CN101328626A - Method for continuously preparing regenerated cellulose fibre - Google Patents

Method for continuously preparing regenerated cellulose fibre Download PDF

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CN101328626A
CN101328626A CNA2007101176839A CN200710117683A CN101328626A CN 101328626 A CN101328626 A CN 101328626A CN A2007101176839 A CNA2007101176839 A CN A2007101176839A CN 200710117683 A CN200710117683 A CN 200710117683A CN 101328626 A CN101328626 A CN 101328626A
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methylimidazole
radical
spinning
cellulose
ionic liquid
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武进
王三元
张军
王东兴
魏广信
何嘉松
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Baoding Swan Co ltd
Institute of Chemistry CAS
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Baoding Swan Co ltd
Institute of Chemistry CAS
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    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
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    • Y02P70/62Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Abstract

The invention discloses a method for continuously preparing regenerated cellulose fibers through the solvent method, comprising the following steps that: a cellulose raw material is dissolved into an ion liquid to prepare a spinning liquid; gel type regenerated cellulose fibers are obtained through spinning; and the regenerated cellulose fibers are obtained through cleaning, rear draft and drying, wherein, the ion liquid is selected from one or a plurality among the following ion liquids: a). an ion liquid with 1, 3-dialkyl imidazole as a cation and formiate radical, radical vinegar or propionate radical as an anion; and b). an ion liquid with 1-R1-3-R2- dialkyl imidazole as the cation and chlorine, bromine, iodine, formiate radical, radical vinegar, sulfate radical, nitrate radical, tetrafluoroborate radical, thiocyanate radical, hexafluorophosphate radical, p-toluenesulfonate radical or trifluoromethanesulfonic acid radical as the anion. The method has the advantages of wide technological range, mild temperature condition, adequate pressure, quick spinning speed and so on, can prepare the regenerated cellulose fibers with superior performance and complete specifications, and has low production cost, high production efficiency and wide application prospect.

Description

A kind of continuous method for preparing regenerated celulose fibre
Technical field
The present invention relates to the method that a kind of solvent method prepares regenerated celulose fibre continuously, specifically, relating to a kind of is the method that solvent prepares regenerated celulose fibre continuously with the low-viscosity ionic liquid.
Background technology
Along with the increase of industrial capacity, mineral resources such as oil are difficult to satisfy the human following demand day by day, and therefore reproducible natural resources have more and more important position.Cellulose is a natural polymer the abundantest on the earth, and it is significant for the mankind's sustainable development to make full use of cellulose resource.
At present, make the field at chemical fibre, utilizing cellulosic mode mainly is so-called adhering process, be about to preparation of cellulose and become alkali cellulose, after aging, carry out chemical reaction with carbon disulfide, generate cellulose xanthate ester, cellulose xanthate ester is dissolved in the alkaline solution, maturation is after deaeration, filtration, spray silk in acid bath, solidification forming, cellulose xanthate ester resolves into cellulose again simultaneously, and then stretch, wash, oil at last, batch or post processing such as cut-out, prepare long fibre of regenerated cellulose or short fiber.
The adhering process technology maturation, but pollute greatly, and waste water is many, the energy consumption height.In order to seek better cellulose fibre manufacture method, the spinning of cellulose direct solvent method is subjected to attention more and more widely.So-called cellulosic direct solvent, be exactly in course of dissolution not with the solvent of cellulose generation chemical reaction.Cellulose still keeps original molecular structure in this solvent, i.e. dissolving only causes physical change to cellulose, does not cause chemical change.Cellulosic direct solvent has had been found that a variety of now, but because the problem of aspects such as toxicity, corrosivity, recovery, many cellulose direct solvent are not suitable for industrial production, the real cellulose direct solvent that has obtained industrial utilization has only NMMO (N-methylmorpholine N-oxide) system, but this technology is still immature at present.
Patent WO 2006/000197 A1 discloses with 1, and 3-dialkylimidazolium haloid ionic liquid is the method that solvent prepares regenerated celulose fibre and regenerated cellulose film.But, 1, ion liquid fusing point of 3-dialkylimidazolium haloid and viscosity are very high, and its fusing point makes in preparation process about 100 ℃ like this, needs higher temperature and lower cellulose concentration, the production cost height, production efficiency is low.
Summary of the invention
The purpose of this invention is to provide the method that ionic liquid prepares regenerated celulose fibre.
The method of utilizing ionic liquid to prepare regenerated celulose fibre provided by the present invention, be that cellulosic material is dissolved in the ionic liquid, obtain spinning solution, spinning obtains the regenerated celulose fibre of gel state, pass through washing, first break draft and oven dry again, obtain regenerated celulose fibre, wherein, ionic liquid is selected from one or more in the following following ionic liquid:
A) CATION is 1, the 3-dialkylimidazolium, and anion is the ionic liquid of formate, acetate or propionate; Wherein, alkyl is the alkyl that contains 1-8 carbon atom;
B) CATION is 1-R 1-3-R 2-dialkyl imidazoles, anion are selected from the ionic liquid of chlorine, bromine, iodine, formate, acetate, propionate, sulfate radical, nitrate radical, tetrafluoroborate, thiocyanate radical, hexafluoro-phosphate radical, p-methyl benzenesulfonic acid root and TFMS root; Wherein, R 1For meeting the alkyl of following rule: 1. contain 2 carbon atoms at least, 3. 2. no more than 20 carbon atoms contain a two key at least; R 2For containing the saturated or undersaturated alkyl of 1~4 carbon atom.
Preferably, ionic liquid is selected from following ionic liquid or its mixture: 1-ethyl-3-methylimidazole formates, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole propionate, 1-propyl group-3-methylimidazole formates, 1-propyl group-3-methylimidazole acetate, 1-propyl group-3-methylimidazole propionate, 1-butyl-3-methylimidazole formates, 1-butyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole propionate, 1-allyl-3-methylimidazole villaumite, 1-allyl-3-methylimidazole formates, 1-allyl-3-methylimidazole acetate, 1-allyl-3-methylimidazole propionate, 1-allyl-3-methylimidazole sulfate, 1-methacrylic-3-methylimidazole villaumite, 1-methacrylic-3-methylimidazole formates, 1-methacrylic-3-methylimidazole acetate, 1-methacrylic-3-methylimidazole propionate, 1-methacrylic-3-methylimidazole sulfate.
In order to reduce the viscosity of spinning solution, also can be added with complex solvent in the ionic liquid, complex solvent is 5~40% of an ionic liquid weight; Described complex solvent is selected from one or more in dimethyl sulfoxide (DMSO), dimethyl formamide, the dimethylacetylamide.
In the present invention, cellulosic average degree of polymerization is 200~3000 in the spinning solution, and mass concentration is 3~30%; Preferably, cellulosic average degree of polymerization is 250~1500 in the spinning solution, and mass concentration is 5~25%.The temperature of spinning solution is 40~180 ℃, and viscosity is 50~10000Pas; Preferably, the temperature of spinning solution is 60~160 ℃, and viscosity is 100~5000Pas.
Use the inventive method, the regenerated celulose fibre that spinning obtains gel state adopts dry-jet wet spinning process to carry out, be spinning solution to be pressed through the spinning appts that has some spinneret orifices enter air, experience stretches in air, enter coagulating bath then and solidify, obtain the regenerated celulose fibre of gel state.
Wherein, orifice diameter is 0.05~1mm, and spray silk pressure is 0.5~4MPa, and spray silk speed is 10~200 meters/minute, and the distance from the spinneret orifice to the coagulating bath is 0.005~0.5 meter, and draw ratio is 1~200; Preferably, orifice diameter is 0.05~0.5mm, and spray silk speed is 20~100 meters/minute, and the distance from the spinneret orifice to the coagulating bath is 0.05~0.3 meter, and draw ratio is 5~100.Coagulating bath is for containing the ion liquid aqueous solution of 0~70% weight, and the temperature of coagulating bath is 10~50 ℃.
Wash at the regenerated celulose fibre that spinning is obtained gel state, when first break draft and oven dry, washing is that washing agent gets final product with water; The multiple of first break draft is 1~5 times, and the first break draft number of times is 0~3 time; Bake out temperature is 80~200 ℃.
The present invention by screening have low melting point, low-viscosity ionic liquids carries out spinning as cellulosic direct solvent, temperature in the time of can reducing cellulose dissolution, spinning, and can improve the concentration of spinning solution, make spinning process condition gentle more, and, process parameters range is wide, has increased the convenience and the controllability of spinning technique.Advantage such as the inventive method has that processing range is wide, temperature conditions is gentle, moderate pressure, spinning speed are fast can processability regenerated celulose fibre good, complete in specifications, and production cost is low, and the production efficiency height has a extensive future.
The specific embodiment
The present invention utilizes ionic liquid to prepare the method for regenerated celulose fibre, be with cellulose dissolution in low-viscosity, low-melting ionic liquid, form cellulose/ionic liquid solution as spinning solution, then, with the spinning solution spinning, can obtain regenerated celulose fibre.Spinning technique has multiple, generally can select dry-jet wet spinning process for use: the spinning solution that is squeezed is entered air from the spinning appts that has some apertures, experience stretches in air, enter coagulating bath then, in coagulating bath, solidify, obtain the regenerated celulose fibre of gel state, pass through washing, first break draft and oven dry again, can obtain regenerated celulose fibre.
In the present invention, spinning solution mainly is made up of ionic liquid and cellulose.Cellulosic kind comprises that the purity of bacteria cellulose, cotton, absorbent cotton, cotton linter, the cotton pulp dregs of rice, wood pulps, bamboo pulp, microcrystalline cellulose and fiber crops, straw, wheat stalk, cotton stalk, maize straw, bagasse and the medium extraction of various grass reaches 90% above cellulose.These cellulosic degree of polymerization are different according to the source, the degree of polymerization as microcrystalline cellulose is 180~250, the degree of polymerization of bamboo pulp is 450~550, the degree of polymerization of the wood oar dregs of rice is 550~650, the degree of polymerization of the cotton pulp dregs of rice is 800~1000, the degree of polymerization of absorbent cotton is 1500~3000, and the degree of polymerization of bacteria cellulose is 100,000~1,000,000.Cellulosic material with different molecular weight is arranged in pairs or groups, and can make cellulosic average degree of polymerization is arbitrary value between 180~3000.Employed ionic liquid is selected from the ionic liquid of following kind:
A) CATION is 1, the 3-dialkylimidazolium, and anion is the ionic liquid of formate, acetate or propionate; Wherein, alkyl is the alkyl that contains 1-8 carbon atom;
B) CATION is 1-R 1-3-R 2-dialkyl imidazoles, anion are selected from the ionic liquid of chlorine, bromine, iodine, formate, acetate, propionate, sulfate radical, nitrate radical, tetrafluoroborate, thiocyanate radical, hexafluoro-phosphate radical, p-methyl benzenesulfonic acid root and TFMS root; Wherein, R 1For meeting the alkyl of following rule: 1. contain 2 carbon atoms at least, 3. 2. no more than 20 carbon atoms contain a two key at least; R 2For containing the saturated or undersaturated alkyl of 1~4 carbon atom.
These ionic liquids have lower fusing point, generally below 20 ℃; Preferably, ionic liquid is AMIMCl (a 1-allyl-3-methylimidazole villaumite), and its fusing point is about 17 ℃; EMIMAc (1-ethyl-3-methylimidazole acetate), AMIMAc (1-allyl-3-methylimidazole acetate), and BMIMAc (1-butyl-3-methylimidazole acetate), their fusing point is far below 0 ℃; Other ionic liquids are keeping liquid always more than 0 ℃.
When adopting dry-jet wet spinning process to carry out spinning, the spinnability of spinning solution is relevant with the viscosity of spinning solution and temperature.Find that in experiment under 40 ℃, viscosity is low to moderate the solution of 10Pas, the microcrystalline cellulose cellulose solution as 4% just can spinning, but fibre strength is relatively poor.Viscosity increases to 100Pas (40 ℃), and the microcrystalline cellulose cellulose solution as 8% just can access intensity fiber preferably.The high viscosity that practical operation allows is relevant with spinning jet used aperture, and the aperture is big more, and spinnable solution viscosity is big more.In our research, the The hole diameter of spinneret of use is 1mm to the maximum, and the enough viscositys of energy are up to the solvent spinning of 100,000 Pas.Generally can select the aperture of spinnerets according to the viscosity of spinning solution, the The hole diameter of spinneret of recommendation and spinning solution viscosity relation see Table 1.
Table 1. The hole diameter of spinneret and spinning solution viscosity
The hole diameter of spinneret (mm) The spinning solution viscosity scope (Pas) that is suitable for
0.05 20~2000
0.1 50~4000
0.2 100~8000
0.5 300~25000
1 500~100000
The viscosity of spinning solution (all herein equal nullings of viscosity data are cut viscosity) determines jointly that by the cellulosic degree of polymerization, concentration of dope and temperature exemplary value sees Table 2.Along with concentration increases, the viscosity of cellulose/AMIMCl solution increases sharply, and is 1500 absorbent cotton solution as the degree of polymerization, and solution concentration progressively increased to 16% o'clock from 1%, and viscosity progressively is increased to greater than 300,000 Pas from 190Pas.The height of cellulosic degree of polymerization also has significant impact to viscosity, is 1500 as the degree of polymerization, and concentration is 8% cellulose solution, and viscosity is greater than 40000Pas in the time of 80 ℃; And under the uniform temp, the degree of polymerization is 600 8% solution, and viscosity is about 2500Pas.Temperature is also very big to the influence of the viscosity of solution, is 600 8% cellulose solution as the degree of polymerization, and viscosity is about 23000Pas in the time of 40 ℃, and when temperature rose to 100 ℃, viscosity drop was low to moderate about 500Pas.According to this Changing Pattern of viscosity, can in bigger scope, regulate the prescription and the spray silk temperature of spinning solution.Comparatively ideal spinning solution viscosity is 50~10000Pas (under the spray silk temperature), better, is 100~5000Pas (under the spray silk temperature).
The relation of the table 2. spinning solution viscosity and the degree of polymerization, concentration, temperature (ionic liquid is AMIMCl)
Figure A20071011768300071
Figure A20071011768300081
In order to prepare the suitable spinning solution of viscosity, crucial alternative condition is cellulose concentration and a cellulosic degree of polymerization in the spinning solution.Concentration is low to moderate 1% absorbent cotton solution can be 60 ℃ of smooth spinning down, and concentration also can spinning under 160~180 ℃ up to 30% microcrystalline cellulose cellulose solution.Concentration is high more, and production efficiency is high more; The degree of polymerization is big more, and is favourable more to improving product quality.Therefore concentration of dope should be more than 5% preferably, but is advisable to be no more than 25%.According to the various combination of raw material, the cellulosic degree of polymerization can change arbitrarily between 180~3000.Because spinning temperature can not improve arbitrarily, the degree of polymerization is high more, and suitable concentration is just low more.Take all factors into consideration the factor of each side, preferred spinning solution prescription is: cellulose concentration 5%~25%, the degree of polymerization 250~1500.
In order to reduce the viscosity of spinning solution, also can be added with complex solvent in the ionic liquid, complex solvent is 5~40% of an ionic liquid weight; Complex solvent is selected from dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide.Also can be added with functional material in the spinning solution, functional material is selected from anti ultraviolet agent, antiseptic, fire retardant, imvite, CNT, shitosan and medical stone; The addition of functional material is 0.01~10% of a cellulose.
It is the process of a multi-parameter that spinning solution is sprayed silk, and main parameter has: spray silk temperature, spray silk pressure, The hole diameter of spinneret, gas length (distance from spinneret orifice to coagulating bath) and draw ratio (being the ratio of the linear velocity and the spinneret orifice spray silk speed of first drawing roller after the coagulating bath).
The viscosity of spray silk temperature effect spinning solution, generally the way with elevated temperature reduces viscosity.The spinning solution temperature can not unrestrictedly improve.Be the cellulose obvious degradation of avoiding at high temperature causing, the spinning solution temperature should not be above 200 ℃.In our experiment, spinning temperature commonly used is 60,80,100,120,140 ℃.For the cellulose solution spinning of high concentration, high polymerization degree, can consider to use 150~180 ℃ high temperature.
When selecting The hole diameter of spinneret, consider to spray the restriction of a pressure and the requirement of fibre number.Though the aperture all can be used at the spinnerets of 0.05~1mm, more satisfactory pore diameter range is between 0.05~0.5mm.
After silk temperature, The hole diameter of spinneret are formed, sprayed to selected spinning solution, spray silk pressure had determined a spray speed.When, The hole diameter of spinneret lower when the spinning solution viscosity was big, it is thread next that the pressure of 0.2MPa just can spray.The slowest spray silk speed can be low to moderate 0.5 meter/minute.Under preferred spinning condition, spray silk pressure is between 0.5MPa~4MPa usually, and spray this moment silk speed can change between 10~200 meters/minute.For ease of drawing-off,, usually spray silk speed is controlled between 20~100 meters/minute by regulating spray silk temperature and pressure.
The bound of gas length is decided by operation factors.For the fluctuation of avoiding coagulating bath touches spinnerets, the air gap minimum of a value is 5mm, and the air gap maximum is 0.5 meter, and operation is just not very convenient when bigger.When using the porous spinnerets, air gap is big more, and fiber is easy more to stick together.Practical air gap scope is 5~30 centimetres, and gas length preferably is no more than 20 centimetres when using the porous spinnerets.
The draw ratio of cellulose/ion liquid spinning system can be less than 1, because the extrusion swelling phenomenon, minimum draw ratio can be 0.1, but does not have application value less than 1 draw ratio, and bigger draw ratio, helps improving the intensity of fiber.The choose reasonable spinning condition can obtain very big draw ratio.As use 10% pulp solution, 0.5mm spinnerets and 50cm air gap, and under 100 ℃, with the pressure spinning of 0.3MPa, spray silk speed is 0.5 meter/minute, and draft speed can reach 100m/ minute, and draw ratio is up to 200.Though high draft requires to have big air gap than helping increasing the spinneret orifice footpath, reducing spray silk speed and spray silk pressure, causes fiber adhesion when using the porous spinnerets easily.Therefore draw ratio preferably is controlled between 1~100, is 3~30 preferably, is 5~20 better.
In dry-jet wet spinning process, can adopt the way of lateral blowing to add the fastfiber cooling in the air gap section.When the spinnerets hole count was less than 20, air-cooled do not have positive effect to improving spinning technique.When hole count was very high, air-cooled ability had certain effect to the stability that improves technology.
After the spinning solution thread of spinneret orifice ejection stretches, in coagulating bath, be frozen into the as-spun fibre of gel state air gap.Coagulating bath should be can dissolved ions liquid, makes cellulose regenerated solvent, such as water, ethanol, methyl alcohol, carrene, chloroform etc.Consider from the economy and the feature of environmental protection, be preferably water.Along with the prolongation of spinning time, the ionic liquid content in the coagulating bath increases gradually.When the weight ratio of ionic liquid in coagulating bath reached 70%, fiber still can solidify rapidly.When the weight ratio of ionic liquid in coagulating bath reached 80%, the fiber curing rate was slack-off, and this moment, draft speed can not surpass 20 meter per seconds.Therefore, can select to contain the ion liquid aqueous solution of 0~70% weight is coagulating bath.The temperature of coagulating bath can have very big adjusting range, can change between the boiling point in freezing point.But consider that from practical standpoint the temperature of coagulating bath should be near room temperature.Consider the utilization of used heat, coagulation bath temperature should be comparatively favourable between 15~50 ℃, generally can be at 10~30 ℃.
It is the important method that improves fibre strength, improves fiber quality that the fiber of primary solidification is carried out that first break draft handles.In discovering, the first break draft multiple that spinning system of the present invention can reach is relevant with the multiple of a drawing-off of carrying out in air gap.One time drafting multiple is high more, and the multiple that first break draft can reach is low more.Multiple as a drawing-off is 0.1 o'clock, and the multiple that can reach of first break draft is 2.2, and maximum is no more than 2.5; A drawing-off is 10 o'clock, and the multiple that first break draft can reach is 1.3, and maximum is no more than 1.5; A drawing-off is greater than 30 the time, and the multiple of first break draft is 1~1.1, promptly can not carry out first break draft basically.
Based on the above fact, when using spinning solution system of the present invention and carrying out dry-jet wet-spinning, feasible process conditions scope is: the spinning solution temperature is 40~180 ℃, the spinning solution viscosity is 50~10000Pas, orifice diameter is 0.05~1mm, spray silk speed is 10~200 meters/minute, and the length of (being air gap) is 0.005~0.5 meter from the spinneret orifice to the coagulating bath, and draw ratio is 1~200.Processing range is preferably: the spinning solution temperature is 60~160 ℃, the spinning solution viscosity is 100~5000Pas, and orifice diameter is 0.05~0.5mm, and spray silk speed is 20~100 meters/minute, the length of (being air gap) is 0.05~0.3 meter from the spinneret orifice to the coagulating bath, and draw ratio is 5~100.
Cellulose concentration is generally 3%~30% (weight) in the spinning solution that uses in the above technology, and the average degree of polymerization of used cellulosic material is general 200~3000.Preferably, concentration of dope is 5%~25%, and the average degree of polymerization of the cellulosic material of preparation spinning solution is 250~1500.
In spinning solution system of the present invention---can also add some solvent in the cellulose/ionic liquid solution, play the effect of further reduction solution viscosity, but not cause Cellulose precipitates.For example, add the dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide of solution weight 15% etc., it is about 40% that solution viscosity is descended, but solution clear still.And used ionic liquid not only can be the ionic liquid of single kind, also can be several ion liquid mixed liquors.For example, add about 40% BMIMCl in AMIMCl, solution viscosity does not only increase, and descends slightly on the contrary.The cellulosic ability of this composite ion liquid dissolving is still fine, and viscosity is suitable with cellulose/AMIMCl solution, and spinning technique is also close.
Utilize cellulose/ion liquid spinning system,,, can also make dyeing, delustring or functional regenerated cellulose fiber by adding dyestuff, pigment, delustering agent or various functional additive except making the crude silk.At the cellulose silk of making dyeing or delustring, spinning technique need not change substantially, because the addition of pigment, dyestuff or delustering agent itself just seldom, the viscosity of spinning system is constant substantially.In cellulose/ionic liquid solution, add various functional form additives,, just can make regenerated cellulose fiber with specific function as anti ultraviolet agent, antiseptic, imvite, CNT, shitosan or medical stone etc.In order spinning technique not to be caused too much influence, the addition of functional additive is generally 0.01~10% of cellulose dry weight.
Use spinning system of the present invention and method and can obtain regenerated cellulose filaments and short silk:
The technology of preparation long filament may further comprise the steps: raw material preparation, mixing, dissolving, filtration, deaeration, spinning, washing and first break draft, dry, oil, coiling etc.
The technology of the short silk of preparation may further comprise the steps: raw material preparation, mixing, dissolving, filtration, deaeration, spinning, washing and first break draft, dry, oil, curl, cut-out, packing etc.
In the raw material preparation process, cellulose is ground into powder, or shredding becomes fluffy state.The purpose of pulverizing or opening fiber element is to increase ionic liquid and soaks into cellulosic speed, makes cellulose easier to be dissolved.The way of using sub-cooled to pulverize can be broken into powder to cellulose powder, perhaps uses opener to be split into the fluffy state that needs to cellulose.Blend step mixes cellulose and ionic liquid.Cellulose is put in the ionic liquid, stirred then and mediate to even.During dissolving, temperature is high more, and dissolution velocity is fast more.But be to use not only energy consumption height of too high solution temperature, and easily cause cellulose degradation and ionic liquid variable color, therefore the highest solution temperature is no more than 200 ℃, and suitable solution temperature is 80~150 ℃.Because the viscosity of high molecular, high concentration cellulose solution is generally very big, and ionic liquid is non-volatile, therefore, deaeration is preferably under the vacuum to be carried out, and vacuum is the highest can be used-0.1MPa.
As previously mentioned, dry-jet wet spinning is adopted in spinning, and concrete parameter is generally: 40~180 ℃ of spray silk temperature, viscosity 100~10000Pas, The hole diameter of spinneret 0.05~0.5mm, spray silk speed is 20~100 meters/minute, 0.005~0.5 meter of gas length, draw ratio 1~200.
The composition of coagulating bath can be for containing the ion liquid aqueous solution of 0~80% weight, and temperature is between 0~90 ℃; Be preferably, concentration is the ion liquid aqueous solution of 0~70% weight, and temperature is 10~50 ℃.3~16 washings of as-spun fibre experience of coming out from coagulating bath are with the ionic liquid in the thorough wash-out fiber.In washing process and after the washing, fiber is carried out 0~3 first break draft, the total stretch ratio of first break draft is 1~5.The baking temperature of fiber is 80~200 ℃, can take the hot-rolling drying, also can take steam drying.
As required, total spinning speed can be adjusted between 50~1000 meters/minute.Can obtain product specification like this is various long filaments and short silk between 0.5~2000dtex.
In process of production, to carrying out conventional filtration, hyperfiltration treatment from the ionic liquid aqueous solution that solidifies, washing procedure reclaims, to remove wherein residual cellulose or other insoluble matter particle of possibility, filtered fluid is handled through decolouring.In conjunction with means such as atmospheric evaporation, multistage flash evaporation, multiple-effect evaporation, thin film evaporation, counter-infiltration, ion-exchanges, perhaps the combination of these means utilization is reclaimed the ionic liquid in the filtered fluid again.By reclaiming, make greater than 99% ionic liquid and realize recycle, and make most of water realize recycle.
Below with specific embodiment technology of the present invention is described.
Embodiment 1~17
Use microcrystalline cellulose, the wooden oar dregs of rice, three kinds of raw materials of absorbent cotton, having prepared mean molecule quantity is 300~800, concentration is at cellulose/AMIMCl solution of 8~18%, after filtration, deaeration carries out dry-jet wet-spinning after handling under various conditions, coagulating bath is that concentration is the AMIMCl aqueous solution of 0~20% (weight).As-spun fibre washs through 6 deionized waters, 80~150 ℃ of oven dry.Place after 48 hours between product fiber constant-temperature house and survey tensile property, each sample is surveyed 10 times, averages.Concrete spray strand spare and product fiber number, TENSILE STRENGTH see Table 3.
Experimental results show that, cellulose/low-viscosity ion liquid system is suitable for carrying out spinning with dry-jet wet-spinning technique, have that processing range is wide, temperature conditions is gentle, advantage such as moderate pressure, spinning speed are fast, can processability regenerated celulose fibre good, complete in specifications.
Simultaneously, experiment shows, just can realize ion liquid recycle by simple reduction vaporization, and the ion liquid rate of recovery can reach more than 99%.
Embodiment 18~35
According to the essentially identical technology of AMIMCl, use 1-ethyl-other low-viscosity ionic liquids such as 3-methylimidazole acetate to carry out the cellulose spinning experiment, typical experimental data is with the results are shown in Table 4.
From these embodiment as can be seen, with to use AMIMCl to do cellulose solvent the same, use these low-viscosity ionic liquids also can spin out regenerated celulose fibre under lower temperature, the gained fibre property is good.
Embodiment 36~40
According to embodiment 1~5 essentially identical technology, use 1-allyl-3-methylimidazole villaumite ionic liquid to be solvent, in cellulose solution, add the different content CNT and carried out the cellulose spinning experiment, typical experimental data is with the results are shown in Table 5, wherein, and cellulose concentration: 8%, cellulosic degree of polymerization: 550, spray silk temperature: 80 ℃, gas length: 5cm, spray silk pressure: 2MPa; Spray silk speed: 40m/s, draft speed: 160m/s, the spinnerets hole count: 1, The hole diameter of spinneret: 0.1mm.
From these embodiment as can be seen, with to use AMIMCl to do cellulose solvent the same, add CNT and can spin out the regenerated celulose fibre with antistatic property in cellulose/ion liquid, the gained fibrous mechanical property is good.
The embodiment of the cellulose of table 5 carbon nanotubes/AMIMCl solution dry-jet wet-spinning
Embodiment CNT is with respect to content of cellulose (weight %) Solution viscosity (Pas) Product fiber number (dtex) TENSILE STRENGTH (cN/dtex) Electrical conductivity (S/cm)
36 1 4400 1.2 2.8 6.3×10 -5
37 3 4850 1.4 3.5 4.76×10 -4
38 5 5730 1.5 4.3 8.33×10 -3
Embodiment 39~41
According to embodiment 1~5 essentially identical technology, use 1-allyl-3-methylimidazole villaumite ionic liquid to be solvent, in cellulose solution, add complex solvent DMSO and carried out the cellulose spinning experiment, typical experimental data is with the results are shown in Table 6, wherein, cellulose concentration: 8%, cellulosic degree of polymerization: 550, spray silk temperature: 80 ℃, gas length: 5cm, spray silk speed: 40m/s, draft speed: 200m/s, the spinnerets hole count: 1, The hole diameter of spinneret: 0.05mm.
From these embodiment as can be seen, to do cellulose solvent the same with independent use AMIMCl, adds complex solvent DMSO and can spin out regenerated celulose fibre equally in cellulose/ion liquid, and the gained fibrous mechanical property is good.Use other complex solvent such as dimethyl formamide, dimethylacetylamide etc. to have same effect, and these complex solvents also can mix use, this does not influence spinning effect yet yet.
Table 6 contains the embodiment of the cellulose/AMIMCl solution dry-jet wet-spinning of complex solvent dimethyl sulfoxide (DMSO) (DMSO)
Embodiment DMSO is with respect to ionic liquid content (weight %) Solution viscosity (Pas) Spray silk pressure (MPa) Product fiber number (dtex) TENSILE STRENGTH (cN/dtex)
39 10 3200 2 1.2 3.2
40 15 2250 1.5 0.9 2.7
41 20 1380 1 0.8 2.5
Figure A20071011768300141
Figure A20071011768300151

Claims (11)

1, a kind of method of utilizing ionic liquid to prepare regenerated celulose fibre, be cellulosic material to be dissolved in form spinning solution in the ionic liquid, spinning obtains the regenerated celulose fibre of gel state, pass through washing, first break draft and oven dry again, obtain regenerated celulose fibre, it is characterized in that: described ionic liquid is selected from one or more in the following following ionic liquid:
A) CATION is 1, the 3-dialkylimidazolium, and anion is the ionic liquid of formate, acetate or propionate; Wherein, alkyl is the alkyl that contains 1-8 carbon atom;
B) CATION is 1-R 1-3-R 2-dialkyl imidazoles, anion are selected from the ionic liquid of chlorine, bromine, iodine, formate, acetate, propionate, sulfate radical, nitrate radical, tetrafluoroborate, thiocyanate radical, hexafluoro-phosphate radical, p-methyl benzenesulfonic acid root and TFMS root; Wherein, R 1For meeting the alkyl of following rule: 1. contain 2 carbon atoms at least, 3. 2. no more than 20 carbon atoms contain a two key at least; R 2For containing the saturated or undersaturated alkyl of 1~4 carbon atom.
2, method according to claim 1, it is characterized in that: described ionic liquid is selected from following ionic liquid or its mixture: 1-ethyl-3-methylimidazole formates, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole propionate, 1-propyl group-3-methylimidazole formates, 1-propyl group-3-methylimidazole acetate, 1-propyl group-3-methylimidazole propionate, 1-butyl-3-methylimidazole formates, 1-butyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole propionate, 1-allyl-3-methylimidazole villaumite, 1-allyl-3-methylimidazole formates, 1-allyl-3-methylimidazole acetate, 1-allyl-3-methylimidazole propionate, 1-allyl-3-methylimidazole sulfate, 1-methacrylic-3-methylimidazole villaumite, 1-methacrylic-3-methylimidazole formates, 1-methacrylic-3-methylimidazole acetate, 1-methacrylic-3-methylimidazole propionate, 1-methacrylic-3-methylimidazole sulfate.
3, method according to claim 1 is characterized in that: also can be added with complex solvent in the described ionic liquid, complex solvent is 5~40% of an ionic liquid weight; Described complex solvent is selected from one or more in dimethyl sulfoxide (DMSO), dimethyl formamide, the dimethylacetylamide.
4, method according to claim 1 is characterized in that: cellulosic average degree of polymerization is 200~3000 in the described spinning solution, and mass concentration is 3~30%; Preferably, cellulosic average degree of polymerization is 250-1500 in the spinning solution, and mass concentration is 5~25%.
5, method according to claim 1, it is characterized in that: described cellulose reaches cellulose more than 90%, the perhaps mixture of these cellulosic materials for the purity extracted from bacteria cellulose, cotton, absorbent cotton, cotton linter, the cotton pulp dregs of rice, wood pulps, bamboo pulp, microcrystalline cellulose and fiber crops, straw, wheat stalk, cotton stalk, maize straw, bagasse and various grass.
6, method according to claim 1 is characterized in that: also be added with functional material in the described spinning solution, functional material is selected from anti ultraviolet agent, antiseptic, fire retardant, imvite, CNT, shitosan and medical stone; The addition of functional material is 0.01~10% of a cellulose.
7, method according to claim 1 is characterized in that: the temperature of spinning solution is 40~180 ℃, and viscosity is 50~10000Pas; Preferably, the temperature of spinning solution is 60~160 ℃, and viscosity is 100~5000Pas.
8, according to the arbitrary described method of claim 1-7, it is characterized in that: the regenerated celulose fibre that spinning obtains gel state adopts dry-jet wet spinning process to carry out, be spinning solution to be pressed through the spinning appts that has some spinneret orifices enter air, experience stretches in air, enter coagulating bath then and solidify, obtain the regenerated celulose fibre of gel state.
9, method according to claim 8 is characterized in that: orifice diameter is 0.05~1mm, and spray silk pressure is 0.5-4MPa, and spray silk speed is 10~200 meters/minute, and the distance from the spinneret orifice to the coagulating bath is 0.005~0.5 meter, and draw ratio is 1~200; Preferably, orifice diameter is 0.05~0.5mm, and spray silk speed is 20~100 meters/minute, and the distance from the spinneret orifice to the coagulating bath is 0.05~0.3 meter, and draw ratio is 5~100.
10, method according to claim 8 is characterized in that: described coagulating bath is for containing the ion liquid aqueous solution of 0~70% weight, and the temperature of coagulating bath is 10~50 ℃.
11, according to the arbitrary described method of claim 1-7, it is characterized in that: described washing is washing agent with water; The multiple of described first break draft is 1~5 times, and the first break draft number of times is 0~3 time; Bake out temperature is 80~200 ℃.
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