CN100572432C - A kind of cellulose solution and preparation method thereof - Google Patents
A kind of cellulose solution and preparation method thereof Download PDFInfo
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- CN100572432C CN100572432C CNB2007100637414A CN200710063741A CN100572432C CN 100572432 C CN100572432 C CN 100572432C CN B2007100637414 A CNB2007100637414 A CN B2007100637414A CN 200710063741 A CN200710063741 A CN 200710063741A CN 100572432 C CN100572432 C CN 100572432C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
A kind of cellulose solution, comprise following component: Mierocrystalline cellulose, account for 7.0%～30.0% of described cellulose solution weight, remaining component be can dissolving cellulos imidazole type ion liquid and the organic solvent that can dissolve each other with imidazole type ion liquid, their weight ratio is 1: 9～24: 1, above-mentioned cellulose solution is prepared from by the following method: the cellulose pulp after will pulverizing is mixed in described all the other components, makes the homogeneous fibre cellulose solution by the processing step that heats up, stirs, mediates, vacuumizes.Adopt the method for preparing cellulose solution, can reduce difficulty of processing, alleviate wearing and tearing production equipment, and cellulose solution concentration height, the uniform and stable difficult degraded of preparation, cost also reduces simultaneously, is suitable for suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of cellulose solution and preparation method thereof.
Background technology
Day by day exhausted along with the resources such as outstanding, oil of problem of environmental pollution, natural resources rationally, effectively, environmental protection ground utilizes becomes the focus that people pay close attention to.
Mierocrystalline cellulose is one of natural resource that distributed in nature is the widest, reserves are maximum, and its renewable and degradability meets contemporary recycling economy, requirements of green environmental protection.But it is in by the link of coming into human society naturally, it is not very environmental protection and meet current friendly process and require at the very start, particularly chemical reaction process that exists in the production process such as paper, viscose fiber and pollution are the problems that people pay close attention to always, and these have expedited the emergence of the birth of direct dissolving cellulos solvent.What Lyocell adopted is exactly that the method that Mierocrystalline cellulose directly is dissolved in organic cellulose solvent N-methylmorpholine-N-oxide compound (NMMO) is prepared, and solvent is nontoxic and recyclable, does not have chemical reaction process, pollution-free in the production process, at present industrialization.
Lyocell also has some shortcomings in process of production: 1) contain nitrogen-oxygen bond among the solvent NMMO, be easy to cause cellulosic oxidative degradation, the solvent Heating temperature is easy to blast above 130 ℃ simultaneously; 2) the solvent recuperation difficulty is big, and along with oil shortage, cost of material goes up, and it is a lot of to go up when present solvent price has begun industrialization than Lyocell; 3) need the high vacuum dehydration in the dissolution process, energy consumption is big; 4) the high-viscosity high-elasticity state can occur in the dissolution process, production equipment requires high; 5) it is limited to reach the concentration of homogeneous solution, and gained fiber species and production cost and efficient are restricted.So need to seek a kind of safer, inexpensive, green, cellulose dissolution solvent efficiently.
The U.S. Pat 6824599 that on November 30th, 2004 announced discloses the cellulose solution prescription in the hydrophilic ionic liquids, described solvent is the hydrophilic solvent that comprises organic cation and non-organic or organic anion, and provided the structure of the compound of a series of possible ionic liquid correspondences, comprising the ion solvent of the imidazole type of using among the present invention.In addition, also disclose in this piece patent a kind of in described hydrophilic ionic liquids the method for dissolving cellulos.Yet this piece patent is not specifically related to the method for dissolving cellulos in the process for processing, as the processing and treating method of the high-viscosity high-elasticity attitude of meeting appearance in the formulations prepared from solutions process.
The application number that on April 28th, 2004 announced is 02147004.9, the Chinese patent that is entitled as " a kind of cellulose solution and preparation method thereof ", providing a kind of is the tencel cellulose solution and preparation method thereof of solvent with the ionic liquid, ionic liquid wherein is the 1-ethyl, 3-methylene diacetate imidazole salts, 1-allyl group, 3-methyl chloride imidazole salts, 1-allyl group, 3-methylene diacetate imidazole salts or 1-butyl, 3-methylene diacetate imidazole salts, described imidazole type ion liquid and cellulosic weight ratio are 3～8: 100.Yet contain undersaturated pair of key for the ionic liquid that wherein relates to, when dissolving cellulos, be easy to cause cellulosic degraded and ion liquid loss.In this piece patent application, among the preparation method of the cellulose solution that the applicant mentions, before ionic liquid, Mierocrystalline cellulose need be activated, and provide the example that Mierocrystalline cellulose is carried out modification with liquefied ammonia in an embodiment simultaneously at cellulose dissolution.
Be entitled as " research of cellulosic material/ionic liquid solution system rheological performance " literary composition in that " Mierocrystalline cellulose science and technology " magazine is delivered in June, 2006, reported the influence of the dimethyl sulfoxide (DMSO) that adds 3% solution weight or N, N-N,N-DIMETHYLACETAMIDE the viscosity of 3% concentration washing steam exploded wheat straw/chlorination 1-butyl-3-Methylimidazole solution of having prepared.Yet the cellulose solution that obtains with the technical scheme of this piece article does not have using value in practice because cellulosic content wherein is low excessively.If make the cellulose solution that obtains with practical value, need the cellulosic content in the cellulose solution to reach more than 7%, adopt the method for the common elevated temperature in this area, then be easy to cause the cellulose degradation in the processing and the problem of ionic liquid loss, the cellulose solution quality that influence obtains.If add in employing this article and identical dimethyl sulfoxide (DMSO) or the N of washing steam exploded wheat straw ratio, the cellulose solution that the N-N,N-DIMETHYLACETAMIDE obtains still has very high viscosity, do not have practical value, simultaneously this article fail to study these organic solvents in the cellulose/ion liquid system by being blended into the influence that realizes in the uniform dissolution process system, do not relate to the preparation of production practice middle and high concentration cellulose solution, more do not relate to the difficulty of processing height that in preparation high density Mierocrystalline cellulose homogeneous solution process, exists, cellulose degradation, problems such as ionic liquid loss.And to problems such as the difficulty of processing height that in preparation high density Mierocrystalline cellulose homogeneous solution process, exists, cellulose degradation, ionic liquid losses.
The inventor finds through test of many times: 1) a high-viscosity high-elasticity attitude can occur in the pure imidazole type ion liquid dissolving cellulos process, cause very big difficulty to processing, particularly common equipment is difficult to prepare uniform solution when concentration surpasses 12%; 2) adopt pure imidazole type ion liquid dissolving cellulos, when solvent temperature or solution temperature meet or exceed 140 ℃, be easy to cellulose initiated degraded.
Summary of the invention
An object of the present invention is to provide a kind of uniform and stable cellulose solution.
The invention provides a kind of cellulose solution, wherein cellulose solution comprises Mierocrystalline cellulose, it accounts for 7.0%～30.0% of cellulose solution weight, remaining component be can dissolving cellulos imidazole type ion liquid and the organic solvent that can dissolve each other with imidazole type ion liquid, their weight ratio is 1: 9～9: 1
Above-mentioned cellulose solution is prepared from by the following method: the cellulose pulp after will pulverizing is mixed in all the other components, makes the homogeneous fibre cellulose solution by the processing step that heats up, stirs, mediates, vacuumizes.
The organic solvent that can dissolve each other with imidazole type ion liquid is N,N-dimethylacetamide, N, one or several in dinethylformamide or the dimethyl sulfoxide (DMSO).
The imidazole type ion liquid of energy dissolving cellulos is chlorination 1-butyl-3-Methylimidazole, chlorination 1, one or several in 3-methylimidazole, chlorination 1-ethyl-3-Methylimidazole, chlorination 1-propyl group-3-Methylimidazole, the acetic acid 1-ethyl-3-Methylimidazole.
Above-mentioned Mierocrystalline cellulose is from the cotton pulp dregs of rice, wood pulp or the straw pulp one or more.
10.0%～20.0% of cellulose comprises cellulose solution weight.
All the other above-mentioned components are dissolved in imidazole type ion liquid in the described organic solvent and obtain.
Cellulose pulp is warmed up to 90 ℃～160 ℃ in described all the other components.
Above-mentioned cellulose pulp is warmed up to 110 ℃～140 ℃ in described all the other components.
In above-mentioned cellulose solution preparation process, in described temperature-rise period, apply vacuum tightness water and other low boiling point organic solvent of 0.1～1.0 crust to remove in cellulose solution or to bring in the operating process.
The inventor is through repeatedly experiment discovery, in the cellulose solution that common imidazole type ion liquid dissolving cellulos forms, when the content of Mierocrystalline cellulose in cellulose solution less than 4% the time, do not need the participation of organic solvent, cellulosic uniform dissolution just reaches than being easier to; When the content of Mierocrystalline cellulose in cellulose solution greater than 4% the time, cellulosic uniform dissolution is just along with the increase of the concentration and the polymerization degree is more and more difficult, the viscosity of resulting cellulose solution can be more and more higher, and then cause many difficulties can for the machine-shaping in the production process, cause many difficulties for actual production process.
Usually after the imidazole type ion liquid dissolving cellulos, too improve temperature and can strengthen cellulosic degraded, increase ion liquid loss, reduce the quality of fibre product, and the loss of molding device etc. also increased, so during the cellulose solution in the preparation ionic liquid, elevated temperature is controlled within 135 ℃ usually.
Yet the cellulose solution among employing the present invention, then can realize the uniform dissolution of 7% above concentration cellulose solution, simultaneously the polymerization degree is at 150～900 Mierocrystalline cellulose, even in the process of mixed dissolution, along with the increase of content of cellulose or the increase of cellulosic degree of polymerization, when uniform dissolution is more and more difficult, can be by the method that heats up or organic solvent is removed in decompression, prepare uniform and stable cellulose solution, regulate the viscosity of cellulose solution simultaneously.Researchist of the present invention prepares cellulose solution of the present invention through test of many times, because the balance and stability effect of solvent system, even the intensification height to 160 of cellulose solution ℃, can not cause the obvious degradation of Mierocrystalline cellulose in cellulose solution by preferred 140 ℃; Because solvent progressively acts on Mierocrystalline cellulose infiltration, swelling, dissolved and the concentrating of solvent system, and can realize the preparation of high density uniform fiber cellulose solution, obtains high-level cellulose solution.Mierocrystalline cellulose need be activated this step when adopting cellulose solution of the present invention and preparation method thereof to remove employing glyoxaline ion liquid dissolving cellulos from simultaneously, production cost also is lower than the cost when adopting NMMO ion liquid dissolving Mierocrystalline cellulose simultaneously, also having removed picture NMMO ionic liquid from must strict control water ratio this necessary processing step wherein when dissolving cellulos, also needn't as the NMMO ionic liquid for increase cellulose dissolution and adopt the technology of twin-screw extruder.
Adopt top described method to prepare cellulose solution and can reduce difficulty of processing, alleviate wearing and tearing production equipment, preparation high density cellulose solution, and the uniform and stable difficult degraded of cellulose solution of preparation, cost also reduces simultaneously, is suitable for suitability for industrialized production.Adopt present method gained solution can be used to prepare the goods of different purposes such as film class, fiber-like with differences such as concentration, temperature, the polymerization degree.
Embodiment
Embodiment 1
110 gram acetic acid 1-ethyl-3-Methylimidazole liquid are added in the 440 gram N,N-dimethylacetamide, and stirring and dissolving obtains mixed uniformly solvent; 48 gram wood pulps are pulverized the back to stir, mediates in the limit adding mixed solvent, behind reinforced the finishing, sealing is stirred down and is warmed up to 105 ℃ gradually, under the vacuum tightness of 0.9 crust, remove volatile impunty and bubble in the solution therebetween, finally obtain the solution of homogeneous transparent, concentration is 7%, and viscosity is 750PaS.
Embodiment 2
554 gram chlorination 1-butyl-3-Methylimidazole solids are added in the 277 gram N,N-dimethylacetamide, and stirring and dissolving obtains mixed uniformly solvent under suitable temperature; To add while stirring in the mixed solvent after the 92 gram wood pulps pulverizing, behind reinforced the finishing, sealing is stirred down and is warmed up to 125 ℃ gradually, under the vacuum tightness of 1.0 crust, remove volatile impunty and bubble in the solution therebetween, finally obtain the solution of homogeneous transparent, concentration is 10%, and viscosity is 950PaS.
Embodiment 3
554 gram chlorination 1-propyl group-3-Methylimidazole weak yellow liquids are added in the 277 gram N,N-dimethylacetamide, and stirring and dissolving obtains mixed uniformly solvent; To add in the mixed solvent while stirring after the 95 gram wood pulps pulverizing, behind reinforced the finishing, sealing is stirred down and is warmed up to 135 ℃ gradually, under the vacuum tightness of 0.5 crust, remove volatile impunty and bubble in the solution therebetween, and remove organic solvent by decompression, finally obtain the solution of homogeneous transparent, concentration is 12%, and viscosity is 1150PaS.
Embodiment 4
554 gram chlorination 1-butyl-3-Methylimidazoles are added in the 184 gram dimethyl sulfoxide (DMSO), and stirring and dissolving obtains mixed uniformly solvent; After 114 gram wood pulps pulverizing, add in the mixed solvent while stirring, behind reinforced the finishing, sealing is stirred down and is warmed up to 145 ℃ gradually, under the vacuum tightness of 0.4 crust, remove volatile impunty and bubble in the solution therebetween, and remove organic solvent, finally obtain the solution of homogeneous transparent by decompression, concentration is 15%, and viscosity is 1350PaS.
Embodiment 5
554 gram chlorination 1-butyl-3-Methylimidazole liquid are added in the 1108 gram dimethyl sulfoxide (DMSO), mix to stir obtaining mixed uniformly solvent; After 150 gram wood pulps pulverizing, add in the mixed solvent while stirring, behind reinforced the finishing, sealing is stirred down and is warmed up to 150 ℃ gradually, under 0.8 crust vacuum tightness, remove volatile impunty and bubble in the solution therebetween, and remove organic solvent, finally obtain the solution of homogeneous transparent by decompression, concentration is 20%, and viscosity is 1550PaS.
Embodiment 6
554 gram chlorination 1-butyl-3-Methylimidazole liquid are added in the 1108 gram dimethyl sulfoxide (DMSO), stir and obtain mixed uniformly solvent; To add in the mixed solvent while stirring after the 195 gram wood pulps pulverizing, behind reinforced the finishing, sealing is stirred down and is warmed up to 155 ℃ gradually, under 0.2 crust vacuum tightness, remove volatile impunty and bubble in the solution therebetween, and remove organic solvent by decompression, finally obtain the solution of homogeneous transparent, concentration is 25%, and viscosity is 1750PaS.
Embodiment 7
554 gram chlorination 1-butyl-3-Methylimidazoles are added in the 1108 gram dimethyl sulfoxide (DMSO), and stirring and dissolving obtains mixed uniformly solvent; After 247 gram wood pulps pulverizing, add in the mixed solvent while stirring, behind reinforced the finishing, sealing is stirred down and is warmed up to 158 ℃ gradually, under 0.6 crust vacuum tightness, remove volatile impunty and bubble in the solution therebetween, and remove organic solvent, finally obtain the solution of homogeneous transparent by decompression, concentration is 30%, and viscosity is 1950PaS.
Embodiment 8
554 gram chlorination 1-benzyl-3-Methylimidazole solids are added in the 277 gram N,N-dimethylacetamide, and stirring and dissolving obtains mixed uniformly solvent under suitable temperature; To add while stirring in the mixed solvent after the 92 gram wood pulps pulverizing, behind reinforced the finishing, sealing is stirred down and is warmed up to 140 ℃ gradually, under the vacuum tightness of 1.0 crust, remove volatile impunty and bubble in the solution therebetween, finally obtain the solution of homogeneous transparent, concentration is 10%, and viscosity is 1150PaS.
Claims (9)
1, a kind of cellulose solution, it is characterized in that described cellulose solution comprises Mierocrystalline cellulose, it accounts for 7.0%～30.0% of described cellulose solution weight, all the other components be can dissolving cellulos imidazole type ion liquid and the organic solvent that can dissolve each other with imidazole type ion liquid, their weight ratio is 1: 9～24: 1, the described organic solvent that can dissolve each other with imidazole type ion liquid is N, N-N,N-DIMETHYLACETAMIDE, N, one or several in dinethylformamide or the dimethyl sulfoxide (DMSO); Described cellulose solution is prepared from by the following method: the cellulose pulp after will pulverizing is mixed in described all the other components, makes the homogeneous fibre cellulose solution by the processing step that heats up, stirs, mediates, vacuumizes.
2, cellulose solution according to claim 1 is characterized in that described weight ratio is 1: 9～9: 1.
3, cellulose solution according to claim 1, the imidazole type ion liquid that it is characterized in that described energy dissolving cellulos is chlorination 1-butyl-3 Methylimidazole, chlorination 1, one or several in 3-methylimidazole, chlorination 1-ethyl-3 Methylimidazole, chlorination 1-propyl group-3 Methylimidazole, acetic acid 1-ethyl-3 Methylimidazole, the chlorination 1-benzyl-3-Methylimidazole.
4, cellulose solution according to claim 1 is characterized in that described Mierocrystalline cellulose is from the cotton pulp dregs of rice, wood pulp or the straw pulp one or more.
5, cellulose solution according to claim 1 is characterized in that 10.0%～20.0% of described cellulose comprises cellulose solution weight.
6, cellulose solution according to claim 1 is characterized in that described all the other components are dissolved in imidazole type ion liquid in the described organic solvent to obtain.
7, cellulose solution according to claim 1 is characterized in that described cellulose pulp is warmed up to 90 ℃～160 ℃ in described all the other components.
8, cellulose solution according to claim 7 is characterized in that described cellulose pulp is warmed up to 110 ℃～140 ℃ in described all the other components.
9, cellulose solution according to claim 1, it is characterized in that in described cellulose solution preparation process, in described temperature-rise period, apply vacuum tightness water and other low boiling point organic solvent of 0.1～1.0 crust to remove in cellulose solution or to bring in the operating process.
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| 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 |
| 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 |
| US8188267B2 (en) | 2008-02-13 | 2012-05-29 | Eastman Chemical Company | Treatment of cellulose esters |
| US8158777B2 (en) | 2008-02-13 | 2012-04-17 | Eastman Chemical Company | Cellulose esters and their production in halogenated ionic liquids |
| 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 |
| 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 |
| 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 |
| JP5677754B2 (en) * | 2010-03-05 | 2015-02-25 | オリンパス株式会社 | Cellulose nanofiber and method for producing the same, composite resin composition, molded article |
| US9975967B2 (en) | 2011-04-13 | 2018-05-22 | Eastman Chemical Company | Cellulose ester optical films |
| CN103694482A (en) * | 2012-09-27 | 2014-04-02 | 中国科学院大连化学物理研究所 | Cellulose solution, cellulose dissolution method and regenerated cellulose |
| CN103172754A (en) * | 2013-04-07 | 2013-06-26 | 中国科学院过程工程研究所 | Method for preparing carboxymethylcellulose from ionic liquid |
| CN104277121B (en) * | 2013-07-03 | 2017-02-08 | 中国科学院大连化学物理研究所 | Method for preparing cellulose ester by using cellulose |
| CN103773054B (en) * | 2013-12-26 | 2015-12-30 | 南京林业大学 | A kind of method preparing lignocellulose bio-based plastics |
| CN104946701A (en) * | 2014-03-27 | 2015-09-30 | 中国科学院大连化学物理研究所 | Method for improving cellulase hydrolysis sugar field |
| 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 |
| CN104047067B (en) * | 2014-05-22 | 2016-05-11 | 北京林业大学 | A kind of cellulose dissolution agent and application thereof |
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