CN101381479A - Method for synthesizing alkaline soluble glycol cellulose for spinning/membrane manufacturing - Google Patents
Method for synthesizing alkaline soluble glycol cellulose for spinning/membrane manufacturing Download PDFInfo
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- CN101381479A CN101381479A CNA2007100456692A CN200710045669A CN101381479A CN 101381479 A CN101381479 A CN 101381479A CN A2007100456692 A CNA2007100456692 A CN A2007100456692A CN 200710045669 A CN200710045669 A CN 200710045669A CN 101381479 A CN101381479 A CN 101381479A
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Abstract
The invention discloses a method for synthesizing alkaline-soluble hydroxyethyl cellulose for spinning/film-making, wherein cellulose raw materials such as cotton linter and so on undergo alkaline leaching, squeezing and crushing treatment to obtain solid alkali cellulose; the solid alkali cellulose directly contacts a gaseous etherifying agent such as ethylene oxide and so on for gas-solid phase etherifying reaction; the etherification degree of the alkali cellulose is controlled, so as to synthesize alkaline-soluble hydroxyethyl cellulose etherifying products which can not be dissolved into water but can be dissolved into a diluted alkaline solution; and the alkaline-soluble hydroxyethyl cellulose etherifying products are dissolved into the diluted alkaline solution to form a stock solution of the hydroxyethyl cellulose for spinning/film-making. The stock solution of the hydroxyethyl cellulose for spinning/film-making has good film-forming property and fiber-forming property. The method has the advantages of short technological flow, simple operation, no pollution, mild reaction condition, small cellulose degradation, small amount of ethylene oxide, no addition of an organic solvent as a diluent, and high product purity, and is favorable for improving the mechanical property of fiber or a film.
Description
Technical field
The present invention relates to a kind of method of synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing, specifically solid base Mierocrystalline cellulose and gasiform etherifying agent oxyethane are carried out gas-solid mutually etherification reaction prepare water insoluble and be dissolved in the method for the Natvosol of diluted alkaline.
Background technology
Plant cellulose is a kind of natural high molecular polymer, is the organic polymer of the abundantest natural formation of originating, and renewable and biodegradable.Because the crystallization and the unformed form of complexity in the fiber, a large amount of hydrogen bonds and very high molecular weight, also are insoluble to many solvents at neither fusion of Mierocrystalline cellulose, and make Mierocrystalline cellulose be far from being fully utilized, therefore, any dissolving method effectively, simply or fast is all significant.
At present, main regenerated cellulose product substantially all adopts traditional adhering process, be with behind the dipping of Mierocrystalline cellulose with 18% sodium hydroxide, generate cellulose sulfonate with the dithiocarbonic anhydride effect, after forming viscose with the diluted alkaline dissolving again, carry out wet-spinning and make viscose fiber or curtain coating formation glassine paper.This method discharges a large amount of poisonous CS in process of production
2And H
2S gas not only damages HUMAN HEALTH, and serious environment pollution.
In recent years, novel solvent N-methyl oxidation beautiful jade (MMNO) occurred, and be acknowledged as the most promising cellosolve.Germany Akzo Nobel company at first obtains its cellulosic fibre solvent-spinning method patent, and obtains 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, oneself comes into the market existing in the world a small amount of Lyocell fiber, but owing to it costs an arm and a leg, spinning temperature is higher, the suitability for industrialized production slower development.
Chinese patent ZL0011485.5 uses the 6wt%Na0H/4wt% aqueous solution of urea as the Mierocrystalline cellulose novel solvent, and successfully prepares the regenerated cellulose film of good strength.But this solvent system must mix with Mierocrystalline cellulose and freezing 3～5 hours ability dissolving cellulos prepare transparent Mierocrystalline cellulose strong solution, therefore, is difficult to realize industrialization.
Chinese patent ZL200310111567.8 discloses a kind of lithium hydroxide with 3.0～7.0wt%, 4.0 the aqueous solution of the urea of～30.0wt% as novel solvent, prepares the method for regenerated cellulose fiber and film by freeze-thaw method or direct dissolving method dissolving cellulos.This dissolving method soluble polymeric degree is up to 2300 natural cellulose and regenerated cellulose, but the Mierocrystalline cellulose solid content of spinning that this method makes or system pleurodiaphragmatic in terspace liquid is lower, generally below 5%, is unfavorable for improving the efficient of industrialization.
Therefore, developing pollution-free, simple, fast and efficient cellulose dissolution novel method, is the key that Mierocrystalline cellulose can be fully utilized, and also is Mierocrystalline cellulose application and development direction.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of alkaline soluble glycol cellulose for spinning/membrane manufacturing.This synthetic method craft flow process is short, simple to operate, pollution-free, reaction conditions is gentle, and the solubleness of etherificate product in dilute alkaline soln is higher.
For achieving the above object, technical scheme provided by the invention is:
The method of synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing, be with cellulosic materials such as linterss after alkali steeping, squeezing, pulverization process, the solid base Mierocrystalline cellulose that obtains directly contacts with gasiform etherifying agent oxyethane etc., carry out gas-solid phase etherification reaction, control its degree of etherification, synthetic water insoluble and can be dissolved in alkaline soluble glycol cellulose etherificate product in the dilute alkaline soln, this alkaline soluble glycol cellulose etherificate product is dissolved in and forms spinning or system film Natvosol stoste in the dilute alkaline soln.This spinning or system film Natvosol stoste have good film forming, fibre-forming performance.
The above-mentioned Mierocrystalline cellulose that is used for alkali steeping can be natural cellulose or regenerated cellulose, and natural cellulose includes but not limited to cotton linter pulp, straw fiber slurry, bagasse pulp, soft wood pulp, hard wood pulp etc.Regenerated cellulose includes but not limited to cellulosic nonwoven fabric, glassine paper, viscose yarn etc.
The described cellulosic polymerization degree is preferably in 400～2300 scopes in 200～5000 scopes.
The cellulosic press ratio of above-mentioned solid base (mass ratio of solid base Mierocrystalline cellulose and cellulosic material) is 2.0～4.0, is preferably between 2.5～3.5.
The consumption of above-mentioned etherifying agent oxyethane is 5～75wt% of cellulose amount, is preferably 15～50wt%.
Above-mentioned gas-solid phase etherification reaction temperature is preferably in 30～60 ℃ of scopes between 20～70 ℃.
The above-mentioned gas-solid phase etherification reaction time is between 40～180 minutes, is preferably between 60～120 minutes.
In the above-mentioned alkali steeping process, employed alkali is aqueous sodium hydroxide solution.
Above-mentioned is dissolved in the spinning that forms in the dilute alkaline soln or makes film hydroxy ethyl fiber cellulose solution, and its solid content is 4～12%, is preferably in 6～10%.
The above-mentioned dilute alkaline soln that is used for directly dissolving alkaline soluble glycol cellulose etherificate product is a diluted sodium hydroxide solution.
The percentage concentration of described diluted sodium hydroxide solution is 2～10%, is preferably 4～8%, to form transparent hydroxy ethyl fiber cellulose solution.
, between 0.15～0.75, be preferably between 0.2～0.5 by aforesaid method synthetic hydroxyethyl ether cellulose degree (MS).
Mierocrystalline cellulose etherificate degree measuring method of the present invention is: at first reaction raw materials Mierocrystalline cellulose and reaction product Natvosol are obtained acetic acid Mierocrystalline cellulose and acetic acid Natvosol through the acetic acid esterification respectively, be dissolved in CDCl then
3, adopt nucleus magnetic resonance
1After the H spectrum obtains spectrogram, after swarming is handled,, go out degree of etherification (MS): MS=(9/4) * (I by the following formula quantitative Analysis by the intensity at integral and calculating proton resonance peak
1/ I
2), in the formula, 9/4: the ratio of proton number in onychostroma subnumber and the oxygen ethylidene in the methyl in the ethanoyl on each glucose ring; I
1: oxygen ethylidene proton structure exists in the replacement chain
1The resonance peak intensity at 3.71ppm and 4.20ppm place on the H spectrogram; I
2: the methyl proton structure exists in the ethanoyl
1The resonance peak intensity at 1.90ppm and 2.10ppm place on the H spectrogram.
The alkaline soluble glycol cellulose of the present invention preparation can directly dissolve and enters spinning or film formation process is made various regenerated fibre cellulose products, as hydroxyethyl cellulose, glassine paper, cellulose blending matrix material etc.Especially the certain degree of etherification alkaline soluble glycol cellulose of synthetic of the present invention, the natural cellulose of solubilized high-polymerization degree and regenerated cellulose, and the Mierocrystalline cellulose solid content in the spinning/membrane manufacturing stoste is increased substantially, therefore, have purposes and industrialization prospect widely.
Compared with the prior art, the present invention has significant technical progress: (1) present method and traditional adhering process are essentially different, got rid of long-term a large amount of dithiocarbonic anhydride that uses, and can handle the high-polymerization degree cellulosic material and carry out the cellulose dissolution of high density, have that technical process is short, simple to operate, pollution-free, the advantage of high-speed and high-efficiency.(2) adopt the synthetic alkaline soluble glycol cellulose of gas-solid phase etherification reaction, make Natvosol, do not need to use organic thinner, saved the recovery technology and the relevant device of thinner with respect to liquid phase method; The add-on of this method oxyethane seldom, ethylene glycol or multicondensed ethylene glycol that side reaction produces increase seldom, and it exists the alkali dissolution to its postorder not influence, the etherificate product can not separate and directly enters dissolution process; (4) compare with Mierocrystalline cellulose novel solvent system, cost reduces greatly, and dissolved efficiency also increases substantially.The present invention can adopt brief technology, and is pollution-free, prepare the spinning/membrane manufacturing stoste of high-polymerization degree, high solids content efficiently, apace, has wide industrialization prospect.
Description of drawings
Fig. 1 is the process flow sheet of the synthetic method of alkaline soluble glycol cellulose for spinning/membrane manufacturing of the present invention.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
The different etherification reaction conditions that 200 gram soda cellulose powder are listed by subordinate list 1 are synthesized the etherificate product that obtains respectively, take out in the Glacial acetic acid that 100 grams are 10wt% with concentration and free alkali, filtering the back uses deionized water and dehydrated alcohol repetitive scrubbing filter cake to PH=7.0, again 60 ℃ of following vacuum-dryings 24 hours, after the pulverizing, measure its degree of etherification and solubility property.Remaining etherificate product 6% diluted sodium hydroxide solution dissolves the stoste that is mixed with different Mierocrystalline cellulose solid contents down at 0 ℃, and the result also lists in the subordinate list 1.
As seen, adopt method provided by the invention, alkaline soluble glycol cellulose that can synthetic-highly polymerized degree and can prepare the spinning/membrane manufacturing stoste of high solids content, technology very simply, at a high speed, high and pollution-free, have very wide industrialization prospect.
Claims (23)
1. the method for a synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing, it is characterized in that: with cellulosic materials such as linterss after alkali steeping, squeezing, pulverization process, the solid base Mierocrystalline cellulose that obtains directly contacts with gasiform etherifying agent oxyethane, carry out gas-solid phase etherification reaction, control its degree of etherification, synthetic water insoluble and can be dissolved in alkaline soluble glycol cellulose etherificate product in the dilute alkaline soln, this alkaline soluble glycol cellulose etherificate product is dissolved in and forms spinning or system film Natvosol stoste in the dilute alkaline soln.
2. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1, it is characterized in that: the described Mierocrystalline cellulose that is used for alkali steeping is natural cellulose or regenerated cellulose.
3, the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 2 is characterized in that: described natural cellulose includes but not limited to cotton linter pulp, straw fiber slurry, bagasse pulp, soft wood pulp, hard wood pulp.
4. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 2, it is characterized in that: described regenerated cellulose includes but not limited to cellulosic nonwoven fabric, glassine paper, viscose yarn.
5. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1, it is characterized in that: the cellulosic degree of polymerization of described cellulosic material is 200～5000.
6. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1, it is characterized in that: the cellulosic degree of polymerization of described cellulosic material is 400～2300.
7. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1, it is characterized in that: the mass ratio of described solid base Mierocrystalline cellulose and cellulosic material is 2.0～4.0.
8. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1, it is characterized in that: the mass ratio of described solid base Mierocrystalline cellulose and cellulosic material is 2.5～3.5.
9. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1, it is characterized in that: the consumption of described etherifying agent oxyethane is 5～75wt% of cellulose amount.
10. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1, it is characterized in that: the consumption of described etherifying agent oxyethane is 15～50wt% of cellulose amount.
11. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1 is characterized in that: described gas-solid phase etherification reaction temperature is between 20～70 ℃.
12. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1 is characterized in that: described gas-solid phase etherification reaction temperature is between 30～60 ℃.
13. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1 is characterized in that: the described gas-solid phase etherification reaction time is 40～180 minutes.
14. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1 is characterized in that: the described gas-solid phase etherification reaction time is 60～120 minutes.
15. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1 is characterized in that: in the alkali steeping process, employed alkali is aqueous sodium hydroxide solution.
16. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1 is characterized in that: described spinning or the system film hydroxy ethyl fiber cellulose solution that forms in the dilute alkaline soln that be dissolved in, its solid content is 4～12%.
17. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1 is characterized in that: described spinning or the system film hydroxy ethyl fiber cellulose solution that forms in the dilute alkaline soln that be dissolved in, its solid content is 6～10%.
18. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1 is characterized in that: the described dilute alkaline soln that is used for directly dissolving alkaline soluble glycol cellulose etherificate product is a diluted sodium hydroxide solution.
19. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 18 is characterized in that: the percentage concentration of described diluted sodium hydroxide solution is 2～10%.
20. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 18 is characterized in that: the percentage concentration of described diluted sodium hydroxide solution is 4～8%.
21. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1 is characterized in that: described hydroxyethyl ether cellulose degree MS is between 0.15～0.75.
22. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1 is characterized in that: described hydroxyethyl ether cellulose degree MS 0.2～) between the .5.
23. the method for synthetic alkaline soluble glycol cellulose for spinning/membrane manufacturing according to claim 1 is characterized in that: described spinning or system film Natvosol stoste directly enter spinning or film formation process.
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| CNA2007100456692A CN101381479A (en) | 2007-09-06 | 2007-09-06 | Method for synthesizing alkaline soluble glycol cellulose for spinning/membrane manufacturing |
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| CNA2007100456692A CN101381479A (en) | 2007-09-06 | 2007-09-06 | Method for synthesizing alkaline soluble glycol cellulose for spinning/membrane manufacturing |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101871129A (en) * | 2009-04-27 | 2010-10-27 | 盐城市兰邦工业纤维有限公司 | Preparation method of alkali-soluble hydroxyethylcellulose fiber spinning solution with high solid content |
| CN102926015A (en) * | 2012-11-20 | 2013-02-13 | 东华大学 | Method for preparing hydroxyethyl cellulose fibers by adopting pre-gel method |
| CN105070865A (en) * | 2015-07-10 | 2015-11-18 | 长兴东方红包装有限公司 | Polyethylene diaphragm for lithium ion battery and preparation method of polyethylene diaphragm |
| CN106519043A (en) * | 2016-11-19 | 2017-03-22 | 王芹 | Cellulose ether production technology |
| CN110551301A (en) * | 2018-05-30 | 2019-12-10 | 华南理工大学 | Water-resistant nano cellulose film and preparation method thereof |
-
2007
- 2007-09-06 CN CNA2007100456692A patent/CN101381479A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101871129A (en) * | 2009-04-27 | 2010-10-27 | 盐城市兰邦工业纤维有限公司 | Preparation method of alkali-soluble hydroxyethylcellulose fiber spinning solution with high solid content |
| CN102926015A (en) * | 2012-11-20 | 2013-02-13 | 东华大学 | Method for preparing hydroxyethyl cellulose fibers by adopting pre-gel method |
| CN102926015B (en) * | 2012-11-20 | 2015-04-08 | 东华大学 | Method for preparing hydroxyethyl cellulose fibers by adopting pre-gel method |
| CN105070865A (en) * | 2015-07-10 | 2015-11-18 | 长兴东方红包装有限公司 | Polyethylene diaphragm for lithium ion battery and preparation method of polyethylene diaphragm |
| CN106519043A (en) * | 2016-11-19 | 2017-03-22 | 王芹 | Cellulose ether production technology |
| CN106519043B (en) * | 2016-11-19 | 2019-06-07 | 山东洲星生物技术有限公司 | A kind of production technology of cellulose ether |
| CN110551301A (en) * | 2018-05-30 | 2019-12-10 | 华南理工大学 | Water-resistant nano cellulose film and preparation method thereof |
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Open date: 20090311 |