CN101220522B - Method for manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine - Google Patents
Method for manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine Download PDFInfo
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- CN101220522B CN101220522B CN200810033109XA CN200810033109A CN101220522B CN 101220522 B CN101220522 B CN 101220522B CN 200810033109X A CN200810033109X A CN 200810033109XA CN 200810033109 A CN200810033109 A CN 200810033109A CN 101220522 B CN101220522 B CN 101220522B
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Abstract
The invention relates to a method for using a double screw extruder to prepare celluloses/ionic liquids spinning solution and the preparation comprises that the celluloses are uniformly mixed with the ionic liquids according to the weight ratio of 5:95 to 25:75, and then the mixture is put into the double screw extruder which has two vacuum orifices and the screw length diameter ratio of which is 36:1 to 60:1, the control range of temperature is 40 to 120 DEG C, and the light brown and transparent celluloses/ionic liquids spinning solution is formed after strongly mixing and dissolving for 8 to 40 minutes and vacuum dehydration; the obtained celluloses/ionic liquids spinning solution is supercharged by a booster pump and sprayed from a spinneret after coming into a metering pump by a pre-filter, and then cellulose fibers are formed by a plurality of steps such as solidification, washing, cutting and drying, etc. The invention not only shortens the dissolution time of the celluloses but also leads to the more fully mixing and dissolving of materials, and achieves the purposes of energy-saving, high efficiency, decreasing degradation and improving the quality of spinning original solution, so the industrialization becomes easier.
Description
Technical field
The invention belongs to the preparation field of cellulose solution, particularly relate to a kind of method with manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine.
Background technology
But cellulose is the natural polymer child resource of renewable natural degradation the abundantest on the earth, and it is widely used in industrial circles such as fiber, papermaking, film, coating.According to estimates, nature can produce several hundred billion tons cellulose by photosynthesis every year, but has only about 6,000,000,000 tons cellulose to be used by people.Therefore, along with the exhaustion day by day of non-renewable resources such as oil, natural gas and the pay attention to day by day of various countries' environmental pollution problem, the development and application of cellulosic material has become one of focus of countries in the world research.But because cellulose has the labyrinth of crystal region and amorphous area coexistence, and reaches intermolecular strong hydrogen bond action in the molecule, make cellulose be difficult to be dissolved in the common solvent, this becomes the biggest obstacle in the cellulose application and development.Therefore, the active solvent system of developing direct dissolving cellulos has great importance.In recent years, the more cellulosic direct solvent of research has paraformaldehyde/dimethyl sulfoxide (DMSO) (PF/DMSO), lithium chloride/dimethylacetylamide (LiCl/DMAc), N-methylmorpholine-N-oxide monohydrate (NMMOH
2O) and alkali metal hydroxide system etc., wherein, with NMMOH
2O be solvent produce cellulose fibre---Lyocell has realized suitability for industrialized production in countries such as Britain, the U.S., Austria and China.
In recent years, a kind of novel green solvent---ionic liquid has caused the great attention of countries in the world as cellulosic direct solvent system.Ionic liquid is the abbreviation of ionic liquid at room temperature, it be by certain cationic and anion constitute in room temperature or be bordering on the material that is in a liquid state under the room temperature, has strong polarity, non-volatile, not oxidation, fine solubility energy and to good characteristics such as most stable reagents, and as cellulosic solvent, need not activate during dissolving cellulos, and ionic liquid is easy to reclaim, and can be recycled, and this has opened up a new road for the development and use of native cellulose.
In recent years, for ion liquid dissolving and processing of cellulose carried out many research and development both at home and abroad, and formed many patents.As: US2003157351, WO2007101812, CA2532989, US2003157351, WO2006108861, WO2007049485, WO2007057235, CN1596282, CN101007853, CN1818160, CN1804161, CN1261496, CN1844214, CN1851063 etc. disclose the method for using the ion liquid dissolving cellulose and preparing cellulose fibre.In the above-mentioned patent, mostly adopt methods such as common heating, pressurization or microwave radiation to come dissolving cellulos, but the complicated operation that these methods have, what have is batch process, dissolved efficiency is low, is unfavorable for the enforcement of industrialization.
Summary of the invention
The problem to be solved in the present invention provides a kind of method with manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine, this method has not only shortened cellulosic dissolution time, and make material mixing, the dissolving more abundant, can reach energy-conservation, efficient, reduce the purpose of degrading, improving the spinning solution quality, be a kind of cellulose spinning liquid and preparation method thereof that is easy to industrialization.
Method with manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine of the present invention comprises:
Cellulose is evenly mixed with 5: 95～25: 75 weight ratio with ionic liquid, form flaxen pastel, then with in the formed pastel feeding double screw extruder, temperature controlling range is 40～120 ℃, strong agitation dissolving and vacuum dehydration through 8～40min can generate the transparent cellulose/ion liquid spinning solution of light brown.
Described cellulose is selected from one or more in wood pulp, cotton pulp, bamboo pulp, the paper pulp.
Described ionic liquid is made up of CATION and anion, and wherein, anion is Cl
-Or CH
3COO
-In a kind of; CATION is the alkyl imidazole ion, and its structural formula is as follows:
Wherein, R1 and R2 are identical or different, are in the alkyl of C1～C8, vinyl, propenyl, the cyclobutenyl one or more.
Described double screw extruder is that the rotary-type in the same way double screw extruder of general high speed is done following transformation: (1) increases by 2 vacuum orifices; (2) screw slenderness ratio is increased to 36: 1～60: 1.Utilize material unidirectional delivery between two screw rods of co-rotating twin screw to finish the intensification (making temperature reach the control temperature) of material, carry, fully mix and deaeration.And utilize its self-cleaning ability, the plunger type that reaches material flows.Because material alternately flows in the screw channel of two screw rods, material has obtained sufficient stirring and has mixed.The increase of screw slenderness ratio can make material can have more opportunity to mix, dissolve and dewater.And in this mixed process,, dissolve acceleration thereby can make because its surface is brought in constant renewal in, and discharge volatile substances or steam in the material, improve the quality of solution.
In order fully to be dewatered and to be dissolved uniform spinning solution, the vacuum ranges of described double screw extruder is-0.05～-0.10Mpa, the range of speeds of screw rod is 10～100r/min, and the cross-head intensity of pressure will be controlled at 0.2～9.8MPa, to guarantee the quality of spinning solution.
A kind of application of the present invention with manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine, step comprises:
The cellulose/ion liquid spinning liquid that aforementioned light brown is transparent through the booster pump supercharging, is sprayed by spinning head after prefilter enters measuring pump again, through operations such as supersolidification, washing, cut-out, dryings, can obtain cellulose fibre.
Beneficial effect of the present invention:
(1) the present invention is a kind of preparation method that can obtain dissolving uniform fibers element/ion liquid spinning liquid who is easy to industrialization, this method is on the basis that utilizes existing double screw extruder dissolving technology, increase the twin-screw that major diameter when increases vacuum orifice by adopting, not only shortened cellulosic dissolution time greatly, save the energy, reduced cost, and make the technology can be continuous, and device be also very simple, is easy to industrialization;
(2) the present invention the more important thing is make that cellulose substances is mixed fully in twin-screw, dissolution strengthens, the gained spinning solution is even, meet spinning requirement, in addition, because the time that cellulose and ionic liquid stop in screw rod is shorter, can avoid or reduce cellulosic signs of degradation, help making the good fiber product of mechanical property;
(3) because cellulose is dissolved as direct dissolving in ionic liquid, do not need other operation, and ionic liquid is nontoxic, non-volatility, rate of recovery height, so dissolution process is simple, environmental friendliness.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The cellulose cotton pulp is evenly mixed with 10: 90 weight ratio with ionic liquid [BMIM] Cl (1-butyl-3-methyl-imidazoles chlorate), form flaxen pastel, then formed pastel is fed continuously and have 2 vacuum orifices, screw slenderness ratio is 48: 1, temperature is in 100 ℃ the double screw extruder, vacuum is-0.10MPa, the rotating speed of screw rod is 20r/min, the intensity of pressure of cross-head (being the exit) is controlled at 1MPa, strong agitation dissolving and vacuum dehydration through 40min, can obtain amber transparent and uniform spinning solution, it zero is cut viscosity and can reach 5487Pas, the good spinning property of solution, can obtain fiber number by dry-wet spinning is 2.22dtex, and fracture strength is the cellulose fibre of 4.09cN/dtex.
Embodiment 2
The cellulose wood pulp is evenly mixed with 8: 92 weight ratio with ionic liquid [EMIM] Ac (1-ethyl-3-methyl-imidazoles acetate), form flaxen pastel, then formed pastel is fed continuously and have 2 vacuum orifices, screw slenderness ratio is 48: 1, temperature is in 50 ℃ the dual-screw-stem machine, vacuum is-0.06MPa, the rotating speed of screw rod is 50r/min, the intensity of pressure of cross-head (being the exit) is controlled at 4MPa, strong agitation dissolving and vacuum dehydration through 15min, can obtain amber transparent even spinning solution, it zero is cut viscosity and can reach 4525Pas, the good spinning property of solution, can obtain fiber number by dry-wet spinning is 2.43dtex, and fracture strength is the cellulose fibre of 3.68cN/dtex.
Claims (4)
1. method with manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine comprises:
Cellulose is evenly mixed with 5: 95～25: 75 weight ratio with ionic liquid, 2 vacuum orifices, screw slenderness ratio are arranged is in 36: 1～60: 1 the rotary-type in the same way double screw extruder in feeding then, temperature controlling range is 40～120 ℃, strong agitation dissolving and vacuum dehydration through 8～40min generate cellulose/ion liquid spinning liquid.
2. the method with manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine according to claim 1, it is characterized in that: described cellulose is selected from one or more in wood pulp, cotton pulp, bamboo pulp, the paper pulp.
3. the method with manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine according to claim 1, it is characterized in that: described ionic liquid is made up of CATION and anion, and wherein, anion is Cl
-Or CH
3COO
-In a kind of; CATION is the alkyl imidazole ion, and its structural formula is as follows:
Wherein, R1 and R2 are identical or different, are in the alkyl, vinyl, propenyl, cyclobutenyl of C1～C8 one or more.
4. the method with manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine according to claim 1, it is characterized in that: the vacuum ranges of described double screw extruder is-0.05～-0.10Mpa, the range of speeds of screw rod is 10～100r/min, and the cross-head intensity of pressure will be controlled at 0.2～9.8MPa.
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| CN200810033109XA CN101220522B (en) | 2008-01-25 | 2008-01-25 | Method for manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine |
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|---|---|---|---|
| CN200810033109XA CN101220522B (en) | 2008-01-25 | 2008-01-25 | Method for manufacturing cellulose/ion liquid spinning liquid with double-screw extrusion machine |
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| CN101220522A CN101220522A (en) | 2008-07-16 |
| CN101220522B true CN101220522B (en) | 2011-02-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978737A (en) * | 2012-11-28 | 2013-03-20 | 东华大学 | Method for preparing blend fibers of celluloses and high-fluidity elastomers |
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| CN101768239B (en) * | 2008-12-31 | 2012-02-08 | 金发科技股份有限公司 | Preparation method and polymerization equipment of acrylonitrile base carbon fiber spinning solution |
| 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 |
| CN101580966B (en) * | 2009-06-17 | 2012-05-23 | 东华大学 | Chinlon 6 melt spinning method with ionic liquid as plasticiser |
| CN101974789B (en) * | 2010-11-04 | 2012-05-02 | 滁州友林科技发展有限公司 | Twin-screw extruder pressurizing system used for blended spinning |
| CN102358957B (en) * | 2011-08-24 | 2015-01-07 | 中国纺织科学研究院 | Method for preparing cellulose spinning stock solution |
| CN103147145A (en) * | 2013-03-20 | 2013-06-12 | 天津工业大学 | Method for preparing modified cellulose fire-retardant fiber through reaction extrusion |
| TWI615516B (en) * | 2014-12-04 | 2018-02-21 | 財團法人紡織產業綜合研究所 | Preparation method of fiber and spinning viscose |
| CN105088371B (en) * | 2015-07-21 | 2017-11-03 | 河南工程学院 | It is a kind of can high drafting melt-spun aliphatic polyamide fiber preparation method |
| CN110172746B (en) * | 2019-05-30 | 2020-07-28 | 当阳市鸿阳新材料科技有限公司 | Method for preparing lyocell fibers by dissolving cellulose in solvent |
| CN116446209A (en) * | 2023-04-27 | 2023-07-18 | 恒天重工股份有限公司 | Swelling method and equipment for cellulose fiber pulp by ionic liquid method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978737A (en) * | 2012-11-28 | 2013-03-20 | 东华大学 | Method for preparing blend fibers of celluloses and high-fluidity elastomers |
| CN102978737B (en) * | 2012-11-28 | 2014-10-15 | 东华大学 | Method for preparing blend fibers of celluloses and high-fluidity elastomers |
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