CN102432892B - Method for dissolving cellulose and method for preparing regenerated fiber - Google Patents
Method for dissolving cellulose and method for preparing regenerated fiber Download PDFInfo
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- CN102432892B CN102432892B CN 201110223103 CN201110223103A CN102432892B CN 102432892 B CN102432892 B CN 102432892B CN 201110223103 CN201110223103 CN 201110223103 CN 201110223103 A CN201110223103 A CN 201110223103A CN 102432892 B CN102432892 B CN 102432892B
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Abstract
The invention relates to a method for dissolving cellulose, comprising the following steps of: under the condition with the temperature being 0-25 DEG C, firstly mixing the cellulose and a solvent with the weight accounting for 30-70wt% of the total weight of the solvent for dissolving the cellulose uniformly by kneading and shearing; then adding the remaining solvent for dissolving the cellulose at the temperature of 15 below zero to 5 DEG C; and putting the mixture at the temperature of 8 below zero to 25 DEG C, kneading, shearing, mixing uniformly and obtaining cellulose solution. The solvent is water solution containing alkali, urea/thiourea and polyethylene glycol. The method can prevent colloidal particles, micelles and white cores from forming when the cellulose is dissolved, thus leading the cellulose to be well dissolved and obtaining uniform solution; and after the cellulose solution is defoamed, spinning solution is treated by secondary coagulating bath with the coagulating liquid being salt solution to obtain the cellulose fiber, the recovery and utilization cost of the solvent and a coagulating agent is reduced greatly, the rapid coagulation is avoided, the drawing and orientation degree is improved and the regenerated cellulose fiber with better strength is prepared.
Description
Technical field
The present invention relates to a kind of method of dissolving cellulos, and the method for preparing regenerated cellulose fibre.
Background technology
Mierocrystalline cellulose is the abundant natural biological macromolecular materials of nature reserves, but have the characteristics such as recyclability, biological degradability, biocompatibility derivatize, be widely used in the fields such as weaving, papermaking, medical treatment, health, environmental engineering, especially regenerated cellulose fibre, with its unique gloss, good water absorbability and textile processibility, it is important textile fibres always.Yet, owing to existing in very strong molecule in Mierocrystalline cellulose and intermolecular hydrogen bonding, make it can not melting, also be difficult to dissolving, thereby also be far from being fully utilized.
At present, the technical bottleneck that is widely applied of restriction Mierocrystalline cellulose is simple, the free of contamination dissolving of its low cost, process and processing.Over more than 100 year, the serious traditional viscose process of environmental pollution is the main method that regenerated cellulose fibre is produced always.Traditional cuprammonium process is produced the shortcoming that copper ammonia fibre also exists environmental pollution, expensive and difficult solvent recovery.In the last thirty years, although found that many solvents can be directly or by derivatize dissolving cellulos, preparation regenerated cellulose fibre, mostly there are environmental pollution, process is numerous and diverse, high in cost of production is such or such problem in prior art and are difficult to industrialization.At present, more noticeable characteristics among new solvents of cellulose mainly contains the composite aqueous solvent system of N-methyl-N-morpholine oxide, ionic liquid and alkali and urea or other material.
The Lyocell fiber of N-methyl-N-morpholine oxide solvent method, Austrian Lenzing company has formed the approximately throughput of 150,000 ton/years, but because solvent is expensive, the solvent recuperation difficulty is large, the problems such as dissolution conditions is harsh, and the potential safety hazard of solvent blast is large, suitability for industrialized production is made slow progress.
The standby regenerated cellulose fibre of ion liquid solvent legal system still is in development, not yet form industrialization, even pilot scale production, and still there are the problems such as solvent costliness in the method.
Aqueous sodium hydroxide solution is most economical cellosolve, but this solvent only can dissolve the lower Mierocrystalline cellulose of molecular weight, and the regenerated cellulose fibre intensity that makes is very low, and its cellulose solution is very unstable, is easy to gelation, is not suitable for industrial applications.In recent years research finds, alkali (sodium hydroxide or lithium hydroxide)/urea or (with) thiocarbamide/water compounded solvents system can dissolve the larger Mierocrystalline cellulose of molecular weight, and give stability of solution.Adopt alkali/urea or (with) method of thiocarbamide/water compounded solvents system dissolving cellulos, can pass through the freeze-thaw dissolving cellulos, or first with sodium hydroxide or lithium hydroxide aqueous solution pretreatment of fiber element, and then add urea or thiourea solution dissolving, perhaps directly Mierocrystalline cellulose is dissolved in the mixed aqueous solution of cooling sodium hydroxide or lithium hydroxide and urea or thiocarbamide.And further exploration ground is arranged or prepare the method for regenerated cellulose fibre with pilot scale by wet-spinning.The method of sodium hydroxide/sodium zincate/urea mixed aqueous solution solvent system and dissolving cellulos thereof is disclosed in CN 101130605A.Donghua University application is open or reported in cooling alkali (sodium hydroxide or lithium hydroxide)/thiocarbamide/urea mixed aqueous solution dissolving cellulos and prepared the method for regenerated cellulose fibre by wet-spinning.
Above-mentioned sodium hydroxide/sodium zincate/urea mixed aqueous solution solvent system because zine ion is poisonous, has strong toxic to freshwater plant, planktonic organism, is unsuitable for industrial application; Adopt above-mentioned freeze-thaw technical scheme, facts have proved, under freezing conditions (20 ℃) maintenance of mixed slurry of Mierocrystalline cellulose and solvent must be frozen into ice in 3～8 hours, then thaw and to make cellulose solution by dissolving cellulos, also be difficult for industrialization; And for first plain with sodium hydroxide or lithium hydroxide aqueous solution pretreatment of fiber, then add the dissolving of urea or thiourea solution, or directly with Mierocrystalline cellulose cooling alkali (sodium hydroxide or lithium hydroxide)/urea or (with) dissolving and prepare the method for regenerated cellulose fibre in the thiocarbamide mixed aqueous solution, have following deficiency: the time that the solubilized stable liquid state is kept is short, easily form irreversible gel, and temperature drift or on the low sidely all can cause gelation, the stability of solution that especially cellulose concentration or molecular weight are higher is poorer; Solvent system still lacks strong dissolving power, and the cellulose concentration that can reach homogeneous solution is lower; Cellulose dissolution is bad, solution is uneven, and perhaps the concentration because of alkaline solution alkali is larger, is easy to cause the Mierocrystalline cellulose fast degradation when generating soda cellulose, thereby the quality of using the made cellulose prods of this kind cellulose solution will obviously be reduced.
When the preparation regenerated cellulose fibre, no matter be one precipitation bath method of employing or twice precipitation bath method, all do precipitation bath with the mixed aqueous solution of aqueous acid or salt brine solution or acid and its salt.These acid and acid-salt, especially acid, have tool corrodibility to equipment and human body skin, and the steam that sucks for a long time these solution also is harmful to HUMAN HEALTH, and the discharge of wastewater that contain these acid and salt pollute the environment; When the spray silk enters precipitation bath, strong neutralization reaction occurs rapidly and generates salt and heat release (heat release be unfavorable for the temperature of precipitation bath control) in these acid and solvent composition alkali in cellulose solution, equally, also can generate salt with urea or the thiocarbamide reaction of solvent composition neutral and alkali, hydrolysis also may occur and emit irritating poisonous ammonia, hydrogen sulfide in urea or thiocarbamide in these precipitation bath; On the other hand, sodium hydroxide or lithium hydroxide meeting and acid-salt and other salt react and generate new salt, also can emit ammonia with the ammonium salt reaction, the existence of these complex reactions, not only consuming solvent and peptizer and make it can not recycle and reuse, and makes the precipitation bath complicated component and increase difficulty and the expense of liquid waste disposal.Therefore, these methods both had been unfavorable for environmental protection, and the cost of production process is increased.
Polyoxyethylene glycol is the environmental friendliness material, is to be considered at present one of nontoxic, safest macromolecular compound, and the compound aqueous solution of its aqueous solution, particularly itself and alkali, salt is considered to novel green solvent.Disclose in publication number CN101397369A a kind of sodium hydroxide/Aqueous Solutions of Polyethylene Glycol solvent system and by freeze-thaw or in the solvent system of precooling the direct method of dissolving cellulos, but facts have proved, this solvent system solubilized Microcrystalline Cellulose and regenerated cellulose, but the natural celluloses such as dissolving Cotton Pulp, wood pulps is limited in one's ability.
Summary of the invention
A kind of method that the purpose of this invention is to provide dissolving cellulos, the formation of micelle, micelle and Bai Xin when the method for this dissolving cellulos can be avoided cellulose dissolution, thus make the Mierocrystalline cellulose excellent dissolution, obtain uniform solution; Also avoided cellulose degradation.
Another object of the present invention is to provide a kind of preparation method of regenerated cellulose fibre, chemical reaction does not occur in this preparation method solvent, peptizer in process of setting, significantly reduce solvent, peptizer recycling cost, simultaneously, avoid rapid solidification, improve the stretch orientation degree, made the better regenerated cellulose fibre of intensity.
A kind of method of dissolving cellulos comprises the steps:
Be under the condition of 0～25 ℃ in temperature, first that Mierocrystalline cellulose is even by mediating shear-mixed with the solvent of the solvent gross weight 30～70wt% that accounts for dissolving cellulos, and then add remaining, temperature to be the solvent of the dissolving cellulos of-15～5 ℃, and, be placed on that to mediate shear-mixed at the temperature of-8～25 ℃ even, namely obtain uniform cellulose solution.
It is to realize the even mixing of material by the equipment that single screw rod or twin screw extruder, kneader, mixing roll, colloidal mill or intensive mixer have good kneading, a shear effect that described kneading is sheared.
The solvent of described dissolving cellulos comprises following component:
The aqueous solution that contains the polyoxyethylene glycol of the urea of sodium hydroxide, 8.5～22.0wt% of 6.0～12.0wt% and 0.4～6.0wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the thiocarbamide of sodium hydroxide, 3.5～6.5wt% of 8.5～12.0wt% and 0.4～6.0wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of lithium hydroxide, 4.5～25.0wt% of 3.5～7.5wt% and 0.3～5.5wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the thiocarbamide of lithium hydroxide, 2.5～6.5wt% of 3.5～7.5wt% and 0.3～5.5wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of thiocarbamide, 2.0～15.5wt% of sodium hydroxide, the 3.0～8.5wt% of 5.0～12.0wt% and 0.2～5.0wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of thiocarbamide, 0.5～15.0wt% of lithium hydroxide, the 2.0～6.5wt% of 3.0～7.5wt% and 0.2～5.0wt%.
Preferably, the solvent of described dissolving cellulos comprises following component:
The aqueous solution that contains the polyoxyethylene glycol of the urea of sodium hydroxide, 10.0～18.0wt% of 7.0～10.0wt% and 0.5～4.5wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the thiocarbamide of sodium hydroxide, 4.0～5.5wt% of 9.0～10.5wt% and 0.5～4.5wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of lithium hydroxide, 6.0～20.0wt% of 4.0～6.5wt% and 0.4～4.0wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the thiocarbamide of lithium hydroxide, 3.0～5.5wt% of 4.0～6.5wt% and 0.4～4.0wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of thiocarbamide, 3.0～10.5wt% of sodium hydroxide, the 4.0～6.5wt% of 7.0～10.0wt% and 0.3～3.5wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of thiocarbamide, 2.0～10.0wt% of lithium hydroxide, the 3.0～5.5wt% of 3.5～6.0wt% and 0.3～3.5wt%.
Preferably, the number-average molecular weight of described polyoxyethylene glycol is 150～1000000, and more preferably the molecular weight of polyoxyethylene glycol is 800～500000.
Preferably, be under the condition of 5～20 ℃ in temperature, first that Mierocrystalline cellulose is even by mediating shear-mixed with the solvent of the solvent gross weight 40～65wt% that accounts for dissolving cellulos, and then add remaining, temperature to be the solvent of the dissolving cellulos of-12～0 ℃, and, be placed on that to mediate shear-mixed at the temperature of-8～20 ℃ even, namely obtain uniform cellulose solution.
Preferably, described Mierocrystalline cellulose comprises bamboo pulp, wood pulps or Cotton Pulp, perhaps viscose fiber, lyocell fiber and non-woven fabrics thereof.
cellulose solution of the present invention forms by solvent is mixed with Mierocrystalline cellulose at twice, for the first time under temperature is the condition of 0～25 ℃, partial solvent is mixed with Mierocrystalline cellulose, Mierocrystalline cellulose is infiltrated, swelling, thereby be easy to dissolving when solubilizing agent dissolving for the second time, because Mierocrystalline cellulose at this temperature does not dissolve, swelling is slow, can guarantee Mierocrystalline cellulose inside to be able to swelling and surface swelling can avoid dissolving the time, dissolve the white core phenomenon of fast and inner indissoluble, simultaneously, this pre-evenly mixing can make when solubilizing agent dissolving for the second time Mierocrystalline cellulose quick, be dispersed in solvent.Like this, then add for the second time solvent remaining, that temperature is in the cellulose dissolution temperature to carry out mixed dissolution, can obtain high-quality cellulose solution.Be same solvent system due to what add for twice, whole material is easy to mix, and the cellulose degradation when avoiding first using high alkali liquid pretreatment of fiber element.
And prior art, directly Mierocrystalline cellulose is joined when dissolving in the solvent that is in its solvent temperature, because of the part Mierocrystalline cellulose fast dissolving soltion viscosity is increased contains not yet be uniformly dispersed or the Mierocrystalline cellulose obstruction solvent of indissoluble to its diffusion, infiltration, thereby make it be difficult to dissolving and easily form micelle, micelle, or because of the cellulose surface swelling, dissolving is too fast easily forms white core, these all cause, and cellulose dissolution is bad, solution is uneven; For first generating soda cellulose with alkaline solution pretreatment of fiber element, and then the method that adds urea or thiocarbamide to dissolve, because of the concentration of alkaline solution alkali larger, be easy to cause the Mierocrystalline cellulose fast degradation when generating soda cellulose, thereby the quality of using the made cellulose prods of this kind cellulose solution will obviously be reduced.
The present invention selects the aqueous solution of urea/sulphur urea, polyoxyethylene glycol and sodium hydroxide/lithium hydroxide as dissolution solvent, due to the synergy between solvent, make cellulose solution stability improve, also make simultaneously cellulose concentration improve, as for the polymerization degree being 250 natural cellulose, can make cellulose concentration up to the uniform and stable solution of 15wt%.
A kind of preparation method of regenerated cellulose fibre comprises the steps:
(1) cellulose solution gets spinning solution after deaeration, stoste through the spinning jet ejection is solidified in the first precipitation bath, described the first precipitation bath is a kind of in 5～30wt% aqueous sodium persulfate solution, 5～25wt% sodium acetate aqueous solution, 10～30wt% sodium chloride aqueous solution or 5～25wt% sodium phosphate aqueous solution, and temperature is 5～30 ℃;
(2) solidify and solidify in the second gelation through the fiber after drawing-off through step (1), through further obtaining cellulosic fibre through follow-up processing again after drawing-off, wherein, described the second gelation be mass percent concentration be 2～15wt% aqueous sodium persulfate solution, sodium acetate aqueous solution, sodium chloride aqueous solution or sodium phosphate aqueous solution in a kind of, be perhaps pure water, coagulation bath temperature is 45～95 ℃.
Described follow-up processing comprise with solidify, fiber after drawing-off successively through wash, oil, drying, winding process, obtain regenerated cellulose fibre.
Preferably, in cellulose solution, cellulosic content is 2～15wt%.
Preferably, the temperature of cellulosic spinning solution is 0～30 ℃.
Preferably, the cellulosic polymerization degree of described cellulose solution is 250-1500; More preferably polymkeric substance is Cotton Pulp or the wood pulps of 300-800.
Preferably, the first precipitation bath is 5～30wt% aqueous sodium persulfate solution; More preferably the first precipitation bath is 10～25wt% aqueous sodium persulfate solution.
Preferably, the second gelation is 3～10wt% aqueous sodium persulfate solution or pure water; Most preferably the second gelation is pure water.
Preferably, the temperature of the second gelation is 55～90 ℃; Most preferably the temperature of the second gelation is 65～85 ℃.
Preferably, described cellulose solution is prepared from by the method for above-mentioned dissolving fiber.
Be peptizer owing to adopting nontoxic neutrality or weakly alkaline salt and pure water, these peptizer can not decompose under the spinning curing condition, can not cause the cellosolve component to be decomposed yet, more not can with cellosolve component generation chemical reaction, thereby not only manufacturing processed environmental protection, also avoided solvent, the chemical depletion of peptizer and the precipitation bath complicated component that causes, thereby the recycling cost of solvent, peptizer is greatly reduced.After precipitation bath purifies after filtration, solvent is separated with peptizer, solvent and peptizer all can be recycled; On the other hand, in precipitation bath of the present invention, the process of setting of Mierocrystalline cellulose strand is not only to relate to the chemical neutralization process for solvent and non-solvent mutual diffusion behavior, process of setting quite relaxes in the first precipitation bath, the Mierocrystalline cellulose strand is evenly solidified, and can implement high stretch orientation between cellulosic molecule before hydrogen bond network not yet being completed into of this process, then by fully solidifying regeneration and further stretch orientation in the second precipitation bath, thereby obtain the good mechanical performance (regenerated cellulose fibre of intensity 〉=2.3cN/dtex).
Compared with prior art, the invention has the advantages that:
First, the method of dissolving cellulos of the present invention, solvent system utilizes polyoxyethylene glycol easily and characteristic and the molecule chain flexibility thereof of Mierocrystalline cellulose and water formation hydrogen bond, with itself and urea or (with) the thiocarbamide Application of composite common with alkali (sodium hydroxide or lithium hydroxide) generation synergistic effect, thereby strengthened the ability of solvent system dissolving cellulos, especially improved the stability of cellulose solution; First use partial solvent dipping, the swollen cellulose of same system, and then add cold solvent to be controlled at solvent temperature to dissolve, bad and the cellulose degradation when first activating with high alkali liquid of cellulose dissolution when having avoided directly under solvent temperature dissolving, thus high-quality homogeneous solution obtained.
Second, the present invention prepares the method for regenerated cellulose fibre, be peptizer owing to adopting nontoxic neutrality or weakly alkaline salt and pure water, avoided take corrosive, the acid that is harmful to health or acid-salt as peptizer because of the consumption of solvent that chemical reaction was caused and peptizer and because the solvent composition hydrolysis give off poisonous gas, thereby made cost, process environmental protection; Simultaneously, avoided because of the rapid solidification due to solvent and peptizer chemical neutralization.Mitigation by implementing segmentation, solidify regenerative process fully, make fiber be able to super drawing in forming process and be orientated and obtain to solidify uniformly revived structure, thus the physical and mechanical properties of raising fiber.Thereby the present invention obviously improved Technical Economy, has better industrial prospect.
Embodiment
Embodiment 1
The wood pulps (polymerization degree 400) of 3.6g drying and 40g 7.5wt% sodium hydroxide/11.0wt% urea/1.5wt% polyoxyethylene glycol (molecular weight 800) mixed aqueous solution are mediated shear-mixed even under 8 ℃, then add wherein the 60g temperature to be the 7.5wt% sodium hydroxide of-15 ℃/11.0wt% urea/1.5wt% polyoxyethylene glycol (molecular weight 800) mixed aqueous solution, and be placed under 25 ℃ that to mediate shear-mixed even, Mierocrystalline cellulose can dissolve fully, obtains the cellulose solution of homogeneous transparent.This cellulose solution was at room temperature deposited 35 days and significantly gelation of nothing.
Embodiment 2
The bamboo pulp (polymerization degree 400) of 3.8g drying and 30g 9.2wt% sodium hydroxide/4.5wt% thiocarbamide/0.4wt% polyoxyethylene glycol (molecular weight 4000) mixed aqueous solution are mediated shear-mixed even under 25 ℃, then add wherein the 70g temperature to be the 9.2wt% sodium hydroxide of-8 ℃/4.5wt% thiocarbamide/0.4wt% polyoxyethylene glycol (molecular weight 4000) mixed aqueous solution, and be placed under-2 ℃ that to mediate shear-mixed even, Mierocrystalline cellulose can dissolve fully, obtains the cellulose solution of homogeneous transparent.This cellulose solution was at room temperature deposited 35 days and significantly gelation of nothing.
Embodiment 3
The Cotton Pulp (polymerization degree 500) of 5.0g drying and 70g 5.0wt% lithium hydroxide/12.0wt% urea/5.5wt% polyoxyethylene glycol (molecular weight 150) mixed aqueous solution are mediated shear-mixed even under 0 ℃, then add wherein the 30g temperature to be the 5.0wt% lithium hydroxide of-15 ℃/12.0wt% urea/5.5wt% polyoxyethylene glycol (molecular weight 150) mixed aqueous solution, and be placed under-8 ℃ that to mediate shear-mixed even, Mierocrystalline cellulose can dissolve fully, obtains the cellulose solution of homogeneous transparent.This cellulose solution was at room temperature deposited 35 days and significantly gelation of nothing.
Embodiment 4
The Cotton Pulp (polymerization degree 620) of 5.3g drying and 50g 3.5wt% lithium hydroxide/6.5wt% thiocarbamide/0.3wt% polyoxyethylene glycol (molecular weight 1,000,000) mixed aqueous solution are mediated shear-mixed even under 15 ℃, then add wherein the 50g temperature to be the 3.5wt% lithium hydroxide of-10 ℃/6.5wt% thiocarbamide 0.3wt% polyoxyethylene glycol (molecular weight 1,000,000) mixed aqueous solution, and be placed under-4 ℃ that to mediate shear-mixed even, Mierocrystalline cellulose can dissolve fully, obtains the cellulose solution of homogeneous transparent.This cellulose solution was at room temperature deposited 35 days and significantly gelation of nothing.
Embodiment 5
The Cotton Pulp (polymerization degree 250) of 17.5g drying and 40g 9.5wt% sodium hydroxide/6.0wt% thiocarbamide/8.0wt% urea/3.0wt% polyoxyethylene glycol (molecular weight 2000) mixed aqueous solution are mediated shear-mixed even under 20 ℃, then add wherein the 60g temperature to be the 9.5wt% sodium hydroxide of-12 ℃/6.0wt% thiocarbamide/8.0wt% urea/3.0wt% polyoxyethylene glycol (molecular weight 2000) mixed aqueous solution, and be placed under-6 ℃ that to mediate shear-mixed even, Mierocrystalline cellulose can dissolve fully, obtains the cellulose solution of homogeneous transparent.This cellulose solution was at room temperature deposited 35 days and significantly gelation of nothing.
Embodiment 6
The wood pulps (polymerization degree 1500) of 2.0g drying and 30g 7.5wt% lithium hydroxide/2.0wt% thiocarbamide/10.0wt% urea/2.5wt% polyoxyethylene glycol (molecular weight 6000) mixed aqueous solution are mediated shear-mixed even under 0 ℃, then add wherein the 70g temperature to be the 7.5wt% lithium hydroxide of-12 ℃/2.0wt% thiocarbamide/10.0wt% urea/2.5wt% polyoxyethylene glycol (molecular weight 6000) mixed aqueous solution, and be placed under 0 ℃ that to mediate shear-mixed even, Mierocrystalline cellulose can dissolve fully, obtains the cellulose solution of homogeneous transparent.This cellulose solution was at room temperature deposited 35 days and significantly gelation of nothing.
Embodiment 7
The regenerated cellulose (polymerization degree 300) of 8.0g drying and 70g 6.0wt% sodium hydroxide/22.0wt% urea/6.0wt% polyoxyethylene glycol (molecular weight 400) mixed aqueous solution are mediated shear-mixed even under 0 ℃, then adding wherein the 30g temperature is the 6.0wt% sodium hydroxide/22.0wt% urea/6.0wt% polyoxyethylene glycol (molecular weight 400) mixed aqueous solution of 5 ℃, and be placed under 4 ℃ that to mediate shear-mixed even, Mierocrystalline cellulose can dissolve fully, obtains the cellulose solution of homogeneous transparent.This cellulose solution was at room temperature deposited 35 days and significantly gelation of nothing.
Embodiment 8
The Cotton Pulp (polymerization degree 500) of 5.0g drying and 60g 7.5wt% lithium hydroxide/4.5wt% urea/3.5wt% polyoxyethylene glycol (molecular weight 400) mixed aqueous solution are mediated shear-mixed even under 5 ℃, then add wherein the 40g temperature to be the 7.5wt% lithium hydroxide of-10 ℃/4.5wt% urea/3.5wt% polyoxyethylene glycol (molecular weight 400) mixed aqueous solution, and be placed under 10 ℃ that to mediate shear-mixed even, Mierocrystalline cellulose can dissolve fully, obtains the cellulose solution of homogeneous transparent.This cellulose solution was at room temperature deposited 35 days and significantly gelation of nothing.
Embodiment 9
The Cotton Pulp (polymerization degree 400) of 125g drying and 1000g 7.0wt% sodium hydroxide/12.0wt% urea/1.2wt% polyoxyethylene glycol (molecular weight 2000) mixed aqueous solution are mediated shear-mixed even under 5 ℃, then add wherein the 2000g temperature to be the 7.0wt% sodium hydroxide of-12 ℃/12.0wt% urea/1.2wt% polyoxyethylene glycol (molecular weight 2000) mixed aqueous solution, and be placed under 0 ℃ that to mediate shear-mixed even, obtain the cellulose solution of homogeneous transparent.This cellulose solution is after deaeration and filtering, and the spinning pack of sending into spinning-drawing machine through volume pump carries out wet-spinning, is 30 ℃ for spinning temperature.At first entering temperature from the stoste thread of spinning jet ejection is the 15wt% sodium acetate aqueous solution of 15 ℃, through solidifying and stretch orientation before the cellulosic molecule hydrogen bond network not yet fully forms, and then enter temperature and be the 5wt% sodium acetate aqueous solution of 65 ℃, through fully solidify regeneration, further after stretch orientation, successively through wash, oil, dry, coiling obtains regenerated cellulose fibre.The breaking tenacity of this regenerated cellulose fibre and elongation at break are respectively 2.4cN/dtex and 7.3%.
Embodiment 10
The bamboo pulp (polymerization degree 500) of 165g drying and 1500g 9.5wt% sodium hydroxide/5.0wt% thiocarbamide/3.0wt% polyoxyethylene glycol (molecular weight 1000) mixed aqueous solution are mediated shear-mixed even under 10 ℃, then add wherein the 1500g temperature to be the 9.5wt% sodium hydroxide of-10 ℃/5.0wt% thiocarbamide/3.0wt% polyoxyethylene glycol (molecular weight 1000) mixed aqueous solution, and be placed under-4 ℃ that to mediate shear-mixed even, obtain the cellulose solution of homogeneous transparent.This cellulose solution is after deaeration and filtering, and the spinning pack of sending into spinning-drawing machine through volume pump carries out wet-spinning, is 0 ℃ for spinning temperature.At first entering temperature from the stoste thread of spinning jet ejection is the 30wt% sodium chloride aqueous solution of 5 ℃, through solidifying and stretch orientation before the cellulosic molecule hydrogen bond network not yet fully forms, and then enter temperature and be the 15wt% sodium chloride aqueous solution of 60 ℃, through fully solidify regeneration, further after stretch orientation, successively through wash, oil, dry, coiling obtains regenerated cellulose fibre.The breaking tenacity of this regenerated cellulose fibre and elongation at break are respectively 2.3cN/dtex and 6.7%.
Embodiment 11
The Cotton Pulp (polymerization degree 600) of 190g drying and 900g 6.5wt% lithium hydroxide/10.0wt% urea/0.8wt% polyoxyethylene glycol (molecular weight 500,000) mixed aqueous solution are mediated shear-mixed even under 25 ℃, then add wherein the 2100g temperature to be the 6.5wt% lithium hydroxide of-12 ℃/10.0wt% urea/0.8wt% polyoxyethylene glycol (molecular weight 500,000) mixed aqueous solution, and be placed under 0 ℃ that to mediate shear-mixed even, obtain the cellulose solution of homogeneous transparent.This cellulose solution is after deaeration and filtering, and the spinning pack of sending into spinning-drawing machine through volume pump carries out wet-spinning, is 20 ℃ for spinning temperature.At first entering temperature from the stoste thread of spinning jet ejection is the 20wt% aqueous sodium persulfate solution of 15 ℃, through solidifying and stretch orientation before the cellulosic molecule hydrogen bond network not yet fully forms, and then enter temperature and be the 3wt% aqueous sodium persulfate solution of 75 ℃, through fully solidify regeneration, further after stretch orientation, successively through wash, oil, dry, coiling obtains regenerated cellulose fibre.The breaking tenacity of this regenerated cellulose fibre and elongation at break are respectively 2.7cN/dtex and 11.5%.
Embodiment 12
The wood pulps (polymerization degree 800) of 158g drying and 2100g 5.5wt% lithium hydroxide/5.0wt% thiocarbamide/1.4wt% polyoxyethylene glycol (molecular weight 50,000) mixed aqueous solution are mediated shear-mixed even under 5 ℃, then add wherein the 900g temperature to be the 5.5wt% lithium hydroxide of-12 ℃/5.0wt% thiocarbamide/1.4wt% polyoxyethylene glycol (molecular weight 50,000) mixed aqueous solution, and be placed under-8 ℃ that to mediate shear-mixed even, obtain the cellulose solution of homogeneous transparent.This cellulose solution is after deaeration and filtering, and the spinning pack of sending into spinning-drawing machine through volume pump carries out wet-spinning, is 20 ℃ for spinning temperature.At first entering temperature from the stoste thread of spinning jet ejection is the 20wt% aqueous sodium persulfate solution of 15 ℃, through solidifying and stretch orientation before the cellulosic molecule hydrogen bond network not yet fully forms, and then enter temperature and be the pure water of 85 ℃, through fully solidify regeneration, further after stretch orientation, successively through wash, oil, dry, coiling obtains regenerated cellulose fibre.The breaking tenacity of this regenerated cellulose fibre and elongation at break are respectively 2.8cN/dtex and 12.4%.
Embodiment 13
Method according to embodiment 5 prepares the solution that the 3525g cellulose concentration is 15wt%.This cellulose solution is after deaeration and filtering, and the spinning pack of sending into spinning-drawing machine through volume pump carries out wet-spinning, is 15 ℃ for spinning temperature.At first entering temperature from the stoste thread of spinning jet ejection is the 10wt% aqueous sodium persulfate solution of 20 ℃, through solidifying and stretch orientation before the cellulosic molecule hydrogen bond network not yet fully forms, and then enter temperature and be the pure water of 95 ℃, through fully solidify regeneration, further after stretch orientation, successively through wash, oil, dry, coiling obtains regenerated cellulose fibre.The breaking tenacity of this regenerated cellulose fibre and elongation at break are respectively 2.6cN/dtex and 8.1%.
Embodiment 14
Other are with embodiment 12, and difference is that at first to enter temperature be the 5wt% sodium phosphate aqueous solution of 30 ℃ to the stoste thread from the spinning jet ejection.The breaking tenacity of gained regenerated cellulose fibre and elongation at break are respectively 2.4cN/dtex and 6.7%.
Embodiment 15
Method according to embodiment 6 prepares the solution that the 3060g cellulose concentration is 2wt%.This cellulose solution is after deaeration and filtering, and the spinning pack of sending into spinning-drawing machine through volume pump carries out wet-spinning, is 10 ℃ for spinning temperature.At first entering temperature from the stoste thread of spinning jet ejection is the 20wt% aqueous sodium persulfate solution of 15 ℃, through solidifying and stretch orientation before the cellulosic molecule hydrogen bond network not yet fully forms, and then enter temperature and be the pure water of 45 ℃, through fully solidify regeneration, further after stretch orientation, successively through wash, oil, dry, coiling obtains regenerated cellulose fibre.The breaking tenacity of this regenerated cellulose fibre and elongation at break are respectively 2.5cN/dtex and 7.6%.
Comparative example 1
This comparative example is to adopt different dissolving methods that Mierocrystalline cellulose is dissolved, the proportioning of dual mode Mierocrystalline cellulose used, solvent and the consumption of solvent are all identical, but the consumption of cellulosic material is different, the proportioning of solvent is referring to embodiment 1, the concrete technology of dissolution mechanism is referring to embodiment 1 at twice, the solvent temperature of a dissolution mechanism is-10 ℃, and result is as seeing Table 1:
The impact of table 1 dissolution mechanism on cellulose dissolution
Can draw from table 1 result, solvent adds in the cellulose solution that this twice dissolution mechanism of dissolving cellulos obtain at twice, there is no undissolved Mierocrystalline cellulose, and the cellulose concentration of dissolving is high, and what solution can be stable deposited 35 days.
Method to other embodiment is also carried out above-mentioned contrast, and result matches with it.
Comparative example 2
This comparative example is to adopt identical dissolving method to the comparison of cellulose dissolution to different solvents, solvent orange 2 A: the aqueous solution of 7.5wt% sodium hydroxide/11.0wt% urea, the aqueous solution of solvent B:7.5wt% sodium hydroxide // 1.5wt% polyoxyethylene glycol (molecular weight 800), solvent C: referring to the formula of experimental example 1 solvent.The consumption of three kinds of solvents is identical, and Mierocrystalline cellulose used is also identical, but cellulosic consumption is different, and dissolving method is dissolving at twice, and dissolution process is with reference to experimental example 1, and result is as seeing Table 2:
The impact of table 2 solvent on cellulose dissolution
From the results shown in Table 2, when containing simultaneously alkali, urea or thiocarbamide and ethylene glycol in solvent, do not have undissolved Mierocrystalline cellulose in the gained cellulose solution, the cellulose concentration of dissolving is also high, and solution kept stable in 35 days.
Method to other embodiment is also carried out above-mentioned contrast, and result matches with it.
Claims (5)
1. the method for a dissolving cellulos, comprise the steps:
Be under the condition of 0～25 ℃ in temperature, first that Mierocrystalline cellulose is even by mediating shear-mixed with the solvent of the solvent gross weight 30～70wt% that accounts for dissolving cellulos, and then add remaining, temperature to be the solvent of the dissolving cellulos of-15 ~ 5 ℃, and, be placed on that to mediate shear-mixed at the temperature of-8 ~ 25 ℃ even, namely obtain uniform cellulose solution;
The solvent of described dissolving cellulos comprises following component:
The aqueous solution that contains the polyoxyethylene glycol of the urea of sodium hydroxide, 8.5～22.0wt% of 6.0～12.0wt% and 0.4～6.0wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the thiocarbamide of sodium hydroxide, 3.5～6.5wt% of 8.5～12.0wt% and 0.4～6.0wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of lithium hydroxide, 4.5～25.0wt% of 3.5～7.5wt% and 0.3～5.5wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the thiocarbamide of lithium hydroxide, 2.5～6.5wt% of 3.5～7.5wt% and 0.3～5.5wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of thiocarbamide, 2.0～15.5wt% of sodium hydroxide, the 3.0～8.5wt% of 5.0～12.0wt% and 0.2～5.0wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of thiocarbamide, 0.5～15.0wt% of lithium hydroxide, the 2.0～6.5wt% of 3.0～7.5wt% and 0.2～5.0wt%.
2. method according to claim 1, is characterized in that, the solvent of described dissolving cellulos comprises following component:
The aqueous solution that contains the polyoxyethylene glycol of the urea of sodium hydroxide, 10.0～18.0wt% of 7.0～10.0wt% and 0.5～4.5wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the thiocarbamide of sodium hydroxide, 4.0～5.5wt% of 9.0～10.5wt% and 0.5～4.5wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of lithium hydroxide, 6.0～20.0wt% of 4.0～6.5wt% and 0.4～4.0wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the thiocarbamide of lithium hydroxide, 3.0～5.5wt% of 4.0～6.5wt% and 0.4～4.0wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of thiocarbamide, 3.0～10.5wt% of sodium hydroxide, the 4.0～6.5wt% of 7.0～10.0wt% and 0.3～3.5wt%;
Perhaps, the aqueous solution that contains the polyoxyethylene glycol of the urea of thiocarbamide, 2.0～10.0wt% of lithium hydroxide, the 3.0～5.5wt% of 3.5～6.0wt% and 0.3～3.5wt%.
3. method according to claim 1, is characterized in that, the number-average molecular weight of described polyoxyethylene glycol is 150～1000000.
4. method according to claim 3, is characterized in that, the molecular weight of described polyoxyethylene glycol is 800～500000.
5. according to claim 1-4 described methods of any one, is characterized in that, described Mierocrystalline cellulose comprises bamboo pulp, wood pulps or Cotton Pulp, perhaps viscose fiber, lyocell fiber and non-woven fabrics thereof.
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