disclosed. The cellulose solution is used in producing various regenerated cellulose products.
Description
Technical field
The present invention relates to a kind of cellulose solution and preparation method thereof.
Background technology
Along with increasingly sharpening and petroleum-based energy, the rapid threat of exhausting of natural resources of global problem of environmental pollution to Sustainable development, and the raising of public's environmental consciousness, green industry is risen once again as the important component part in the Green Revolution.Plant cellulose is a renewable resources the abundantest on the earth, belongs to environment-friendly material.
Mierocrystalline cellulose is compared with synthetic macromolecule has that 1. natural reserves are huge and 2. can regenerate rapidly that (only the annual regeneration amount of Mierocrystalline cellulose just reaches 1.0 * 10
10Ton) 3. easily degrades, is easy to advantage such as modification.
As everyone knows, because the characteristics of aggregated structure, and higher degree of crystallinity and intermolecular and molecular memory a large amount of hydrogen bonds, make natural cellulose have not melt, undissolved characteristics in most of solvents, be that processing characteristics is relatively poor, this becomes the major limitation of natural cellulose in application, and this also is the topmost aspect that the various product developments of restriction Mierocrystalline cellulose are restricted.Therefore, by using effective cellosolve, obtaining the natural fiber cellulose solution, thereby realize the regeneration and the functionalization of natural fiber cellulosic material, is an important channel of exploitation natural fiber cellulosic material.
Research at most and business-like technology be adopt oxidation methyl morpholine (NMMO) for solvent (referring to Chinese invention patent: the manufacture method of cellulose fiber by solvent method, ZL97107819.X; The manufacture method of Lyocell fibre, CN1151194A; Regenerated cellulose fibre and manufacture method thereof, CN1238016A).In order to improve dissolving power, perhaps reduce the viscosity of cellulose solution, can also adopt the method for mixed solvent, a kind of manufacture method of low viscocity cellulose solution is disclosed as CN 1201802A, by changing solvent composition, mix mutually by oxidation methyl morpholine (NMMO), positive methyl caprolactam (NMC), tetramethyl ammonium chloride (TMAC), to improve dissolving power, reduce soltion viscosity, improve solvent recovering rate, to reduce solvent cost.People are also at the cellosolve of constantly making great efforts other kind of exploitation in addition.As CN 1318582 disclosure of the Invention a kind of preparation method of cellulose membrane.With 4～8% sodium hydroxide/2～8% urea mixed aqueous solutions is solvent, and at 0～10 ℃ of following dissolving cellulos, used peptizer is CaCl
2The aqueous solution, HCl solution or aqueous acetic acid.It is said that this method is pollution-free, cost is low, can dissolve viscosity-average molecular weight is 8.5 * 10
4Following various cellulose slurries.CN1210566 discloses the method that a kind of preparation contains isotropic spinnable solution of Mierocrystalline cellulose, phosphoric acid and/or the phosphoric anhydride of 94-100 (weight) % and all compositions of water, this solution is by cellulose dissolution is made in the solvent of phosphoric acid, and this solvent contains 68-85 (weight) % Vanadium Pentoxide in FLAKES (in the total amount of water in the solvent and phosphoric acid).
Comparatively speaking, the price comparison costliness of oxidation methyl morpholine (NMMO), and also owing to can produce tangible Degradation to Mierocrystalline cellulose during high-temperature digestion, these have all limited its industrialized process.The preparation of double solvents is more loaded down with trivial details, and some double solvents particularly the phosphoric acid kind solvent corrosive nature of hardware also be can not be ignored.Though the NaOH kind solvent is cheap, dissolving cellulos limited in one's ability, and because cold operation, industrializing implementation gets up to have any problem.Seek more green cellosolve and seem particularly necessary.
Ionic liquid is the environment-friendly solvent that a class of rising in recent years has application prospect, is paid close attention to by common people day by day in the application of numerous areas such as chemosynthesis, electrochemistry, extracting and separating, material preparation.Ionic liquid refers to that those contain ionic liquid, or claims that fused salt is more suitable.Compare with traditional organic solvent, water, supercutical fluid etc., ionic liquid has the following advantages: (1) comprises that to a lot of chemical substances organism and inorganics have the good solubility energy; (2) has higher ionic conductivity; (3) higher thermostability; (4) the liquid temperature scope of broad; (5) higher polarity, solvation performance.(6) volatilization, not oxidation hardly, do not burn; (7) viscosity is low, thermal capacitance is big; (8) to water, all stable to air; (9) easily reclaim, can be recycled; (10) equipment is simple, easy to manufacture.Its kind is existing hundreds of and even more.Existing foreign scholar and company China applied for relevant ion liquid preparation and application facet patent (referring to Chinese invention patent: CN1326936A, CN1140422A, CN1123031A).
Summary of the invention
By ion liquid chemical structure is carried out molecular designing, thereby can adjust ion liquid every physical and chemical performance, as performances such as zero pour, polarity, viscosity.By more different ionic liquids, we find that some ionic liquids with ad hoc structure can dissolving cellulos, and can be used as cellulosic solvent.And up to the present, also not having relevant is the report that solvent prepares cellulose solution with the ionic liquid.
It is the tencel cellulose solution and preparation method thereof of solvent with the ionic liquid that the object of the invention has been to provide a kind of.
A kind of cellulose solution of the present invention is that 3～8: 100 ionic liquid and Mierocrystalline cellulose are formed by weight ratio.
Described ionic liquid is the 1-ethyl, 3-methylene diacetate imidazole salts ionic liquid (EMIMAC), 1-allyl group, 3-methyl chloride imidazole salts ionic liquid (AMIMCl), 1-allyl group, 3-methylene diacetate imidazole salts ionic liquid (AMIMAC) or 1-butyl, 3-methylene diacetate imidazole salts ionic liquid (BMIMAC).Described ionic liquid with before should pass through vacuum-drying.Described preparation method of ionic liquid is seen document " Bonhote P, Dias A P, Amand M.Hydrophobic Highly ConductiveAmbient-Temperature Molten Salt.Inorg Chem, Vol.35, P1168-1178,1996 ".
Described Mierocrystalline cellulose is the non-solubility wood pulp cellulose, can be macrofiber, staple fibre, and its polymerization degree can be in 150～800 scopes.Described Mierocrystalline cellulose adopts the conventional NaOH aqueous solution or liquefied ammonia activation with preceding, or other some activating treatment processs, dodges method such as quick-fried as steam and also can adopt vacuum-drying then.Concrete activating treatment process is seen document " Wang Yuanlong, Cheng Bowen, Zhao Jiasen.Cellulosic activation.Tianjin University of Technology's journal, Vol.21, No.2, P83 ~ 86,2002 ".
The preparation method of a kind of cellulose solution of the present invention, carry out as follows: with weight ratio be after 3～8: 100 the vacuum-drying ionic liquid and the activatory Mierocrystalline cellulose be heated to 70～110 ℃ with oil bath, stir or apply machinery simultaneously and mediated 8～24 hours, can obtain the transparent and uniform cellulose ionic liquid solution.
To desiring the dissolved Mierocrystalline cellulose and carrying out thorough drying as the ionic liquid of solvent is necessary because in the system free moisture can the deterioration ionic liquid to cellulosic dissolving power.
Solution is carried out spinning (or shop film), regeneration, washing, drying, can obtain regenerated fibre cellulose products such as regenerated cellulose fibre, diaphragm, nonwoven fabric, film, in addition, other the known purposes that also can be used for cellulose solution is as Mierocrystalline cellulose homogeneous phase derivative reaction in its solution etc.
Simple, the low price, nontoxic, harmless of employed method for synthesizing ionic liquid in the present patent application, the cellulose/ionic liquid solution viscosity of preparation is low, and ionic liquid reclaims easily, and is safe.
Embodiment
Providing some embodiment below and just further specify the present invention, is not to have a mind to limit scope involved in the present invention.
Embodiment 1
Take by weighing and in the 150ml NaOH aqueous solution (20%), behind the immersion 2h, clean three times after 1.0g pulp fibers element tears up with ethanol, stand-by after the vacuum-drying.Take by weighing the vacuum drying EMIMAC ionic liquid of 2.0g, add the 0.06g activated cellulose, in 80 ℃ of oil baths, heat, and carry out magnetic agitation.Along with the prolongation of time, swelling takes place earlier in Mierocrystalline cellulose; Form muddy solution immediately, polarizing microscope is observed down has tangible fiber yarn to exist; At last, the solution clear that becomes is gradually observed under polarizing microscope, and the full visual field is black, illustrates that Mierocrystalline cellulose dissolves fully, and whole dissolution process is 24 hours, makes the cellulose solution that concentration is 2.91wt% thus.
Embodiment 2
Take by weighing and put into pressure vessel after 1.0g pulp fibers element tears up, introduce liquefied ammonia (being as the criterion soaking Mierocrystalline cellulose fully), at room temperature carrying out pressure is that 1.03MPa handles, through behind the 2h, liquefied ammonia is removed in evaporation, and the taking-up activated cellulose is preserved in vacuum drier and substituted.Take by weighing the 4.8gBMIMAC ionic liquid, add the pulp fibers element of 0.2g after the liquefied ammonia activation, in 100 ℃ of oil baths, heat, and carry out magnetic agitation.Mierocrystalline cellulose begins dissolving gradually from winding state originally; 3 hours, solution was homodisperse muddy state; Continue to stir, the solution clarification that becomes is gradually dissolved fully until Mierocrystalline cellulose, and polarizing microscope is observed down, the existence of cellulose-less filament, and this dissolution process is 18 hours.Make the cellulose solution of 4wt% thus.
Embodiment 3
Take by weighing 0.947g AMIMAC ionic liquid, add the Mierocrystalline cellulose (activation method is with embodiment 2) after 0.0474g liquefied ammonia activates, in 100 ℃ of oil baths, heat, and carry out magnetic agitation.Profit rises Mierocrystalline cellulose beginning to occur obviously, and 2 hours, the muddy state of solution becomes yellowly; Continue to stir, the solution clarification that becomes gradually until dissolving fully, is viewed as full visual field black under the polarizing microscope, and this dissolution process is 12 hours.Obtain the cellulose solution of 4.8wt% thus.
Embodiment 4
Take by weighing 23.00g AMIMCl ionic liquid in the 100ml round-bottomed flask, the Mierocrystalline cellulose (activation method is with embodiment 1) after the adding 1.21g NaOH activated in water solution heats in 100 ℃ of oil baths, and carries out magnetic agitation.Profit rises Mierocrystalline cellulose beginning to occur obviously, and 3 hours, the muddy state of solution becomes yellowly: continue to stir, the solution clarification that becomes gradually obtained settled solution in 8 hours, was viewed as full visual field black under the polarizing microscope, illustrated that Mierocrystalline cellulose dissolves fully.Obtain the cellulose solution of 5wt% thus.
Embodiment 5
The Cellulose/EMIMAC solution that the embodiment 1 that takes a morsel prepares evenly is layered in the tetrafluoroethylene mould, soaks repeatedly with distilled water, cleans several times, until rete clear, colorless (ionic liquid is by complete wash-out), remove the upper strata clear water, make rete ventilation at room temperature, dry naturally.Make transparent regenerated cellulose rete, the toughness of film is better.
Embodiment 6
Cellulose/AMIMCl solution with a small amount of embodiment 4 preparations evenly is layered in the tetrafluoroethylene mould, soak repeatedly, clean with distilled water,, remove the upper strata clear water until range estimation rete clear, colorless (ionic liquid is by complete wash-out), make rete ventilation at room temperature, dry naturally.Make water white regenerated cellulose film, mechanical property is better.
Claims (3)
1. cellulose solution is that 3～8: 100 ionic liquid and Mierocrystalline cellulose are formed by weight ratio; Described ionic liquid is the 1-ethyl, 3-methylene diacetate imidazole salts ionic liquid, 1-allyl group, 3-methyl chloride imidazole salts ionic liquid, 1-allyl group, 3-methylene diacetate imidazole salts ionic liquid or 1-butyl, 3-methylene diacetate imidazole salts ionic liquid, described Mierocrystalline cellulose is the non-solubility wood pulp cellulose.
2. according to a kind of cellulose solution of claim 1, it is characterized in that: described cellulosic degree of polymerization is in 150～800 scopes.
3. the preparation method of a cellulose solution, carry out as follows: with weight ratio be after 3～8: 100 the vacuum-drying ionic liquid and the activatory Mierocrystalline cellulose be heated to 70～110 ℃ with oil bath, stir or apply machinery simultaneously and mediated 8～24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02147004.9A CN1261496C (en) | 2002-10-22 | 2002-10-22 | Cellulose solution and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN02147004.9A CN1261496C (en) | 2002-10-22 | 2002-10-22 | Cellulose solution and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1491974A true CN1491974A (en) | 2004-04-28 |
| CN1261496C CN1261496C (en) | 2006-06-28 |
Family
ID=34232916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN02147004.9A Expired - Fee Related CN1261496C (en) | 2002-10-22 | 2002-10-22 | Cellulose solution and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1261496C (en) |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334270C (en) * | 2006-01-23 | 2007-08-29 | 东华大学 | Production of spinning stoste with cellulose base fibre |
| CN100362149C (en) * | 2004-09-23 | 2008-01-16 | 中国石化上海石油化工股份有限公司 | Wet spinning method for polyacryl-nitrile fibre |
| CN100362151C (en) * | 2004-09-23 | 2008-01-16 | 中国石化上海石油化工股份有限公司 | Wet spinning method for polyacryl-nitrile fibre |
| CN100362150C (en) * | 2004-09-23 | 2008-01-16 | 中国石化上海石油化工股份有限公司 | Wet spinning method for polyacryl-nitrile fibre |
| CN100375796C (en) * | 2005-06-21 | 2008-03-19 | 中国科学院过程工程研究所 | Method for preparing regenerated protein fiber using ion liquid dissolving animal hair |
| CN100400579C (en) * | 2004-12-28 | 2008-07-09 | 中国科学院化学研究所 | Method for preparing functional material of regenerated cellulose |
| DE102007035322A1 (en) | 2007-07-25 | 2009-01-29 | Friedrich-Schiller-Universität Jena | Preparing low substituted water-soluble cellulose sulfate used in biomedical application for spherical simplex membrane, by dissolving cellulose in ionic liquid and adding sulfurizing reagent to the medium |
| CN100487059C (en) * | 2005-01-20 | 2009-05-13 | 中国科学院过程工程研究所 | Method for preparing degradable material using stalk |
| CN1806945B (en) * | 2005-01-20 | 2010-05-12 | 中国科学院过程工程研究所 | Method for complete enzymolysis of straw cellulose by utilizing pretreatment and enzymolysis process |
| EP2199319A1 (en) | 2008-12-19 | 2010-06-23 | Gambro Lundia AB | Virus filter |
| US7919631B2 (en) | 2007-02-14 | 2011-04-05 | Eastman Chemical Company | Production of ionic liquids |
| CN101497699B (en) * | 2009-02-24 | 2011-05-11 | 华南理工大学 | Method for improving dissolution performance of cellulose in ion liquid |
| CN101649571B (en) * | 2009-08-31 | 2011-06-08 | 中国科学院广州化学研究所 | Method for dissolving and extracting cellulose in bagasse |
| US8067488B2 (en) | 2009-04-15 | 2011-11-29 | Eastman Chemical Company | Cellulose solutions comprising tetraalkylammonium alkylphosphate and products produced therefrom |
| WO2011154890A1 (en) * | 2010-06-10 | 2011-12-15 | Basf Se | Process for reusing ionic liquids |
| CN101768790B (en) * | 2008-12-29 | 2011-12-28 | 中国纺织科学研究院 | Sheath core composite fibre of chitin and cellulose and preparation method thereof |
| CN102344685A (en) * | 2010-08-05 | 2012-02-08 | 中国科学院化学研究所 | Method for preparing nano cellulose microfibril reinforced polymer composite material |
| US8158777B2 (en) | 2008-02-13 | 2012-04-17 | Eastman Chemical Company | Cellulose esters and their production in halogenated ionic liquids |
| US8188267B2 (en) | 2008-02-13 | 2012-05-29 | Eastman Chemical Company | Treatment of cellulose esters |
| CN102838761A (en) * | 2012-08-27 | 2012-12-26 | 中国热带农业科学院农产品加工研究所 | Method of preventing cellulose from being degraded in ionic liquid |
| US8354525B2 (en) | 2008-02-13 | 2013-01-15 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
| CN102965752A (en) * | 2012-11-28 | 2013-03-13 | 东华大学 | Cellulose in-situ urea modified plastification melt spinning method |
| CN103031608A (en) * | 2012-12-06 | 2013-04-10 | 青岛科技大学 | Preparation method and product of sea squirt cellulose fiber spinning solution |
| US8729253B2 (en) | 2011-04-13 | 2014-05-20 | Eastman Chemical Company | Cellulose ester optical films |
| CN103937011A (en) * | 2014-04-11 | 2014-07-23 | 华南理工大学 | Cellulose dissolving liquid as well as preparation method and application thereof |
| CN104610557A (en) * | 2013-11-01 | 2015-05-13 | 中国科学院化学研究所 | Regenerated cellulose membrane, functional membrane, and preparation method of regenerated cellulose membrane and functional membrane |
| CN104711377A (en) * | 2006-05-25 | 2015-06-17 | 马来西亚国家石油公司 | Conversion method |
| CN105175760A (en) * | 2015-07-16 | 2015-12-23 | 广西科开成林科技有限公司 | Preparation method of cellulose acetate butyrate membrane |
| CN106188629A (en) * | 2015-05-04 | 2016-12-07 | 中国科学院化学研究所 | A kind of functional fiber element composite and preparation method thereof |
| CN106319664A (en) * | 2016-08-20 | 2017-01-11 | 张太平 | Magnetic fiber shell fabric and manufacturing method thereof |
| US9777074B2 (en) | 2008-02-13 | 2017-10-03 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
| US9834516B2 (en) | 2007-02-14 | 2017-12-05 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom |
| US10174129B2 (en) | 2007-02-14 | 2019-01-08 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom |
| CN112397849A (en) * | 2020-10-28 | 2021-02-23 | 中国地质大学（北京） | High-temperature-resistant flame-retardant battery diaphragm and preparation method and application thereof |
| CN114097785A (en) * | 2021-10-18 | 2022-03-01 | 中国科学院化学研究所 | Polysaccharide-based photothermal sterilization material and application thereof in seed protection and grain storage |
| CN116102746A (en) * | 2023-02-20 | 2023-05-12 | 四川大学 | Method for dissolving cellulose based on proton type ionic liquid |
-
2002
- 2002-10-22 CN CN02147004.9A patent/CN1261496C/en not_active Expired - Fee Related
Cited By (58)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362149C (en) * | 2004-09-23 | 2008-01-16 | 中国石化上海石油化工股份有限公司 | Wet spinning method for polyacryl-nitrile fibre |
| CN100362151C (en) * | 2004-09-23 | 2008-01-16 | 中国石化上海石油化工股份有限公司 | Wet spinning method for polyacryl-nitrile fibre |
| CN100362150C (en) * | 2004-09-23 | 2008-01-16 | 中国石化上海石油化工股份有限公司 | Wet spinning method for polyacryl-nitrile fibre |
| CN100400579C (en) * | 2004-12-28 | 2008-07-09 | 中国科学院化学研究所 | Method for preparing functional material of regenerated cellulose |
| CN100487059C (en) * | 2005-01-20 | 2009-05-13 | 中国科学院过程工程研究所 | Method for preparing degradable material using stalk |
| CN1806945B (en) * | 2005-01-20 | 2010-05-12 | 中国科学院过程工程研究所 | Method for complete enzymolysis of straw cellulose by utilizing pretreatment and enzymolysis process |
| CN100375796C (en) * | 2005-06-21 | 2008-03-19 | 中国科学院过程工程研究所 | Method for preparing regenerated protein fiber using ion liquid dissolving animal hair |
| CN100334270C (en) * | 2006-01-23 | 2007-08-29 | 东华大学 | Production of spinning stoste with cellulose base fibre |
| CN104711377A (en) * | 2006-05-25 | 2015-06-17 | 马来西亚国家石油公司 | Conversion method |
| US10174129B2 (en) | 2007-02-14 | 2019-01-08 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom |
| US7919631B2 (en) | 2007-02-14 | 2011-04-05 | Eastman Chemical Company | Production of ionic liquids |
| US9834516B2 (en) | 2007-02-14 | 2017-12-05 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a carboxylated ionic liquid process and products produced therefrom |
| US8153782B2 (en) | 2007-02-14 | 2012-04-10 | Eastman Chemical Company | Reformation of ionic liquids |
| US8148518B2 (en) | 2007-02-14 | 2012-04-03 | Eastman Chemical Company | Cellulose esters and their production in carboxylated ionic liquids |
| DE102007035322A1 (en) | 2007-07-25 | 2009-01-29 | Friedrich-Schiller-Universität Jena | Preparing low substituted water-soluble cellulose sulfate used in biomedical application for spherical simplex membrane, by dissolving cellulose in ionic liquid and adding sulfurizing reagent to the medium |
| US9777074B2 (en) | 2008-02-13 | 2017-10-03 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
| US8354525B2 (en) | 2008-02-13 | 2013-01-15 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
| US9175096B2 (en) | 2008-02-13 | 2015-11-03 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a halogenated ionic liquid process and products produced therefrom |
| US8158777B2 (en) | 2008-02-13 | 2012-04-17 | Eastman Chemical Company | Cellulose esters and their production in halogenated ionic liquids |
| US9156918B2 (en) | 2008-02-13 | 2015-10-13 | Eastman Chemical Company | Treatment of cellulose esters |
| US8188267B2 (en) | 2008-02-13 | 2012-05-29 | Eastman Chemical Company | Treatment of cellulose esters |
| US8273872B2 (en) | 2008-02-13 | 2012-09-25 | Eastman Chemical Company | Cellulose esters and their production in halogenated ionic liquids |
| EP2199319A1 (en) | 2008-12-19 | 2010-06-23 | Gambro Lundia AB | Virus filter |
| CN101768790B (en) * | 2008-12-29 | 2011-12-28 | 中国纺织科学研究院 | Sheath core composite fibre of chitin and cellulose and preparation method thereof |
| CN101497699B (en) * | 2009-02-24 | 2011-05-11 | 华南理工大学 | Method for improving dissolution performance of cellulose in ion liquid |
| US9926384B2 (en) | 2009-04-15 | 2018-03-27 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a tetraalkylammonium alkylphosphate ionic liquid process and products produced therefrom |
| CN102459350A (en) * | 2009-04-15 | 2012-05-16 | 伊士曼化工公司 | Cellulose solutions comprising tetraalkylammonium alkylphosphate and products produced therefrom |
| US8871924B2 (en) | 2009-04-15 | 2014-10-28 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a tetraalkylammonium alkylphosphate ionic liquid process and products produced therefrom |
| US8524887B2 (en) | 2009-04-15 | 2013-09-03 | Eastman Chemical Company | Regioselectively substituted cellulose esters produced in a tetraalkylammonium alkylphosphate ionic liquid process and products produced therefrom |
| US8067488B2 (en) | 2009-04-15 | 2011-11-29 | Eastman Chemical Company | Cellulose solutions comprising tetraalkylammonium alkylphosphate and products produced therefrom |
| CN101649571B (en) * | 2009-08-31 | 2011-06-08 | 中国科学院广州化学研究所 | Method for dissolving and extracting cellulose in bagasse |
| WO2011154890A1 (en) * | 2010-06-10 | 2011-12-15 | Basf Se | Process for reusing ionic liquids |
| CN102344685B (en) * | 2010-08-05 | 2014-03-12 | 中国科学院化学研究所 | Method for preparing nano cellulose microfibril reinforced polymer composite material |
| CN102344685A (en) * | 2010-08-05 | 2012-02-08 | 中国科学院化学研究所 | Method for preparing nano cellulose microfibril reinforced polymer composite material |
| US9096691B2 (en) | 2011-04-13 | 2015-08-04 | Eastman Chemical Company | Cellulose ester optical films |
| US10836835B2 (en) | 2011-04-13 | 2020-11-17 | Eastman Chemical Company | Cellulose ester optical films |
| US8729253B2 (en) | 2011-04-13 | 2014-05-20 | Eastman Chemical Company | Cellulose ester optical films |
| US10494447B2 (en) | 2011-04-13 | 2019-12-03 | Eastman Chemical Company | Cellulose ester optical films |
| US9975967B2 (en) | 2011-04-13 | 2018-05-22 | Eastman Chemical Company | Cellulose ester optical films |
| US9796791B2 (en) | 2011-04-13 | 2017-10-24 | Eastman Chemical Company | Cellulose ester optical films |
| CN102838761A (en) * | 2012-08-27 | 2012-12-26 | 中国热带农业科学院农产品加工研究所 | Method of preventing cellulose from being degraded in ionic liquid |
| CN102965752A (en) * | 2012-11-28 | 2013-03-13 | 东华大学 | Cellulose in-situ urea modified plastification melt spinning method |
| CN102965752B (en) * | 2012-11-28 | 2014-07-23 | 东华大学 | Cellulose in-situ urea modified plastification melt spinning method |
| CN103031608A (en) * | 2012-12-06 | 2013-04-10 | 青岛科技大学 | Preparation method and product of sea squirt cellulose fiber spinning solution |
| CN104610557B (en) * | 2013-11-01 | 2018-03-02 | 中国科学院化学研究所 | A kind of regenerated cellulose film, functional membrane and preparation method thereof |
| CN104610557A (en) * | 2013-11-01 | 2015-05-13 | 中国科学院化学研究所 | Regenerated cellulose membrane, functional membrane, and preparation method of regenerated cellulose membrane and functional membrane |
| CN103937011A (en) * | 2014-04-11 | 2014-07-23 | 华南理工大学 | Cellulose dissolving liquid as well as preparation method and application thereof |
| CN103937011B (en) * | 2014-04-11 | 2017-01-04 | 华南理工大学 | A kind of cellulose dissolution liquid and preparation method and application |
| CN106188629A (en) * | 2015-05-04 | 2016-12-07 | 中国科学院化学研究所 | A kind of functional fiber element composite and preparation method thereof |
| CN105175760A (en) * | 2015-07-16 | 2015-12-23 | 广西科开成林科技有限公司 | Preparation method of cellulose acetate butyrate membrane |
| CN105175760B (en) * | 2015-07-16 | 2018-12-04 | 广西科开成林科技有限公司 | A kind of preparation method of acetylbutyrylcellulose film |
| CN106319664B (en) * | 2016-08-20 | 2019-03-01 | 浙江罗卡芙家纺有限公司 | A kind of Magnetic fiber fabric and its manufacturing method |
| CN106319664A (en) * | 2016-08-20 | 2017-01-11 | 张太平 | Magnetic fiber shell fabric and manufacturing method thereof |
| CN112397849A (en) * | 2020-10-28 | 2021-02-23 | 中国地质大学（北京） | High-temperature-resistant flame-retardant battery diaphragm and preparation method and application thereof |
| CN114097785A (en) * | 2021-10-18 | 2022-03-01 | 中国科学院化学研究所 | Polysaccharide-based photothermal sterilization material and application thereof in seed protection and grain storage |
| CN114097785B (en) * | 2021-10-18 | 2023-04-07 | 中国科学院化学研究所 | Polysaccharide-based photothermal sterilization material and application thereof in seed protection and grain storage |
| CN116102746A (en) * | 2023-02-20 | 2023-05-12 | 四川大学 | Method for dissolving cellulose based on proton type ionic liquid |
| CN116102746B (en) * | 2023-02-20 | 2024-04-12 | 四川大学 | Method for dissolving cellulose based on proton type ionic liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1261496C (en) | 2006-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1261496C (en) | Cellulose solution and its preparing method | |
| Wang et al. | Extraction of cellulose nanocrystals using a recyclable deep eutectic solvent | |
| Xu et al. | Carboxylate ionic liquid solvent systems from 2006 to 2020: thermal properties and application in cellulose processing | |
| Zhu et al. | Dissolution of cellulose with ionic liquids and its application: a mini-review | |
| Zhong et al. | Choline hydroxide based deep eutectic solvent for dissolving cellulose | |
| Sun et al. | Dissolution of cellulose with a novel solvent and formation of regenerated cellulose fiber | |
| EP2845874B1 (en) | Method for dissolving cellulose | |
| CN108641102B (en) | High-efficiency cellulose solvent system and application thereof | |
| CN107177040B (en) | A kind of cellulose solution and its dissolving method and application | |
| Li et al. | Structure and properties of regenerated cellulose fibers based on dissolution of cellulose in a CO2 switchable solvent | |
| MXPA04003029A (en) | Dissolution and processing of cellulose using ionic liquids. | |
| JP2009203467A (en) | Solvent for dissolving cellulose and molded article from cellulose solution | |
| CN101037479A (en) | Method for dissolving cellulos | |
| CN102304238B (en) | Renewable cellulose composite film and preparation method thereof | |
| CN101654522A (en) | Anti-degradable solvent for dissolving cellulose and preparation method of spinning dope thereof | |
| Zhou et al. | Structure and properties of blend membranes prepared from cellulose and alginate in NaOH/urea aqueous solution | |
| CN104710627A (en) | Process method for improving dissolving property of cellulose in tetrabutyl ammonium hydroxide aqueous solution | |
| CN105037760B (en) | A kind of preparation method of cellulose nano-fibrous flexible transparent film | |
| Chen et al. | Super solvent of cellulose with extra high solubility for tunable cellulose structure with versatile application | |
| CN104047067A (en) | Cellulose dissolving agent and application thereof | |
| CN1252163C (en) | Lithium hydrate and carbamide composition solvent for dissolving cellulous fiber and its use | |
| Xie et al. | Preparation of degradable wood cellulose films using ionic liquids | |
| Suzuki et al. | Air-jet wet-spinning of curdlan using ionic liquid | |
| CN104262642A (en) | Method for dissolving cellulose in aqueous solution of NaOH/thiourea at normal temperature | |
| Jiang et al. | Effective preparation of bamboo cellulose fibers in quaternary ammonium/DMSO solvent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: WEIFANG HENGLIAN CELLOPHANE Co.,Ltd. Assignor: Institute of Chemistry, Chinese Academy of Sciences Contract record no.: 2011370000336 Denomination of invention: Cellulose solution and its preparing method Granted publication date: 20060628 License type: Exclusive License Open date: 20040428 Record date: 20110715 |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180914 Address after: 261106 Hanting District, Weifang, Shandong Province solid embankment street office Lingang Industrial Park North District Patentee after: Shandong Zhongke Heng Lian biological base material Co.,Ltd. Address before: 100080 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Patentee before: Institute of Chemistry, Chinese Academy of Sciences |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060628 Termination date: 20211022 |