CN1184364C - Prepn process of spinning dope for producing cellulose fibre through solvent process - Google Patents
Prepn process of spinning dope for producing cellulose fibre through solvent process Download PDFInfo
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- CN1184364C CN1184364C CNB011267135A CN01126713A CN1184364C CN 1184364 C CN1184364 C CN 1184364C CN B011267135 A CNB011267135 A CN B011267135A CN 01126713 A CN01126713 A CN 01126713A CN 1184364 C CN1184364 C CN 1184364C
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Abstract
The preparing invention relates to a preparation technology for producing a spinning stock solution of cellulose fibers by a solvent method, which is characterized in that fiber powder crushed by a pulp crusher is dried for 6 to 12h under the conditions that the vacuum degree is from-9*10<4> to-5*10<4>Pa and a temperature is from 30 to 50 DEG C; the water content of the powder is from 2% to 4%; a water solution of N-methyl-morpholine oxide (NMMO) is treated by inspissation under an alkali pressure condition, and the water content of the solution is equal to or smaller than 15%; the powder and NMMO are stirred for 10 to 30 min in a mixer in certain proportion at 70 90 DEG C to form a yellowish pasty substance; the pasty substance is fed in a double-screw extruder of which the screw length-diameter ratio is from 1:42 to 1:52 for dissolution and deaeration for 3 to 15 min; and then the produced maple transparent solution can be used for spinning. By adopting the technology, not only the dissolution time is shortened, but also the mixing and the dissolution of materials are sufficient. The present invention achieves the purpose of energy saving, high efficiency, degradation reduction, and improvement of the quality of spinning stock solutions.
Description
Technical field
The present invention relates to the preparation technology of the spinning solution of producing cellulose fibre through solvent in the chemical fibre manufacturing, the fiber that is made by this spinning solution is widely used in fabrics for industrial use and decorates the clothes textiles.
Background technology
Because cellulose fiber fiber products hygroscopicity, poisture-penetrability are good, wear comfortable, and abundant raw material, but product abandonment thing natural degradation again is decomposed into carbon dioxide and water by enzyme, therefore, the production of this fibrous material receives much attention in recent years.Traditional cellulose fibre is mainly produced with the viscose glue route, and this method has been used carbon disulfide and a large amount of bronsted lowry acids and bases bronsted lowries, has caused severe contamination to environment, and the viscose wet strength that makes is low, and these factors have all limited the development of viscose.
As far back as the thirties in 20th century just the someone propose, the direct dissolving cellulos of available tertiary amino oxides prepares fiber, and has formed basic patent (USP-2,179,181) with this.Rise the seventies in 20th century, Courtaulds company and Lenzing company have carried out big quantity research to this area, up to a hundred patents have been applied for, wherein representational have an EP-A-0553070, EP-A-0356419, DE-A-2913589, WO93/19230, WO95/04173, DD-A-218121, EP-A-0574870, AT-B-397392, GB-A-1,017,855, WO92/14871, WO92/07124, DE-A-4219658, WO96/18760, US-A-4,246,221, USP-2,179,181, and Chinese patent application 96197127,96191362,96191361,95193763,95193716,94192192,94192048,98801167,98800540,97190439,96193341 etc.In the above-mentioned patent, adopt thin film evaporator to carry out cellulosic dissolving mostly.The crowded film machine (DE-OS-2011493) that adopts Switzerland Buss AG company to make is also arranged.For energy-conservation and raising output, each patent has proposed different device and technology improves cellulose dissolution efficient, but these install all more complicated.As: the dissolver of describing among the WO94/28217 is a big horizontal drum, in rotor is arranged, arrange an agitating unit along axle, the apparatus structure complexity, operation is also inconvenient.Also have the particle of suggestion prefabricated cellulose of elder generation and solvent in addition, dissolve (USP4,211,579) again.
All patents are sorted out, can be thought that dissolution mechanism is divided into two big classes:
1. indirect dissolution method.Cellulose is placed on moisture greater than swelling among 22% the NMMO, treat abundant swelling after, in elevated temperature, under vacuum, take out excessive moisture, make cellulose finally reach dissolving.
2. direct dissolution method.Moisture Control among the NMMO below 15%, is made it directly to mix mutually with cellulose, reach quick dissolving by intensification.
A large amount of patents belong to the 1st class.The 1st class dissolvers is easy to the expansion scale, and the quality of dissolving, but solvent time of staying in dissolvers is often longer, makes NMMO and cellulose be easy to degraded so first, contains the solvent cellulose in a large number simultaneously and at high temperature has bigger potential safety hazard.
In the direct dissolution method of the 2nd class, the easiest method is a twin-screw method.
Korea S science and technology research institute has proposed a patent (WO97/47790) in 1996, utilize twin-screw to come dissolving cellulos.In the method, used twin-screw is without special transformation, and the NMMO of cellulose and fusing injects twin-screw in zones of different.Though this method is simplified whole dissolution process greatly, dissolution time also shortens greatly, and has reduced storing material, but it has special requirement for the cellulosic material particle, nonetheless, also having the gel that is unfavorable for spinning in the spinning solution that is made by this method constantly produces.
The patent that apply for domestic Yibin City Chemical Fibre Factory (application number 97107819.X) though in also mentioned twin-screw, clearly do not write the effect of its twin-screw exactly.From its application claim, the cellulose dissolution time needs 6～12h, and this illustrates that used twin-screw has not been dissolution and be the conveying effect therein.And the dissolution time of 6～12h not only makes production efficiency descend, and also very easily causes the degraded of cellulose and solvent.
Summary of the invention
The problem to be solved in the present invention provides and can make the direct dissolving method that the spinning solution preparation efficiency is higher, quality is more stable.
For addressing this problem, adopted following technical scheme:
1. be 400～1000 cellulose wood pulp or cotton pulp with the degree of polymerization (DP), be ground into cellulose powder with the pulp pulverizer of common viscose fiber factory.With this powder in vacuum-9 * 10
4～-5 * 10
4Pa and 30～50 ℃ of down dry 6～12h make its moisture content reach 2%～4%;
With aqueous solution inspissation under reduced pressure of N-methylmorpholine oxide (NMMO), making wherein, water content is equal to or less than 15%.
Above-mentioned comminuted powder and the NMMO aqueous solution had in the blender of agitator one mix with certain proportion, and stir 10～30min down in 70～90 ℃, until generating flaxen pastel, powder and NMMO mixed proportion are weight ratio 7: 93～15: 85.
With general high speed in the same way revolving reaction type double screw extruder do following corrigendum: (A) sealing 2 vacuum orifices.(B) draw ratio is increased to 1: 42～1: 52.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 two screw channels, material has obtained sufficient stirring and mixed.The increase of screw slenderness ratio can make material can have more opportunity to mix, dissolve.And in this mixed process, because its surface continual renovation, thereby can discharge material interior volatile substances or steam, improve the quality of lysate.
3. the flaxen pastel in aforementioned 1 is fed in above-mentioned 2 the twin-screw, the control twin-screw is respectively distinguished temperature and rotating speed, through dissolving, the deaeration of 3～15min, generating temperature and be 90～130 ℃, viscosity is that 400～1200Pas, refraction index are 1.480～1.488 light brown clear solution.This kind solution is through the booster pump supercharging, again after prefilter enters measuring pump by 1000～6000 hole spinning heads ejections, through solidify, washing, cut-out, drying, can obtain cellulose fibre.The temperature controlling range of described twin-screw is 80～130 ℃: each is distinguished temperature range and is respectively 80～120 ℃, 80～120 ℃, 85～125 ℃, 90～130 ℃; The velocity interval of screw rod is 30～100r/min.
4. in order to obtain bubble-free spinning solution, the cross-head intensity of pressure will be controlled at 295～785N/cm
2, sufficient deaeration is arranged to guarantee stoste.
The spinning solution preparation technology that advantage of the present invention provides is on the basis that utilizes existing double screw extruder dissolving technology, adopt the twin-screw that increases draw ratio not only to make cellulosic dissolving only need 3～15min, saved the energy, reduced cost, install also very simply, the more important thing is the mixing of material in twin-screw, dissolution are strengthened; And, can avoid or reduce the signs of degradation of material, the raising that helps the recovery of solvent and make fiber quality in screw rod because the time that cellulose and solvent stop under the high temperature is short.The present invention has increased a blender before twin-screw, make dried cellulose powder and moisture 15% and below NMMO just fully mix before entering twin-screw, help the uniformity of spinning solution and the raising of spinning quality.
The specific embodiment
With DP is that 700 wood pulp utilizes the common pulverizer of viscose glue factory to pulverize, and (is decompressed to-7 * 10 under decompression state
4Pa) dry 6h and under 50 ℃ of conditions, the moisture of the pulp that obtains (being cellulose powder) is 2%;
With NMMO aqueous solution inspissation under reduced pressure, making wherein, water content equals 13% (concentration that is NMMO is 87%).
With the above-mentioned pulp of 7.2kg and 82.8kg concentration is that 87% the NMMO aqueous solution places the blender that has agitator, and blended under agitation 10min under 80 ℃ of conditions for preventing oxidation, adds 90g tangerine propyl propionate before mixing;
It is to dissolve in 1: 48 the double screw extruder that material after the blend is fed screw slenderness ratio continuously, and it is 90,90,95 and 95 ℃ that twin-screw is respectively distinguished temperature, speed of gyration 60r/min, and cross-head (the being the exit) intensity of pressure is controlled at 490N/cm
2, can obtain refraction index behind the 5min and be 1.4840 transparent even spinning solution, its good spinning property.
Claims (4)
1. the preparation technology of the spinning solution of producing cellulose fibre through solvent is characterized in that:
With the degree of polymerization is that 400～1000 cellulose wood pulp or cotton pulp are ground into cellulose powder with common pulp pulverizer, and this powder is placed-9 * 10
4～-5 * 10
4Dry 6～12h makes its moisture content reach 2%～4% under the vacuum of Pa and 30～50 ℃ of conditions;
Aqueous solution inspissation under reduced pressure with the N-methylmorpholine oxide makes its moisture be equal to or less than 15%;
Above-mentioned cellulose powder and N-methylmorpholine oxide water solution are mixed in the blender of belt stirrer with 7: 93～15: 85 weight ratio, and under 70～90 ℃ of conditions, stir 10～30min, until forming faint yellow pastel.
2. preparation technology as claimed in claim 1, it is characterized in that with 2 vacuum ports of formed faint yellow pastel feeding be closed, screw slenderness ratio be do dissolving in 1: 42～1: 52 the type of the revolving reaction in the same way double screw extruder, 3～15min is handled in deaeration, generating temperature and be 90～130 ℃, viscosity is that 400～1200Pas, refraction index are 1.480～1.488 light brown clear solution, the spinning after the supercharging of routine, filtration, metering of this solution.
3. preparation technology as claimed in claim 2, the head pressure intensity that it is characterized in that described extruder is 295～785N/cm
2
4. as claim 2 or 3 described preparation technologies, it is characterized in that it is 80～120 ℃, 80～120 ℃, 85～125 ℃, 90～130 ℃ that described double screw extruder is respectively distinguished temperature range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011267135A CN1184364C (en) | 2001-09-11 | 2001-09-11 | Prepn process of spinning dope for producing cellulose fibre through solvent process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011267135A CN1184364C (en) | 2001-09-11 | 2001-09-11 | Prepn process of spinning dope for producing cellulose fibre through solvent process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1336451A CN1336451A (en) | 2002-02-20 |
| CN1184364C true CN1184364C (en) | 2005-01-12 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011267135A Expired - Fee Related CN1184364C (en) | 2001-09-11 | 2001-09-11 | Prepn process of spinning dope for producing cellulose fibre through solvent process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100395385C (en) * | 2005-11-16 | 2008-06-18 | 东华大学 | Preparation method of lyocell fiber used for cord thread |
| CN102634895A (en) * | 2011-03-07 | 2012-08-15 | 如皋市丁堰纺织有限公司 | Cotton pulp solvent method cellulose fiber pure/blended yarn and production process thereof |
| CN107541801A (en) * | 2016-06-29 | 2018-01-05 | 吉林富博纤维研究院有限公司 | A kind of preparation method of cellulose spin dope |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085838B (en) * | 2007-07-03 | 2011-03-30 | 中国科学院化学研究所 | Method for continuously preparing cellulose/ionic liquid solution |
| CN101736426B (en) * | 2008-11-07 | 2012-01-25 | 中国科学院化学研究所 | Method for preparing regenerated cellulose fibers from plant fibrous pulp of reeds and stalks |
| CN103025931B (en) * | 2010-06-30 | 2015-07-08 | 可隆工业株式会社 | Dope for spinning lyocell, method for preparing a lyocell filament fiber using same, and method for preparing a lyocell staple fiber using same |
| CN105442055A (en) * | 2014-08-26 | 2016-03-30 | 江苏南纬悦达纺织研究院有限公司 | Mugwort fiber and preparation method thereof |
| CN105113033B (en) * | 2015-10-15 | 2018-08-28 | 五邑大学 | A kind of preparation method of antibiosis anti-acarien sulfur-bearing viscose rayon |
| CN109304110B (en) * | 2018-09-29 | 2021-08-06 | 郑州中远氨纶工程技术有限公司 | Spiral ribbon mixer and preparation method of Lyocell fiber spinning solution |
| CN110067034B (en) * | 2019-04-22 | 2021-09-21 | 东华大学 | Flame-retardant regenerated cellulose fiber and preparation method thereof |
| CN110258162A (en) * | 2019-06-12 | 2019-09-20 | 当阳市鸿阳新材料科技有限公司 | Prepare cellulose spinning slurries device and preparation method thereof |
-
2001
- 2001-09-11 CN CNB011267135A patent/CN1184364C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100395385C (en) * | 2005-11-16 | 2008-06-18 | 东华大学 | Preparation method of lyocell fiber used for cord thread |
| CN102634895A (en) * | 2011-03-07 | 2012-08-15 | 如皋市丁堰纺织有限公司 | Cotton pulp solvent method cellulose fiber pure/blended yarn and production process thereof |
| CN107541801A (en) * | 2016-06-29 | 2018-01-05 | 吉林富博纤维研究院有限公司 | A kind of preparation method of cellulose spin dope |
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|---|---|
| CN1336451A (en) | 2002-02-20 |
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