CN102691125A - Method for preparing regenerated cellulose fibers with cellulose carbamate - Google Patents
Method for preparing regenerated cellulose fibers with cellulose carbamate Download PDFInfo
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Abstract
The invention relates to a method for preparing regenerated cellulose fibers with cellulose carbamate. The method is characterized by using a solvent composition for dissolving the cellulose carbamate, uniformly dispersing a certain amount of cellulose carbamate in the solvent composition, freezing to the temperature below minus 10 DEG C at a low temperature condition, taking out the frozen mixture and thawing the frozen mixture at a temperature not higher than 50 DEG C, carrying out wet spinning and obtaining the regenerated cellulose fibers after solidifying, washing and drying silk, wherein the solvent composition is a water solution containing 6-10wt% of sodium hydroxide and 0.1-3wt% of zinc oxide. The method has the effect of solving the two problems of difficult dissolution of the cellulose carbamate and instable solution in the previous processes and has high industrial application value.
Description
Invention field
The present invention relates to a kind ofly prepare the method for regenerated celulose fibre, belong to natural polymer and field of textiles by cellulose carbamate.
Technical background
For a long time, viscose production Technology backward relatively becomes the bottleneck that regenerated celulose fibre further develops.Along with the raising of environmental protection consciousness in the worldwide, this contradiction is outstanding day by day.Seeking the novel solvent of regenerated celulose fibre green processing, is the new way that solves this contradiction.Wherein the most noticeable is N-methylmorpholine-N-oxide (NMMO), NaOH/ urea water system, ionic liquid and cellulose carbamate technology.
Cellulose carbamate technology is to be the new technology of feedstock production regenerated celulose fibre with the cellulose carbamate, and its basic principle is that urea and pretreated cellulose are reacted generation cellulose carbamate (CC) under hot conditions.CC can well be dissolved in dilute alkaline soln or other solvent and process spinning solution, utilizes acid, alkali, heating or other method that CC is separated out from solution, can make regenerated celulose fibre through post processing.This technology can maximally utilise the production equipment of original viscose acetal fibre, and it is the most potential alternative to be considered to the viscose acetal fibre production technology, and the report of many related process has been arranged at present both at home and abroad.The method that wherein discloses among patent WO 03099877, DE 101127189, CN 100516326C and the US 2005/0234229A1 is that a synthetic cellulose carbamate dissolution in low temperature that obtains is in the NaOH solvent; Solidification forming in containing 8-12% sulfuric acid and the coagulating bath of 20-25% sodium sulphate (adding a certain amount of ammonium sulfate or aluminum sulfate sometimes again); Involve by solidifying roller; In dilute alkaline soln or in the water, regenerate again; Obtain the regenerated cellulose carbamate fibre of nitrogen content between 0.1-0.3 at last, intensity is 1.0-1.7cN/dtex, and elongation at break is 9-28%.Wherein coagulation bath temperature is 15-25 ℃; The temperature that regeneration is bathed and washing is bathed is 40-60 ℃; Alkali content was preferably 0.01-1% during regeneration was bathed, and the preferred 0.08mm of spinneret * 35 holes, the strand of solidification forming are elongated by five roller drawing-offs altogether; Their linear velocity is between 10-120m/min, and the linear differential of adjacent roller is 20m/min.Be that solvent, sodium carbonate are coagulating bath with NaOH in the method that patent JP 61085452 and US 6234778B1 disclose, coagulating bath can recycle, design simultaneously utilized a kind of can be to spinning head and the coagulating tank spinning equipment of setting flexibly.Though above-mentioned technology is benefited our pursuits to the CC spinning technique, the quality of the spinning solution for preparing and stability are all poor, need the protection of low temperature environment in the spinning process, are unfavorable for industrializing implementation.To the problems referred to above; Changing with the ionic liquid in the method that patent US 2009/0258561A1, US 2009/0259032AI, US 2009/0258227A1 disclose is solvent; The spinning solution for preparing involves through high temperature gas flow under 90-120 ℃ of condition, solidification forming in the ionic liquid of water or 2-25% again, and it is the 0.5-5% cellulose carbamate fibre that washing and drying obtains nitrogen content; Intensity is 4.1-6.2cN/dtex, and elongation at break is 8-30%.The method that patent US 2008/0023874A1 discloses then is to be that solvent obtains spinning solution with N-methyl-N-oxide morpholine (NMMO); Extruding solidification forming in the NMMO aqueous solution 10% through spinning head under the 85-95 ℃ of condition; And be 0.3-1.0% at mass fraction, temperature is to regenerate in 60-95 ℃ the sodium hydroxide solution, washing, drying obtain the cellulose carbamate fibre of certain intensity; The intensity of fiber is 3.5-6.9cN/dtex, and elongation at break is 4.5-9.0%; Though NMMO solvent and ionic liquid solvability are stronger, receive dissolution conditions harsh, the restriction of unfavorable factors such as cost height is difficult to industrializing implementation.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of spinning solution the stable and lower-cost method that is prepared regenerated celulose fibre by cellulose carbamate.
This method is come the dissolving cellulos carbamate with a kind of new solvent compositions, dissolves through the method for freeze-thaw to obtain cellulose carbamate solution; At normal temperature or be higher than under the condition of normal temperature; This spinning solution through filter, after the vacuum defoamation compressed air or nitrogen is suppressed and measuring pump suction and pumping effect under; Solidification forming in acid bath, the strand after the shaping involves by solidifying roller, and stretches through the washing roller; Wash in the drip washing district, just prepare the regenerated celulose fibre of function admirable again according to common process.
For realizing above-mentioned purpose, technical scheme provided by the invention is:
Cellulose carbamate is dissolved in the aqueous solution that contains 6-10wt% NaOH, 0.1-3wt% zinc oxide; Be refrigerated to below-10 ℃; Thaw not being higher than under 50 ℃ the condition then; Obtain cellulose carbamate solution, after filtration, the deaeration, obtain the cellulose carbamate spinning solution; Carry out wet spinning, strand obtains regenerated celulose fibre after supersolidification, washing, drying.
The aqueous solution of dissolving cellulos carbamate can be preferably the aqueous solution that contains 7-8wt% NaOH, 1.2-1.8wt% zinc oxide.
Described wet spinning is the cellulose carbamate spinning solution to be clamp-oned in the coagulating bath through spinning head solidify.
The aperture of used spinning head is 0.08-0.14mm, and hole count is the 30-100 hole.
The composition of described coagulating bath can for: the sodium sulphate of the sulfuric acid of 4.8-12wt%, the zinc sulfate of 0-5wt%, 0-21wt%, remaining be water.Coagulation bath temperature is 15-40 ℃, and the time of strand submergence in sour coagulating bath is 0.02-0.04s.
Cellulose carbamate can be applied for a patent (application number: 200910062951.0 from this laboratory; Publication number: microwave synthesis method known CN101597336A) prepares; Promptly at first cellulose is immersed in and makes it fully adsorb urea in the aqueous solution of urea, squeeze out unnecessary aqueous solution of urea then; Drying obtains the homogeneous mixture of cellulose/urea; Obtain the cellulose carbamate product through washing, drying at last through heating using microwave cellulose/urea solid mixture then.Because the inventive method only relates to the dissolving of cellulose carbamate, so be applicable to the cellulose carbamate of other method preparation naturally.
Cellulose carbamate spinning solution according to the inventive method prepares is highly stable; But storage-stable is tens of days under normal temperature condition; In filtration, vacuum defoamation, store, suppress the protection that does not need the low temperature chuck in the whole link that is transported to spinning head, room temperature or be not higher than under 50 ℃ the condition and can implement.
Sodium hydrate content is lower in the cellulose carbamate spinning solution for preparing according to the inventive method, has reduced the consumption to sour coagulating bath, and the zinc sulfate that generates in the process of setting can be used as coagulating agent and use, and is economical convenient.
The mechanical property of the regenerated celulose fibre for preparing according to the inventive method is higher, and dried fracture strength is 1.44-2.86cN/dtex, and wet breaking strength is 0.46-0.60cN/dtex, and dried elongation at break is 7-15%.Residual sulphur, residual zinc amount is 0, nitrogen content lower (< 0.3%), safety and comfort.Dyeability is good, and it is than viscose easy dyeing more, and dye uniformity also reaches 4 grades of ash card levels.
The inventive method is a solvent with a kind of new solvent compositions; Dissolving obtains the cellulose carbamate solution of low alkali number, high stability, and wet spinning obtains the regenerated celulose fibre of excellent performance, and is with short production cycle; Cost is low; Simple to operation, solved CC dissolving difficulty and unstable this two hang-up of solution in the open in the past cellulose carbamate technology of inventing, have very high industrial applications and be worth.
Compared with present technology, advantage of the inventive method and beneficial effect are:
1) in the conventional method, when the nitrogen content of cellulose carbamate was 2-3%, cellulose carbamate could dissolve preferably.Use this method not have and explicitly call for to dissolving the plain carbamate nitrogen content of used cellulose.Particularly when nitrogen content lower (0.5-1.2%), still can dissolve the cellulose carbamate solution that obtains 5.0-8.0wt%.Because the nitrogen content of the cellulose carbamate raw material that uses is lower,, only need in acid bath, regenerate with the washing of water wash district by solidification forming with respect to previous technology; Can remove the process of in sig water, regenerating from; Cost reduces, and technological process tails off, and efficient improves.
When 2) cellulose carbamate solution that obtains of dissolving was used for spinning, low alkali content (6.0-8.0wt%) had reduced the consumption of sulfuric acid in the sour coagulating bath, and the zinc sulfate that generates in the process of setting can be used as coagulating agent and use, and is economical convenient.
When 3) sulfuric acid concentration (4.8-7.0wt%) is low in the coagulating bath, still can holomorphosis obtain high-intensity regenerated celulose fibre, help the reduction of cost.
4) the used solvent compositions of the inventive method can significantly improve the solubility of cellulose carbamate and the stability of gained solution, leaves standstill under the normal temperature condition 12-240 hour and gel not, and cost is low, and solute effect is good, helps suitability for industrialized production.Have only the freezing link in the course of dissolution to require low temperature environment; Thawing, filtration, vacuum defoamation, storing, suppressing the protection that does not need the low temperature chuck in the residue production link that is transported to spinning head; Room temperature or be higher than under the condition of room temperature and can implement had solved in the past cellulose carbamate dissolving difficulty and and unstable this two hang-up of solution in the cellulose carbamate technology of open invention.
Specific embodiments
Below in conjunction with concrete instance technical scheme of the present invention and application are described further, rather than limit the invention.
Embodiment 1
A, to get 700 gram nitrogen contents be 1.232% cellulose carbamate sample (viscosity average molecular weigh 10.2 * 10
4) be dispersed in 10.00 * 10
4Gram by 7.5wt% NaOH, 1.6wt% zinc oxide is water-soluble and obtain in the solvent, putting into refrigerator and cooled freezes to-10 ℃, take out from refrigerator the freezing back that finishes, 50 ℃ of environmental conditions are thawed, and stir to obtain the 6.54wt% cellulose carbamate solution.
B, the cellulose carbamate solution that dissolving is obtained filter, the vacuum standing and defoaming is handled; Gas pressure intensity is 0.2MPa during filtration, and filter cloth is that fineness is 350 purpose cottons, and deaeration vacuum is 0.01MPa; Time is 5 hours, obtains the used cellulose carbamate spinning solution of spinning.
C, spinning solution is extruded solidification forming in acid bath through spinning head under compressed air and measuring pump suction and pumping effect; Wherein the fluid reservoir gas pressure intensity is 0.5MPa; Spinning head is 0.14mm * 75 holes; Acid bath consists of 12wt% sulfuric acid, 1wt% zinc sulfate, 21wt% sodium sulphate, and coagulation bath temperature is 25 ℃, and strand Immersion time in acid bath is 0.04s; Tow after the shaping is by drench district's washing regeneration through water after solidifying roller and involving again, and solidifying the roller rotating speed is 27m/min, and the washing roller is 1.02 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 28 ℃; Can obtain the high-intensity cellulose carbamate fibre of tool through last oil drying at last, oil bath temperature is 45 ℃, and bake out temperature is 75 ℃; The dried fracture strength of the regenerated celulose fibre that oven dry obtains is 1.91cN/dtex,, dried elongation at break is 8%, and residual nitrogen amount is 0.1%, and the dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 2
The preparation process of cellulose carbamate spinning solution is as embodiment 1.
Spinning solution is extruded solidification forming in acid bath through spinneret orifice under compressed air or nitrogen and measuring pump suction and pumping effect; Wherein the fluid reservoir gas pressure intensity is 0.2MPa during spinning; Spinning head is 0.08mm * 75 holes; Acid bath consists of 11wt% sulfuric acid, 1.5wt% zinc sulfate, 20wt% sodium sulphate, and coagulation bath temperature is 25 ℃, and strand Immersion time in acid bath is 0.04s; Tow after the shaping is by drench district's washing regeneration through water after solidifying roller and involving again, and solidifying the roller rotating speed is 27m/min, and the washing roller is 1.02 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 28 ℃; Can obtain the high-intensity cellulose carbamate fibre of tool through last oil drying at last, oil bath temperature is 45 ℃, and bake out temperature is 75 ℃; The dried fracture strength of the regenerated celulose fibre that oven dry obtains is 2.86cN/dtex, and dried elongation at break is 12.1%, and residual nitrogen amount is 0.2%.The dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 3
A, to get 700 gram nitrogen contents be 1.785% cellulose carbamate (viscosity average molecular weigh 10.0 * 10
4) be dispersed in 10.0 * 10
4Gram by 7.5wt% NaOH, 1.6wt% zinc oxide is water-soluble and obtain in the solvent, putting into refrigerator and cooled freezes to-12 ℃, take out from refrigerator the freezing back that finishes, 25 ℃ of environmental conditions are thawed, and stir just to obtain the 6.54wt% cellulose carbamate solution.
B, the cellulose carbamate solution that dissolving is obtained filter, the vacuum standing and defoaming is handled; Gas pressure intensity is 0.3MPa during filtration, and filter cloth is that fineness is 300 purpose cottons, and deaeration vacuum is 0.02MPa; Time is 8 hours, obtains the used cellulose carbamate spinning solution of spinning.
C, with spinning solution compressed air or nitrogen is suppressed and measuring pump suction and pumping effect under extrude solidification forming in acid bath through spinneret orifice; Wherein the fluid reservoir gas pressure intensity is 0.4MPa; Spinning head is 0.12mm * 75 holes; Acid bath consists of 10wt% sulfuric acid, 1.2wt% zinc sulfate, 19wt% sodium sulphate, and coagulation bath temperature is 28 ℃, and strand Immersion time in acid bath is 0.04s; Tow after the shaping is by drench district's washing regeneration through water after solidifying roller and involving again, and solidifying the roller rotating speed is 30m/min, and the washing roller is 1.03 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 27 ℃; Can obtain the high-intensity cellulose carbamate fibre of tool through last oil drying at last, oil bath temperature is 45 ℃, and bake out temperature is 75 ℃; The dried fracture strength of the regenerated celulose fibre that oven dry obtains is 1.50cN/dtex, and dried elongation at break is 7%, and residual nitrogen amount is 3%.The dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 4
A, to get 650 gram nitrogen contents be 2.262% cellulose carbamate (viscosity average molecular weigh 5.6 * 10
4) be dispersed in 9.35 * 10
4In the gram 7.5wt%NaOH/1.6wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-12 ℃, take out from refrigerator the freezing back that finishes, and 35 ℃ of environmental conditions are thawed, and stir just to obtain the 6.5wt% cellulose carbamate solution.
B, the cellulose carbamate solution that dissolving is obtained filter, the vacuum standing and defoaming is handled; Gas pressure intensity is 0.4MPa during filtration; Filter cloth is that fineness is 350 purpose nylon cloths; Deaeration vacuum is 0.02MPa, and the time is 10 hours, obtains the used cellulose carbamate spinning solution of spinning.
C, with spinning solution compressed nitrogen suppress and measuring pump suction and pumping effect under extrude solidification forming in acid bath through spinneret orifice; Wherein the fluid reservoir gas pressure intensity is 0.42MPa; Spinning head is 0.14mm * 75 holes; Acid bath consists of 6.84wt% sulfuric acid, and coagulation bath temperature is 15 ℃, and strand Immersion time in acid bath is 0.04s; Tow after the shaping is by drench district's washing regeneration through water after solidifying roller and involving again, and solidifying the roller rotating speed is 30m/min, and the washing roller is 1.23 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 40 ℃; At last through oiling, drying can obtain the high-intensity regenerated celulose fibre of tool, oil bath temperature is 55 ℃, bake out temperature is 65 ℃; The dried fracture strength of the regenerated celulose fibre that oven dry obtains is 1.69cN/dtex, and wet breaking strength is 0.56cN/dtex, and dried elongation at break is 11.45%, and residual sulfur content is 0.The dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 5
The preparation process of cellulose carbamate spinning solution is as embodiment 4.
With spinning solution compressed air suppress and measuring pump suction and pumping effect under extrude solidification forming in first coagulating tank through spinneret orifice; Tow after the shaping involves continuation regeneration in entering second coagulating bath of back by solidifying roller; After being stretching in water and drenching district's washing through the washing roller again, at last through oiling, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.40MPa, and spinning head is 0.08mm * 30 holes, and first coagulating bath is the 6.84wt% sulfuric acid solution, and temperature is 20 ℃, and strand Immersion time in first coagulating bath is 0.04s; The composition of second coagulating bath and first coagulating bath is identical with temperature, and solidifying the roller rotating speed is 30m/min, and the washing roller is 1.23 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 36 ℃; Oil bath temperature is 45 ℃, and bake out temperature is 75 ℃; The dried fracture strength of the regenerated celulose fibre that wet spinning obtains is 1.44cN/dtex, and wet breaking strength is 0.46cN/dtex, and dried elongation at break is 15%, and residual sulfur content is 0.The dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 6
The preparation process of cellulose carbamate spinning solution is as embodiment 4.
With spinning solution compressed air suppress and measuring pump suction and pumping effect under extrude solidification forming in first coagulating tank through spinneret orifice; Tow after the shaping involves continuation regeneration in entering second coagulating bath of back by solidifying roller; After being stretching in water and drenching district's washing through the washing roller again, at last through oiling, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.30MPa, and spinning head is 0.08mm * 100 holes, and first to solidify coagulating bath be the 6.05wt% sulfuric acid solution, and temperature is 19 ℃, and strand Immersion time in acid bath is 0.04s; Second coagulating bath is the 1wt% sodium hydroxide solution, and temperature is 50-60 ℃.Solidifying the roller rotating speed is 30m/min, and the washing roller is 1.23 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 20 ℃; Oil bath temperature is 46 ℃, and bake out temperature is 72 ℃; The dried fracture strength of the regenerated celulose fibre that wet spinning obtains is 1.65cN/dtex, and wet breaking strength is 0.46cN/dtex, and dried elongation at break is 11.04%, and residual sulfur content is 0.The dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 7
The preparation process of cellulose carbamate spinning solution is as embodiment 4.
With spinning solution compressed air suppress and measuring pump suction and pumping effect under extrude solidification forming in first coagulating tank through spinneret orifice; Tow after the shaping involves continuation regeneration in entering second coagulating bath of back by solidifying roller; After being stretching in water and drenching district's washing through the washing roller again, at last through oiling, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.45MPa, and spinning head is 0.12mm * 75 holes, and first coagulating bath is the 6.05wt% sulfuric acid solution, and temperature is 21 ℃, and strand Immersion time in first coagulating bath is 0.04s; Second coagulating bath is a high-temperature water, and temperature is 53-63 ℃; Solidifying the roller rotating speed is 30m/min, and the washing roller is 1.23 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 22 ℃; Oil bath temperature is 46 ℃, and the drier roll temperature is 72 ℃; The dried fracture strength of the regenerated celulose fibre that wet spinning obtains is 1.66cN/dtex, and wet breaking strength is 0.46cN/dtex, and dried elongation at break is 10.66%, and residual sulfur content is 0.The dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 8
A, to get 700 gram nitrogen contents be 2.262% cellulose carbamate (viscosity average molecular weigh 5.6 * 10
4) be dispersed in 9.3 * 10
4In the gram 8.5wt%NaOH/1.2wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-18 ℃, take out from refrigerator the freezing back that finishes, and 42 ℃ of environmental conditions are thawed, and stir just to obtain the 7.0wt% cellulose carbamate solution.
B, the cellulose carbamate solution that dissolving is obtained filter, the vacuum standing and defoaming is handled; Gas pressure intensity is 0.6MPa during filtration; Filter cloth is that fineness is 300 purpose nylon cloths; Deaeration vacuum is 0.01MPa, and the time is 24 hours, obtains the used cellulose carbamate spinning solution of spinning.
C, with spinning solution compressed air suppress and measuring pump suction and pumping effect under extrude solidification forming in the solid bath of acid cure through spinneret orifice, after being stretching in water and drenching district's washing through the washing roller again, at last through oiling, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.40MPa, and spinning head is 0.08mm * 75 holes, and sour coagulating bath is the 6.01wt% sulfuric acid solution, and temperature is 18 ℃, and strand Immersion time in acid bath is 0.04s; Solidifying the roller rotating speed is 30m/min, and the washing roller is 1.23 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 40 ℃; Oil bath temperature is 46 ℃, and the drier roll temperature is 75 ℃; The dried fracture strength of the regenerated celulose fibre that wet spinning obtains is 1.69cN/dtex, and wet breaking strength is 0.50cN/dtex, and dried elongation at break is 10.64cN/dtex, and residual sulfur content is 0.The dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 9
A, to get 570 gram nitrogen contents be 1.952% cellulose carbamate (viscosity average molecular weigh 10.2 * 10
4) be dispersed in 9.43 * 10
4In the gram 7.0wt%NaOH/0.8wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-12 ℃, take out from refrigerator the freezing back that finishes, and 48 ℃ of environmental conditions are thawed, and stir just to obtain the 5.70wt% cellulose carbamate solution.
B, the cellulose carbamate solution that dissolving is obtained filter, the vacuum standing and defoaming is handled; Gas pressure intensity is 0.8MPa during filtration, and filter cloth is that fineness is 350 purpose nylon cloths, and deaeration vacuum is 0.03MPa; Time is 6 hours, obtains the used cellulose carbamate spinning solution of spinning.
C, with spinning solution compressed nitrogen suppress and measuring pump suction and pumping effect under extrude solidification forming in the solid bath of acid cure through spinneret orifice, after being stretching in water and drenching district's washing through the washing roller again, at last through oiling, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.40MPa, and spinning head is 0.14mm * 75 holes, and acid bath consists of the 7.21wt% aqueous sulfuric acid, and coagulation bath temperature is 21 ℃, and strand Immersion time in acid bath is 0.03s; Solidifying the roller rotating speed is 35m/min, and the washing roller is 1.07 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 45 ℃; Oil bath temperature is 51 ℃, and bake out temperature is 75 ℃; The dried fracture strength of the regenerated celulose fibre that wet spinning obtains is 1.58cN/dtex, and wet breaking strength is 0.60cN/dtex, and dried elongation at break is 8.49%, and residual sulphur, residual zinc amount are 0, and the dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 10
A, to get 550 gram nitrogen contents be 2.089% cellulose carbamate (viscosity average molecular weigh 10.7 * 10
4) be dispersed in 9.45 * 10
4In the gram 8.0wt%NaOH/1.8wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-11 ℃, take out from refrigerator the freezing back that finishes, and thaws, stirs under 50 ℃ of conditions just to obtain the 5.5wt% cellulose carbamate solution.
B, the cellulose carbamate solution that dissolving is obtained filter, the vacuum standing and defoaming is handled; Gas pressure intensity is 0.5MPa during filtration, and filter cloth is that fineness is 300 purpose cottons, and deaeration vacuum is 0.015MPa; Time is 8 hours, obtains the used cellulose carbamate spinning solution of spinning.
C, with spinning solution compressed air suppress and measuring pump suction and pumping effect under extrude solidification forming in the solid bath of acid cure through spinneret orifice, after being stretching in water and drenching district's washing through the washing roller again, at last through oiling, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.30MPa, and spinning head is 0.12mm * 75 holes, and acid bath consists of the 6.02wt% sulfuric acid solution, and temperature is 20 ℃, and strand Immersion time in acid bath is 0.03s; Solidifying the roller rotating speed is 35m/min, and the washing roller is 1.07 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 29 ℃; Oil bath temperature is 46 ℃, and bake out temperature is 76 ℃; The dried fracture strength of the regenerated celulose fibre that wet spinning obtains is 1.55cN/dtex, and wet breaking strength is 0.54cN/dtex, and dried elongation at break is 7.57%, and residual sulphur, residual zinc amount are 0, and the dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 11
A, to get 650 gram nitrogen contents be 1.163% cellulose carbamate (viscosity average molecular weigh 5.8 * 10
4) be dispersed in 9.35 * 10
4In the gram 9.0wt%NaOH/2.5wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-24 ℃, take out from refrigerator the freezing back that finishes, and 50 ℃ of environmental conditions are thawed, and stir just to obtain the 6.5wt% cellulose carbamate solution.
B, the cellulose carbamate solution that dissolving is obtained filter, the vacuum standing and defoaming is handled; Gas pressure intensity is 0.4MPa during filtration, and filter cloth is that fineness is 350 purpose cottons, and deaeration vacuum is 0.025MPa; Time is 12 hours, obtains the used cellulose carbamate spinning solution of spinning.
C, with spinning solution compressed nitrogen suppress and measuring pump suction and pumping effect under extrude solidification forming in the solid bath of acid cure through spinneret orifice, after being stretching in water and drenching district's washing through the washing roller again, at last through oiling, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.40MPa, and spinning head is 0.08mm * 100 holes, and acid bath consists of the 4.8wt% sulfuric acid solution, and temperature is 22 ℃, and strand Immersion time in acid bath is 0.03s; Solidifying the roller rotating speed is 35m/min, and the washing roller is 1.07 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 41 ℃; Oil bath temperature is 45 ℃, and bake out temperature is 74 ℃; The dried fracture strength of the regenerated celulose fibre that wet spinning obtains is 1.62cN/dtex, and wet breaking strength is 0.57cN/dtex, and dried elongation at break is 10.29%, and residual sulphur, residual zinc amount are 0, and the dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 12
A, to get 750 gram nitrogen contents be 1.163% cellulose carbamate (viscosity average molecular weigh 5.8 * 10
4) be dispersed in 9.25 * 10
4In the gram 6.5wt%NaOH/0.5wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-12 ℃, take out from refrigerator the freezing back that finishes, and thaws, stirs under 45 ℃ of environmental conditions just to obtain the 7.5wt% cellulose carbamate solution.
B, the cellulose carbamate solution that dissolving is obtained filter, the vacuum standing and defoaming is handled; Gas pressure intensity is 0.6MPa during filtration; Filter cloth is that fineness is 300 purpose nylon cloths; Deaeration vacuum is 0.01MPa, and the time is 15 hours, obtains the used cellulose carbamate spinning solution of spinning.
C, with spinning solution compressed air suppress and measuring pump suction and pumping effect under extrude solidification forming in the solid bath of acid cure through spinneret orifice, after being stretching in water and drenching district's washing through the washing roller again, at last through oiling, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.80MPa, and spinning head is 0.12mm * 50 holes, and acid bath consists of the 7.21wt% sulfuric acid solution, and temperature is 20 ℃, and strand Immersion time in acid bath is 0.03s; Solidifying the roller rotating speed is 35m/min, and the washing roller is 1.07 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 41 ℃; Oil bath temperature is 46 ℃, and bake out temperature is 90 ℃; The dried fracture strength of the regenerated celulose fibre that wet spinning obtains is 1.49cN/dtex, and wet breaking strength is 0.46cN/dtex, and dried elongation at break is 12.50%, and residual sulphur, residual zinc amount are 0, and the dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 13
A, to get 500 gram nitrogen contents be 1.009% cellulose carbamate (viscosity average molecular weigh 7.8 * 10
4) be dispersed in 9.50 * 10
4In the gram 6.0wt%NaOH/0.1wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-15 ℃, take out from refrigerator the freezing back that finishes, and thaws, stirs under 30 ℃ of environmental conditions just to obtain the 5.0wt% cellulose carbamate solution.
B, the cellulose carbamate solution that dissolving is obtained filter, the vacuum standing and defoaming is handled; Gas pressure intensity is 0.5MPa during filtration, and filter cloth is that fineness is 350 purpose cottons, and deaeration vacuum is 0.02MPa; Time is 10 hours, obtains the used cellulose carbamate spinning solution of spinning.
C, with spinning solution compressed nitrogen suppress and measuring pump suction and pumping effect under extrude solidification forming in the solid bath of acid cure through spinneret orifice, after being stretching in water and drenching district's washing through the washing roller again, at last through oiling, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.30MPa, and spinning head is 0.08mm * 75 holes, and acid bath consists of the 7.21wt% sulfuric acid solution, and temperature is 21 ℃, and strand Immersion time in acid bath is 0.03s; Solidifying the roller rotating speed is 35m/min, and the washing roller is 1.07 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 32 ℃; Oil bath temperature is 50 ℃, and bake out temperature is 75 ℃; The dried fracture strength of the regenerated celulose fibre that wet spinning obtains is 1.50cN/dtex, and wet breaking strength is 0.57cN/dtex, and dried elongation at break is 8.61%, and residual sulphur, residual zinc amount are 0, and the dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 14
A, to get 800 gram nitrogen contents be 1.2% cellulose carbamate (viscosity average molecular weigh 5.5 * 10
4) be dispersed in 9.20 * 10
4In the gram 10.0wt%NaOH/3.0wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-14 ℃, take out from refrigerator the freezing back that finishes, and 40 ℃ of environmental conditions are thawed, and stir just to obtain the 8.0wt% cellulose carbamate solution.
B, the cellulose carbamate solution that dissolving is obtained filter, the vacuum standing and defoaming is handled; Gas pressure intensity is 0.6MPa during filtration; Filter cloth is that fineness is 300 purpose nylon cloths; Deaeration vacuum is 0.025MPa, and the time is 18 hours, obtains the used cellulose carbamate spinning solution of spinning.
C, with spinning solution compressed air suppress and measuring pump suction and pumping effect under extrude solidification forming in the solid bath of acid cure through spinneret orifice, after being stretching in water and drenching district's washing through the washing roller again, at last through oiling, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.50MPa, and spinning head is 0.08mm * 75 holes, and acid bath consists of the 7.21wt% sulfuric acid solution, and temperature is 21 ℃, and strand Immersion time in acid bath is 0.03s; Solidifying the roller rotating speed is 35m/min, and the washing roller is 1.07 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 41 ℃; Oil bath temperature is 45 ℃, and bake out temperature is 74 ℃; The dried fracture strength of the regenerated celulose fibre that wet spinning obtains is 1.51cN/dtex, and wet breaking strength is 0.48cN/dtex, and dried elongation at break is 13.27%, and residual sulphur, residual zinc amount are 0, and the dye uniformity ash card rank of the ankle socks that establishment obtains is 4.
Embodiment 15
A, to get 500 gram nitrogen contents be 0.50% cellulose carbamate (viscosity average molecular weigh 10.7 * 10
4) be dispersed in 9.50 * 10
4In the gram 8.0wt%NaOH/2.0wt%ZnO aqueous solution, put into refrigerator and cooled and freeze to-12 ℃, take out from refrigerator the freezing back that finishes, and 35 ℃ of environmental conditions are thawed, and stir just to obtain the 5.0wt% cellulose carbamate solution.
B, the cellulose carbamate solution that dissolving is obtained filter, the vacuum standing and defoaming is handled; Gas pressure intensity is 0.3MPa during filtration; Filter cloth is that fineness is 300 purpose nylon cloths; Deaeration vacuum is 0.025MPa, and the time is 8 hours, obtains the used cellulose carbamate spinning solution of spinning.
C, with spinning solution compressed nitrogen suppress and measuring pump suction and pumping effect under extrude solidification forming in the solid bath of acid cure through spinneret orifice, after being stretching in water and drenching district's washing through the washing roller again, beat to twist with the fingers and get into the collection of high speed centrifugation jar.The spinning cake of collecting through compress and wash, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.50MPa, and spinning head is 0.12mm * 50 holes, and acid bath consists of the 10wt% sulfuric acid solution, and temperature is 40 ℃, and strand Immersion time in acid bath is 0.04s; Solidifying the roller rotating speed is 27m/min, and the washing roller is 1.02 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 33 ℃; The regenerated celulose fibre that finally prepares has higher intensity.
Embodiment 16
The preparation process of cellulose carbamate spinning solution is as embodiment 14.
With spinning solution compressed air suppress and measuring pump suction and pumping effect under extrude solidification forming in the solid bath of acid cure through spinneret orifice, after being stretching in water and drenching district's washing through the washing roller again, beat to twist with the fingers and get into the collection of high speed centrifugation jar.The spinning cake of collecting through compress and wash, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.20MPa, and spinning head is 0.08mm * 50 holes, and acid bath consists of the 12wt% sulfuric acid solution, and temperature is 35 ℃, and strand Immersion time in acid bath is 0.03s; Solidifying the roller rotating speed is 39m/min, and the washing roller is 1.05 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 34 ℃; The regenerated celulose fibre that finally prepares has higher intensity.
Embodiment 17
The preparation process of cellulose carbamate spinning solution is as embodiment 14.
With spinning solution compressed nitrogen suppress and measuring pump suction and pumping effect under extrude solidification forming in the solid bath of acid cure through spinneret orifice, after being stretching in water and drenching district's washing through the washing roller again, beat to twist with the fingers and get into the collection of high speed centrifugation jar.The spinning cake of collecting through compress and wash, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.60MPa, and spinning head is 0.08mm * 75 holes, and acid bath consists of the 8wt% sulfuric acid solution, and temperature is 18 ℃, and strand Immersion time in acid bath is 0.03s; Solidifying the roller rotating speed is 50m/min, and the washing roller is 1.02 with the commentaries on classics degree ratio that solidifies roller, and washing temperature is 28 ℃; The regenerated celulose fibre that finally prepares has higher intensity.
Embodiment 18
The preparation process of cellulose carbamate spinning solution is as embodiment 14.
With spinning solution compressed air suppress and measuring pump suction and pumping effect under extrude solidification forming in the solid bath of acid cure through spinneret orifice, after being stretching in water and drenching district's washing through the washing roller again, beat to twist with the fingers and get into the collection of high speed centrifugation jar.The spinning cake of collecting through compress and wash, drying can obtain cellulose carbamate fibre.Wherein the fluid reservoir gas pressure intensity is 0.80MPa, and spinning head is 0.08mm * 100 holes, coagulating bath consist of 6wt% sulfuric acid, 5wt% zinc sulfate, 12wt% sodium sulphate and water, temperature is 32 ℃, strand Immersion time in acid bath is 0.02s; Solidifying the roller rotating speed is 44m/min, and the washing roller is 0.9 with the rotating ratio that solidifies roller.Washing temperature is 32 ℃; The regenerated celulose fibre that finally prepares has higher intensity.
Claims (6)
1. one kind prepares the method for regenerated celulose fibre by cellulose carbamate, and its characteristic exists:
Cellulose carbamate is dissolved in the aqueous solution that contains 6-10 wt% NaOH, 0.1-3 wt% zinc oxide; Be refrigerated to-10 ° below the C; Under the condition that is not higher than 50 ° of C, thaw then; Obtain cellulose carbamate solution, after filtration, the deaeration, obtain the cellulose carbamate spinning solution; Carry out wet spinning, strand obtains regenerated celulose fibre after supersolidification, washing, drying.
2. method according to claim 1 is characterized in that, the aqueous solution of dissolving cellulos carbamate contains the aqueous solution of 7-8 wt% NaOH, 1.2-1.8 wt% zinc oxide.
3. method according to claim 1 and 2 is characterized in that, described wet spinning is the cellulose carbamate spinning solution to be clamp-oned in the coagulating bath through spinning head solidify.
4. method according to claim 3 is characterized in that, the aperture of used spinning head is 0.08-0.14 mm, and hole count is the 30-100 hole.
5. method according to claim 3 is characterized in that, the consisting of of described coagulating bath: the sodium sulphate of the sulfuric acid of 4.8-12 wt%, the zinc sulfate of 0-5wt%, 0-21 wt%, remainingly be water.
6. method according to claim 3 is characterized in that, coagulation bath temperature is 15-40 ° of C, and the time of strand submergence in coagulating bath is 0.02-0.04 s.
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| CN103012822A (en) * | 2012-12-11 | 2013-04-03 | 武汉大学 | Method for preparing regenerated cellulose membrane using cellulose carbamate |
| CN103233290A (en) * | 2013-04-12 | 2013-08-07 | 湖北天思科技股份有限公司 | Preparation method for cellulose carbamate fiber tow for cigarette |
| CN103319737A (en) * | 2013-06-21 | 2013-09-25 | 武汉大学 | Preparation method of cellulose/zinc oxide nanoparticle composite material |
| CN104195662A (en) * | 2013-11-10 | 2014-12-10 | 湖北金环股份有限公司 | CC cellulose filament producing method by semicontinuous spinning |
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| CN106702515A (en) * | 2015-09-17 | 2017-05-24 | 宜宾丝丽雅集团有限公司 | Production technology of cellulose carbamate fiber filaments |
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