CN104047067A - Cellulose dissolving agent and application thereof - Google Patents
Cellulose dissolving agent and application thereof Download PDFInfo
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- CN104047067A CN104047067A CN201410220133.XA CN201410220133A CN104047067A CN 104047067 A CN104047067 A CN 104047067A CN 201410220133 A CN201410220133 A CN 201410220133A CN 104047067 A CN104047067 A CN 104047067A
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- cellulose
- ionic liquid
- cellulose dissolution
- dissolution agent
- spinning solution
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Abstract
The invention provides a cellulose dissolving agent and application thereof. The cellulose dissolving agent is a mixture of an ionic liquid and an organic solvent; cations in the ionic liquid are alkyl imidazole ions and alkyl quaternary ammonium ions; anions in the ionic liquid are one or more than two selected from Cl<->, CH3COO<->, CF3COO<->, CF3SO3<->, BF4<->, (CF3SO2)3C<->, PF6<-> and (CF3SO2)2N<->; the organic solvent is one or more than two selected from N,N-dimethyl formamide, N,N-dimethylacetamide, N-methyl pyrrolidone and dimethyl sulfoxide. The cellulose dissolving agent provided by the invention can directly and rapidly dissolve natural cellulose and regenerated cellulose and have high solubility.
Description
Technical field
The present invention relates to cellulose regenerated field, specifically, relate to a kind of cellulose dissolution agent and application thereof.
Background technology
Day by day exhausted along with resources such as outstanding, the oil of problem of environmental pollution, natural resources rationally, effectively utilize and become the focus that people pay close attention to.
Regenerated celulose fibre (Regenerated Cellulose Fibre) is that raw material is made with cellulose, the regenerated fiber that structure is cellulose II.Due to the exhaustion day by day of the minimizing of ploughing and petroleum resources, the output of natural fabric, synthetic fiber will be subject to increasing restriction; People in environmental-protecting performance, re-recognize and excavate the value of regenerated celulose fibre in attention textiles process of consumption.Nowadays the application of regenerated celulose fibre has obtained a unprecedented opportunity to develop.
Cellulose is one of natural resources that occurring in nature distributes the most extensively, reserves are maximum, belongs to environmental friendliness shaped material, and the mankind have long-term applicating history and application technology, and its elaboration products are applied widely at aspects such as fiber, papermaking, film, polymer.Making full use of cellulose resource not only can protection of the environment, and can save limited petroleum resources.But current more than 90% fiber enterprise is still taking traditional viscose as main.Production technology is: boiling refined natural cellulose, remove the impurity such as polysaccharide, lignin, hemicellulose, through CS
2sulfonation, then be dissolved in alkali lye, rayon spinning liquid made.In this explained hereafter, can produce CS
2, H
2the toxic gases such as S and some waste water, serious environment pollution.Along with the enhancing of people to environmental consciousness, the production of viscose is restricted.In order to meet better the requirement of people to cellulose fibre, a lot of researchers are devoted to the research of novel cellulose fibre manufacturing technique always.Recent two decades comes, various free of contamination organic or inorganic novel solvents have been obtained larger progress, wherein have LiCl/DMAc, N-methyl-N-morpholine oxide (NMMO), dimethyl sulfoxide (DMSO) (DMSO)/nitrogen oxide, also have novel dissolvent ionic liquid etc.Come into the market with Lyocell fibers prepared by N-methyl-N-morpholine oxide, this solvent is nontoxic and recyclable, in production process without chemical reaction process, pollution-free, industrialization at present.But it also has some shortcomings in process of production: 1) solvent is expensive, and up-trend is obvious; 2) in solvent NMMO, contain nitrogen-oxygen bond, be easy to cause cellulosic degraded; 3) course of dissolution more complicated, power consumption is large; 4) can reach the concentration of homogeneous solution limited, production cost and efficiency are restricted; 5) because spinning temperature is higher, solvent recovery is more difficult, causes suitability for industrialized production slow.U.S. Patent Publication No. is that the patent of invention of US2003157351A1 discloses a kind of method that cellulose dissolves and processes in ionic liquid, with other solvent phase ratios, boiling point is high, non-volatile, exist with liquid state in wider temperature range, having good heat endurance, is the good solvent of many organic matters, inorganic matter and macromolecular material.But ionic liquid is as the same existent defect of cellulose solvent: 1) in the time that cellulose concentration is higher, solution there will be high-viscosity high-elasticity state, causes very large difficulty to processing; 2) while adopting pure imidazole type ion liquid dissolving cellulos, when temperature reaches or during higher than 140 DEG C, is easy to cause cellulosic degraded.
Summary of the invention
In order to solve problems of the prior art, the object of this invention is to provide a kind of cellulose dissolution agent and the application in cellulose dissolution and regeneration thereof.
In order to realize the object of the invention, first the present invention provides a kind of cellulose dissolution agent, and described cellulose dissolution agent is the mixture of ionic liquid and organic solvent;
CATION in described ionic liquid is alkyl imidazole ion and alkyl quaternary ammonium ion;
Described alkyl imidazole ion and alkyl quaternary ammonium ion are as shown in following chemical formula:
Wherein R1, R2, R3, R4, R5 are identical or different, are respectively the one in H, C1-C8 alkyl, vinyl, propenyl, cyclobutenyl, ethoxy;
Anion in described ionic liquid is Cl
-, CH
3cOO
-, CF
3cOO
-, CF
3sO
3 -, BF
4 -, (CF
3sO
2)
3c
-, PF
6 -, (CF
3sO
2)
2n
-in one or more;
Described organic solvent is one or more in DMF, DMA, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
As preferably, the anion in described ionic liquid is CH
3cOO
-.
As preferably, described organic solvent is dimethyl sulfoxide (DMSO).
More preferred, the ratio of described ionic liquid and organic solvent is 4:7; In described ionic liquid, the ratio of alkyl imidazole ion and alkyl quaternary ammonium ion is 1:3.
The present invention also provides a kind of regenerated celulose fibre, and described regenerated celulose fibre prepares by the following method:
Comminuted fibres raw material and aforementioned fibers element lytic agent is evenly mixed, at 30～120 DEG C, dissolve 0.4～10 hour, obtain cellulose concentration and be 4～20% spinning solution; By the deaeration under vacuum of the spinning solution of gained, utilize homemade small wet spinning equipment, by the spinning solution after deaeration from extruding from syringe, after spinning head, enter coagulating bath, by stretching action, collected by gathering-device, through washing, dry supervisor, obtain regenerated celulose fibre.
As preferably, the mixed proportion of comminuted fibres raw material and aforementioned fibers element lytic agent is 1:25～1:5.
As preferably, the aqueous solution that described coagulating bath is ethanol, temperature is 15～20 DEG C.
The present invention also provides the application of aforementioned fibers element lytic agent in cellulose dissolution and regeneration.
The present invention also provides a kind of preparation method of regenerated celulose fibre, and comminuted fibres raw material and aforementioned fibers element lytic agent is evenly mixed, and dissolves 0.4～10 hour at 30～120 DEG C, obtains cellulose concentration and be 4～20% spinning solution; By the deaeration under vacuum of the spinning solution of gained, utilize homemade small wet spinning equipment, by the spinning solution after deaeration from extruding from syringe, after spinning head, enter coagulating bath, by stretching action, collected by gathering-device, through washing, dry supervisor, obtain regenerated celulose fibre.
As preferably, the mixed proportion of comminuted fibres raw material and aforementioned fibers element lytic agent is 1:25～1:5.
Beneficial effect of the present invention is:
Cellulose dissolution agent of the present invention adopts ionic liquid and ORGANIC SOLVENT MIXTURES, is applicable to cellulosic dissolving and the spinning of different component, different molecular weight, and process route and product adjustable range are broader; When cellulose dissolves in cellulose dissolution agent of the present invention, without carrying out the operations such as sulfonation, experienced and maturation, greatly shorten technological process; Cellulose dissolution agent of the present invention, has at a high speed, the advantage such as efficient, nontoxic, pollution-free, low energy consumption, and relatively existing cellulose solvent and dissolving technology have potential superiority; By adjusting the proportioning of ionic liquid and organic solvent, the solvability of adjusting cellulose dissolution agent that can be controlled, for native cellulose and regenerated cellulose, can directly dissolve and have larger solubility fast.
Detailed description of the invention
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
Wood pulp fibre (degree of polymerization DP value is 1050) after pulverizing is joined respectively in the 1-butyl-3-methylimidazole chlorate ([BMIM] Cl) and dimethyl sulfoxide (DMSO) composition that does not add/be added with alkyl quaternary ammonium salts solion.The wood pulp fibre of pulverizing and the ratio of lytic agent are 3:50.
Concrete data are as shown in table 1:
The impact of table 1 alkyl quaternary ammonium salts solion on wood pulp fibre rate of dissolution
Experimental result is as follows:
1, do not add the wood pulp fibre of alkyl quaternary ammonium salts solion, be documented at 90 DEG C and dissolve according to prior art, formed even, stable, transparent spinning solution through 5 hours, the concentration of spinning solution is 6%.Spinning solution carries out wet spinning after filtration, deaeration, and coagulating bath is water, and temperature is 20 DEG C.Draw ratio when spinning is 2, through washing, dry procedure, makes the cellulose fibre that intensity is 6.5cN/dtex.
2, add the wood pulp fibre of alkyl quaternary ammonium salts solion, according to preparation method of the present invention, at 50 DEG C, dissolve, can form even, stable, transparent spinning solution through 1 hour, the concentration of spinning solution is 6%.Spinning solution carries out wet spinning after filtration, deaeration, the aqueous solution that coagulating bath is ethanol, and temperature is 20 DEG C.Draw ratio when spinning is 2, through washing, dry procedure, makes the cellulose fibre that intensity is 7.0cN/dtex.
Visible, cellulose dissolution agent of the present invention, because alkyl quaternary ammonium salts solion adds, makes the dissolving of wood pulp fibre more rapid, and solubility still keeps higher level.
Embodiment 2
Cotton linter (degree of polymerization DP value is 850) after pulverizing is joined respectively in the 1-butyl-3-methylimidazole acetate ([BMIM] Ac) and dimethyl sulfoxide (DMSO) composition that does not add/be added with alkyl quaternary ammonium salts solion.The wood pulp fibre of pulverizing and the ratio of lytic agent are 1:25.Concrete data are as shown in table 2:
The impact of table 2 alkyl quaternary ammonium salts solion on cotton linter rate of dissolution
Experimental result is as follows:
1, do not add the cotton linter of alkyl quaternary ammonium salts solion, be documented at 90 DEG C and dissolve according to prior art, formed even, stable, transparent spinning solution through 4.5 hours, the concentration of spinning solution is 4%.Spinning solution carries out wet spinning after filtration, deaeration, and coagulating bath is water, and temperature is 20 DEG C.Draw ratio when spinning is 2, through washing, dry procedure, makes the cellulose fibre that intensity is 6cN/dtex.
2, add the cotton linter of alkyl quaternary ammonium salts solion, according to preparation method of the present invention, at 50 DEG C, dissolve, can form even, stable, transparent spinning solution through 0.8 hour, the concentration of spinning solution is 4%.Spinning solution carries out wet spinning after filtration, deaeration, the aqueous solution that coagulating bath is ethanol, and temperature is 20 DEG C.Draw ratio when spinning is 2, through washing, dry procedure, makes the cellulose fibre that intensity is 6.8cN/dtex.
Visible, cellulose dissolution agent of the present invention, because alkyl quaternary ammonium salts solion adds, makes the dissolving of cotton linter more rapid, and solubility still keeps higher level.
Embodiment 3
Microcrystalline cellulose (degree of polymerization DP value is 220) after pulverizing is joined respectively in the 1-butyl-3-methylimidazole acetate ([BMIM] Ac) and dimethyl sulfoxide (DMSO) composition that does not add/be added with alkyl quaternary ammonium salts solion.The wood pulp fibre of pulverizing and the ratio of lytic agent are 1:5.Concrete data are as shown in table 3:
The impact of table 3 alkyl quaternary ammonium salts solion on microcrystalline cellulose rate of dissolution
Experimental result is as follows:
1, do not add the microcrystalline cellulose of alkyl quaternary ammonium salts solion, be documented at 90 DEG C and dissolve according to prior art, formed even, stable, transparent spinning solution through 4.5 hours, the concentration of spinning solution is 20%.Spinning solution carries out wet spinning after filtration, deaeration, and coagulating bath is water, and temperature is 20 DEG C.Draw ratio when spinning is 2, through washing, dry procedure, makes the cellulose fibre that intensity is 2.8cN/dtex.
2, add the microcrystalline cellulose of alkyl quaternary ammonium salts solion, according to preparation method of the present invention, at 50 DEG C, dissolve, can form even, stable, transparent spinning solution through 0.5 hour, the concentration of spinning solution is 20%.Spinning solution carries out wet spinning after filtration, deaeration, the aqueous solution that coagulating bath is ethanol, and temperature is 20 DEG C.Draw ratio when spinning is 2, through washing, dry procedure, makes the cellulose fibre that intensity is 3.5cN/dtex.
Visible, cellulose dissolution agent of the present invention, because alkyl quaternary ammonium salts solion adds, makes the dissolving of microcrystalline cellulose more rapid, and solubility still keeps higher level.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. a cellulose dissolution agent, is characterized in that, described cellulose dissolution agent is the mixture of ionic liquid and organic solvent;
CATION in described ionic liquid is alkyl imidazole ion and alkyl quaternary ammonium ion;
Described alkyl imidazole ion and alkyl quaternary ammonium ion are as shown in following chemical formula:
Wherein R1, R2, R3, R4, R5 are identical or different, are respectively the one in H, C1-C8 alkyl, vinyl, propenyl, cyclobutenyl, ethoxy;
Anion in described ionic liquid is Cl
-, CH
3cOO
-, CF
3cOO
-, CF
3sO
3 -, BF
4 -, (CF
3sO
2)
3c
-, PF
6 -, (CF
3sO
2)
2one or more in N-;
Described organic solvent is one or more in DMF, DMA, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO).
2. cellulose dissolution agent according to claim 1, is characterized in that, the anion in described ionic liquid is CH
3cOO
-.
3. cellulose dissolution agent according to claim 1, is characterized in that, described organic solvent is dimethyl sulfoxide (DMSO).
4. according to the cellulose dissolution agent described in claim 1-3 any one, it is characterized in that, the ratio of described ionic liquid and organic solvent is 4:7; In described ionic liquid, the ratio of alkyl imidazole ion and alkyl quaternary ammonium ion is 1:3.
5. a regenerated celulose fibre, is characterized in that, described regenerated celulose fibre prepares by the following method:
Comminuted fibres raw material is evenly mixed with the cellulose dissolution agent described in claim 1-4 any one, at 30～120 DEG C, dissolve 0.4～10 hour, obtain cellulose concentration and be 4～20% spinning solution; By the deaeration under vacuum of the spinning solution of gained, utilize homemade small wet spinning equipment, by the spinning solution after deaeration from extruding from syringe, after spinning head, enter coagulating bath, by stretching action, collected by gathering-device, through washing, dry supervisor, obtain regenerated celulose fibre.
6. regenerated celulose fibre according to claim 5, is characterized in that, the mixed proportion of the cellulose dissolution agent described in comminuted fibres raw material and claim 1-4 any one is 1:25～1:5.
7. regenerated celulose fibre according to claim 5, is characterized in that, the aqueous solution that described coagulating bath is ethanol, and temperature is 15～20 DEG C.
8. the application of the cellulose dissolution agent described in claim 1-4 any one in cellulose dissolution and regeneration.
9. the preparation method of regenerated celulose fibre described in claim 5, it is characterized in that, comminuted fibres raw material is evenly mixed with the cellulose dissolution agent described in claim 1-4 any one, at 30～120 DEG C, dissolve 0.4～10 hour, obtain cellulose concentration and be 4～20% spinning solution; By the deaeration under vacuum of the spinning solution of gained, utilize homemade small wet spinning equipment, by the spinning solution after deaeration from extruding from syringe, after spinning head, enter coagulating bath, by stretching action, collected by gathering-device, through washing, dry supervisor, obtain regenerated celulose fibre.
10. preparation method according to claim 9, is characterized in that, the mixed proportion of the cellulose dissolution agent described in comminuted fibres raw material and claim 1-4 any one is 1:25～1:5.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788691A (en) * | 2015-03-24 | 2015-07-22 | 北京林业大学 | Cellulose dissolving agent and application of cellulose dissolving agent in aspect of cellulose esterification modification |
| CN105113035A (en) * | 2015-08-06 | 2015-12-02 | 北京林业大学 | Regenerated fiber and preparing method thereof |
| CN106283239A (en) * | 2016-08-09 | 2017-01-04 | 东华大学 | A kind of concentration cellulose element spinning liquid spinning technique |
| CN106283245A (en) * | 2016-08-09 | 2017-01-04 | 东华大学 | A kind of spinning technique of small molecule liquid crystal modified cellulose fibre |
| CN106609401A (en) * | 2016-11-10 | 2017-05-03 | 北京林业大学 | Flexible fiber having flame retardancy and preparation method thereof |
| CN109627216A (en) * | 2018-12-26 | 2019-04-16 | 陕西科技大学 | A kind of chlorination 1- aminoacyl methyl -3- vinyl iminazole ionic liquid and preparation method thereof |
| CN109851820A (en) * | 2019-01-23 | 2019-06-07 | 杜润宇 | A kind of dissolving method of cellulose |
| CN114082218A (en) * | 2021-12-03 | 2022-02-25 | 齐鲁工业大学 | Preparation and application of controllable and selective lignin extraction switch type eutectic solvent |
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|---|---|---|---|---|
| CN101240085A (en) * | 2007-02-08 | 2008-08-13 | 中国纺织科学研究院 | Cellulose solution and preparation thereof thereof |
| CN101654522A (en) * | 2009-09-08 | 2010-02-24 | 中国科学院过程工程研究所 | Anti-degradable solvent for dissolving cellulose and preparation method of spinning dope thereof |
-
2014
- 2014-05-22 CN CN201410220133.XA patent/CN104047067B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240085A (en) * | 2007-02-08 | 2008-08-13 | 中国纺织科学研究院 | Cellulose solution and preparation thereof thereof |
| CN101654522A (en) * | 2009-09-08 | 2010-02-24 | 中国科学院过程工程研究所 | Anti-degradable solvent for dissolving cellulose and preparation method of spinning dope thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788691A (en) * | 2015-03-24 | 2015-07-22 | 北京林业大学 | Cellulose dissolving agent and application of cellulose dissolving agent in aspect of cellulose esterification modification |
| CN105113035A (en) * | 2015-08-06 | 2015-12-02 | 北京林业大学 | Regenerated fiber and preparing method thereof |
| CN106283239A (en) * | 2016-08-09 | 2017-01-04 | 东华大学 | A kind of concentration cellulose element spinning liquid spinning technique |
| CN106283245A (en) * | 2016-08-09 | 2017-01-04 | 东华大学 | A kind of spinning technique of small molecule liquid crystal modified cellulose fibre |
| CN106609401A (en) * | 2016-11-10 | 2017-05-03 | 北京林业大学 | Flexible fiber having flame retardancy and preparation method thereof |
| CN106609401B (en) * | 2016-11-10 | 2018-12-04 | 北京林业大学 | A kind of flexible fiber and preparation method thereof with flame retardant property |
| CN109627216A (en) * | 2018-12-26 | 2019-04-16 | 陕西科技大学 | A kind of chlorination 1- aminoacyl methyl -3- vinyl iminazole ionic liquid and preparation method thereof |
| CN109851820A (en) * | 2019-01-23 | 2019-06-07 | 杜润宇 | A kind of dissolving method of cellulose |
| CN114082218A (en) * | 2021-12-03 | 2022-02-25 | 齐鲁工业大学 | Preparation and application of controllable and selective lignin extraction switch type eutectic solvent |
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| CN104047067B (en) | 2016-05-11 |
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