CN102965752A - Cellulose in-situ urea modified plastification melt spinning method - Google Patents
Cellulose in-situ urea modified plastification melt spinning method Download PDFInfo
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- CN102965752A CN102965752A CN2012104965989A CN201210496598A CN102965752A CN 102965752 A CN102965752 A CN 102965752A CN 2012104965989 A CN2012104965989 A CN 2012104965989A CN 201210496598 A CN201210496598 A CN 201210496598A CN 102965752 A CN102965752 A CN 102965752A
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Abstract
The invention relates to a cellulose in-situ urea modified plastification melt spinning method comprising the following steps of: (1) drying the cellulose and the urea under a vacuum condition; (2) uniformly mixing 10-20wt% of cellulose, 50-70wt% of ionic liquid and 10-40wt% of urea; (3) extruding the mixture by a co-rotating twin screw extruder, defoaming, filtering and ejecting from a spinneret port; (4) drawing and coiling the quickly solidified fiber to form cellulose fiber. The method can be used for get the cellulose grafted copolymer which is easy to process, high-efficiency, green and clean, and can prompt development of the novel cellulose fiber which is low in energy consumption, economical, practical and environmentally-friendly.
Description
Technical field
The invention belongs to cellulosic derivatization modification and high-temperature fusion spinning field thereof, particularly the urea-modified plasticized melt spinning method of a kind of cellulose original position.
Background technology
Cellulose extensively derives from nature, such as fiber crops, straw, straw etc.Owing on each glucose cell rings of cellulose two secondary hydroxyls and a primary hydroxyl are arranged, be easy to form in the molecule and intermolecular hydrogen bonding, degree of crystallinity is very high, so cellulose is difficult to be dissolved in the general inorganic and organic solvent, needs to adopt special solvent or will just be convenient to processing and utilization after its derivatization modification.Cellulose-derivedization mainly comprises esterification, etherificate and graft copolymerization etc.Wherein, cellulose and urea reaction generate cellulose carbamate, process is comparatively simple, good spinning property, environmental pollution is little, cellulose carbamate has the advantages such as hygroscopicity, gas permeability, antistatic behaviour, easy dyeing, spinnability, degradability, has a wide range of applications in fields such as weaving, health care, articles for daily use.
As far back as 1938, just there is research to find that the cellulose carbamate that adopts cellulose and urea reaction to synthesize can be dissolved in usual vehicle, after this, all carried out a large amount of research both at home and abroad.Yet, it is very slow that progress is produced in the industrialization of China's cellulose carbamate fibre, main cause is that present China adopts wet spinning process to prepare cellulose carbamate fibre mostly, and cellulose carbamate solution viscosity is lower, and spinnability is not as viscose solution.In recent years, China scientific research personnel mainly selects liquefied ammonia, supercritical carbon dioxide, and DMF, DMA etc. are as cellulose and urea reaction medium.For above-mentioned various solvents, along with investigative technique reaches its maturity, ionic liquid will be their ideal substitute.Ionic liquid tasteless, pollution-free, nonflammable, easily and product separation, easily the advantage such as reclaim, can repeated multiple timesly recycle, ionic liquid generally can not form steam, even so at high temperature also can not produce pernicious gas, be eco-friendly green solvent.Common ionic liquid is mainly by alkyl pyridine or di-alkyl-imidazole quaternary ammonium cation and BF
4 -, PF
6 -, NO
3 -, X
-Form Deng anion.
If adopt the high-temperature fusant spin processes, by selecting suitable extrusion temperature and screw speed, can control suitable spinning viscosity, and cellulose derivative melt spinning use melt-spun equipment commonly used, do not need spinning equipment is improved especially.Behind the derivative reaction, import submissiveer alkane chain in cellulosic backbone, can make the cellulose melting point depression of not melting, improve cellulosic flowability, realize melt spinning.This spinning technique both can improve spinning speed, and the fault of construction of fiber has also reduced the pollution to environment after the minimizing fibroblast, and resulting cellulose derivative fibres has good mechanical performance.
Summary of the invention
Technical problem to be solved by this invention provides the urea-modified plasticized melt spinning method of a kind of cellulose original position, and the method can obtain to be easy to the cellulose graft copolymer that machine-shaping, efficient green clean; Can promote the exploitation of low energy consumption, economically feasible, eco-friendly tencel cellulose fiber.
The urea-modified plasticized melt spinning method of a kind of cellulose original position of the present invention comprises:
(1) with cellulose and urea vacuumize;
(2) with the cellulose of 10-20%, the ionic liquid of 50-70%, the urea of 10-40% mixes, and content is mass percent;
(3) adopt parallel dual-screw extruding machine that mixture is extruded, sprayed by spinning nozzle after the deaeration, filtration;
(4) fiber is frozen into rapidly solid, more stretched, be wound in cellulose fibre.
Baking temperature in the described step (1) is 50-90 ℃, and the time is 12-36h.
Cellulose source in the described step (1) is the common cotton fiber, and the degree of polymerization is 300-600.
Ionic liquid in the described step (2) is 1-butyl-3-methylimidazole villaumite [BMIM] Cl or 1-ethyl-3-methylimidazole acetate [EMIM] Ac.
The screw slenderness ratio of the parallel dual-screw extruding machine in the described step (3) is 1:35-1:55.
Extrusion temperature in the described step (3) is 100-180 ℃, screw speed is 250-400rpm, and cross-head pressure is 3-5MPa, vacuum pump pressure 0.8-1Mpa, high temperature high shear forces by continous mode improves cellulosic grafting efficiency, meltbility and spinnability.
The present invention relates to cellulosic derivatization modification and high-temperature fusion thereof and extrude, especially relate to in-situ modified in the high temperature extrusion of cellulose; Adopt double screw extruder, under the plasticization of ionic liquid, cellulose and urea carry out the derivatization modification, then carry out the high temperature melt-spun; Under the powerful shearing force effect of extruder, make material mixing, melting, react more fully, for realizing that cellulosic high temperature melt-spun through engineering approaches, industrialization produce significant.
Take ionic liquid as plasticizer, under the effect of catalyst, select urea in-situ modified to cellulose in double screw extruder, sprayed by spinning nozzle through after deaeration, filtration and the supercharging again, after the tank washing, cut-out, the dry cellulose carbamate fibre that obtains are on the basis that keeps the cellulose self performance, give its good processing characteristics and mechanical property, prepared the material of application of aspects such as can adapting to industry and life.
Beneficial effect
(1) processing modified technique of the present invention can obtain to be easy to the cellulose graft copolymer that machine-shaping, efficient green clean;
(2) compare with soluble modified cellulose in beaker, the high temperature high shear forces fused fiber element of continous mode has more effectively destroyed in the cellulosic molecule and intermolecular hydrogen bond in the extruder, can promote the exploitation of low energy consumption, economically feasible, eco-friendly tencel cellulose fiber, for significant contribution is made in the sustainable development of fiber industry.
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 for explanation the present invention 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 limited range equally.
Embodiment 1
With cellulose and urea 50 ℃ of lower vacuumizes 12 hours, with 100g cellulose, 300g urea, 800g[BMIM] Cl joins in the homogenizer and mixes.
Double screw extruder one district's temperature is 100 ℃, and two district's temperature are 110 ℃, and three district's temperature are 120 ℃, and four district's temperature are 120 ℃, and five district's temperature are 130 ℃, and six district's temperature are 140 ℃, and seven district's temperature are 150 ℃, and eight district's temperature are 160 ℃, and head temperature is 160 ℃.Screw speed is 250rpm, and extrusion pressure is 3MPa, and vacuum pump pressure is 0.8MPa.
The good spinning property of cellulose melt, finally can obtain fiber number is 2.64dtex, and fracture strength is 4.31cN/dtex, and percentage elongation is 26.7%.
Embodiment 2
With cellulose and urea 70 ℃ of lower vacuumizes 24 hours, with 100g cellulose, 400g urea, 1000g[BMIM] Cl joins in the homogenizer and mixes.
Double screw extruder one district's temperature is 100 ℃, and two district's temperature are 110 ℃, and three district's temperature are 120 ℃, and four district's temperature are 130 ℃, and five district's temperature are 140 ℃, and six district's temperature are 150 ℃, and seven district's temperature are 160 ℃, and eight district's temperature are 170 ℃, and head temperature is 165 ℃.Screw speed is 300rpm, and extrusion pressure is 4MPa, and vacuum pump pressure is 0.9MPa.
The good spinning property of cellulose melt, finally can obtain fiber number is 2.35dtex, and fracture strength is 4.42cN/dtex, and percentage elongation is 28.1%.
Embodiment 3
With cellulose and urea 90 ℃ of lower vacuumizes 36 hours, with 100g cellulose, 500g urea, 1200g[BMIM] Cl joins in the homogenizer and mixes.
Double screw extruder one district's temperature is 100 ℃, and two district's temperature are 110 ℃, and three district's temperature are 120 ℃, and four district's temperature are 135 ℃, and five district's temperature are 145 ℃, and six district's temperature are 155 ℃, and seven district's temperature are 165 ℃, and eight district's temperature are 175 ℃, and head temperature is 160 ℃.Screw speed is 350rpm, and extrusion pressure is 5MPa, and vacuum pump pressure is 1MPa.
The good spinning property of cellulose melt, finally can obtain fiber number is 2.58dtex, and fracture strength is 4.32cN/dtex, and percentage elongation is 27.6%.
Embodiment 4
With cellulose and urea 70 ℃ of lower vacuumizes 24 hours, with 100g cellulose, 400g urea, 1000g[EMIM] Ac joins in the homogenizer and mixes.
Double screw extruder one district's temperature is 100 ℃, and two district's temperature are 110 ℃, and three district's temperature are 120 ℃, and four district's temperature are 130 ℃, and five district's temperature are 140 ℃, and six district's temperature are 150 ℃, and seven district's temperature are 160 ℃, and eight district's temperature are 170 ℃, and head temperature is 165 ℃.Screw speed is 400rpm, and extrusion pressure is 4MPa, and vacuum pump pressure is 0.8MPa.
The good spinning property of cellulose melt, finally can obtain fiber number is 2.86dtex, and fracture strength is 4.83cN/dtex, and percentage elongation is 26.5%.
Embodiment 5
With cellulose and urea 70 ℃ of lower vacuumizes 24 hours, with 100g cellulose, 500g urea, 1200g[EMIM] Ac joins in the homogenizer and mixes.
Double screw extruder one district's temperature is 100 ℃, and two district's temperature are 110 ℃, and three district's temperature are 120 ℃, and four district's temperature are 130 ℃, and five district's temperature are 140 ℃, and six district's temperature are 155 ℃, and seven district's temperature are 165 ℃, and eight district's temperature are 175 ℃, and head temperature is 170 ℃.Screw speed is 300rpm, and extrusion pressure is 4MPa, and vacuum pump pressure is 0.8MPa.
The good spinning property of cellulose melt, finally can obtain fiber number is 2.74dtex, and fracture strength is 4.72cN/dtex, and percentage elongation is 25.9%.
Claims (6)
1. urea-modified plasticized melt spinning method of cellulose original position comprises:
(1) with cellulose and urea vacuumize;
(2) with the cellulose of 10-20%, the ionic liquid of 50-70%, the urea of 10-40% mixes, and content is mass percent;
(3) adopt parallel dual-screw extruding machine that mixture is extruded, sprayed by spinning nozzle after the deaeration, filtration;
(4) fiber is frozen into rapidly solid, more stretched, be wound in cellulose fibre.
2. the urea-modified plasticized melt spinning method of a kind of cellulose original position according to claim 1, it is characterized in that: the baking temperature in the described step (1) is 50-90 ℃, the time is 12-36h.
3. the urea-modified plasticized melt spinning method of a kind of cellulose original position according to claim 1 is characterized in that: the cellulose source in the described step (1) is the common cotton fiber, and the degree of polymerization is 300-600.
4. the urea-modified plasticized melt spinning method of a kind of cellulose original position according to claim 1, it is characterized in that: the ionic liquid in the described step (2) is 1-butyl-3-methylimidazole villaumite [BMIM] Cl or 1-ethyl-3-methylimidazole acetate [EMIM] Ac.
5. the urea-modified plasticized melt spinning method of a kind of cellulose original position according to claim 1, it is characterized in that: the screw slenderness ratio of the parallel dual-screw extruding machine in the described step (3) is 1:35-1:55.
6. the urea-modified plasticized melt spinning method of a kind of cellulose original position according to claim 1, it is characterized in that: the extrusion temperature in the described step (3) is 100-180 ℃, screw speed is 250-400rpm, and cross-head pressure is 3-5MPa, vacuum pump pressure 0.8-1Mpa.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276473A (en) * | 2013-06-19 | 2013-09-04 | 东华大学 | Method for preparing celluloses and modified biodegradable polymer blend fibers |
| CN103290504A (en) * | 2013-06-19 | 2013-09-11 | 东华大学 | Cellulose in-situ chemical modification and plasticizing melt spinning method thereof |
| CN103290503A (en) * | 2013-06-19 | 2013-09-11 | 东华大学 | Process and devices for chemical modification of cellulose and for continuous low temperature solution spinning |
| CN104045720A (en) * | 2014-07-01 | 2014-09-17 | 东华大学 | Method for low-temperature dissolution of urea-modified cellulose |
| CN106498548A (en) * | 2016-11-01 | 2017-03-15 | 安徽依采妮纤维材料科技有限公司 | A kind of enhance immunity radiation resistant fiber fabric |
| CN106567150A (en) * | 2016-11-04 | 2017-04-19 | 天津工业大学 | Preparation method of plasticized cellulose carbamate fiber |
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| CN102358957A (en) * | 2011-08-24 | 2012-02-22 | 中国纺织科学研究院 | Method for preparing cellulose spinning stock solution |
| CN202208780U (en) * | 2011-08-24 | 2012-05-02 | 中国纺织科学研究院 | Device for continuous preparation of cellulose spinning solution |
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- 2012-11-28 CN CN201210496598.9A patent/CN102965752B/en not_active Expired - Fee Related
Patent Citations (4)
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| CN1491974A (en) * | 2002-10-22 | 2004-04-28 | 中国科学院化学研究所 | Cellulose solution and its preparing method |
| US20110152413A1 (en) * | 2009-12-21 | 2011-06-23 | Dawkins Bobby G | Polybenzimidazole solution in an ionic liquid |
| CN102358957A (en) * | 2011-08-24 | 2012-02-22 | 中国纺织科学研究院 | Method for preparing cellulose spinning stock solution |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276473A (en) * | 2013-06-19 | 2013-09-04 | 东华大学 | Method for preparing celluloses and modified biodegradable polymer blend fibers |
| CN103290504A (en) * | 2013-06-19 | 2013-09-11 | 东华大学 | Cellulose in-situ chemical modification and plasticizing melt spinning method thereof |
| CN103290503A (en) * | 2013-06-19 | 2013-09-11 | 东华大学 | Process and devices for chemical modification of cellulose and for continuous low temperature solution spinning |
| CN103290503B (en) * | 2013-06-19 | 2015-08-12 | 东华大学 | Cellulosic chemical modification and continuous low-temperature dissolving spinning technology and equipment |
| CN103276473B (en) * | 2013-06-19 | 2016-01-06 | 东华大学 | A kind of method preparing cellulose and the polymer blended fiber of modified degradable |
| CN104045720A (en) * | 2014-07-01 | 2014-09-17 | 东华大学 | Method for low-temperature dissolution of urea-modified cellulose |
| CN106498548A (en) * | 2016-11-01 | 2017-03-15 | 安徽依采妮纤维材料科技有限公司 | A kind of enhance immunity radiation resistant fiber fabric |
| CN106567150A (en) * | 2016-11-04 | 2017-04-19 | 天津工业大学 | Preparation method of plasticized cellulose carbamate fiber |
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