CN101555321A - Solvent composition and preparation method and application thereof - Google Patents
Solvent composition and preparation method and application thereof Download PDFInfo
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- CN101555321A CN101555321A CNA2008100666178A CN200810066617A CN101555321A CN 101555321 A CN101555321 A CN 101555321A CN A2008100666178 A CNA2008100666178 A CN A2008100666178A CN 200810066617 A CN200810066617 A CN 200810066617A CN 101555321 A CN101555321 A CN 101555321A
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Abstract
The invention discloses a solvent composition and a preparation method and the application thereof. The water solvent is formed by a quaternary system containing lithium hydroxide, sodium hydroxide, thiourea and water , and has highest solvent power when the temperature is ranged from 15 DEG C below zero to 5 DEG C. The invention also discloses a method for fast dissolving cellulose by utilizing the water solvent and preparing regenerated cellulose membranes, fibers, porous materials and carbon materials with good properties. The water solvent system has the characteristics of high solvent power on the cellulose, stable obtained cellulose solution, good product property, no toxicum or pollution in the production process and low production cost, and overcomes the defect existing in the prior art, thereby having outstanding superiority.
Description
Technical field
The present invention relates to solvent compositions and its production and use, belong to the natural polymer field, also belong to fields such as material, weaving, chemical, agricultural, environmental engineering.
Background technology
Mierocrystalline cellulose is a renewable resources the abundantest on the earth, may become the renewable resources that substitutes petrochemicals.From most of plants such as trees, cotton, rice straw, corn and some bacterium, can both obtain Mierocrystalline cellulose.Yet,, also can not make full use of it far away because natural cellulose is difficult to water-soluble and usual vehicle, and is difficult to melt-processed.For a long time, the regenerated cellulose product still adopts traditional viscose process to produce artificial silk and glassine paper.Mierocrystalline cellulose generates cellulose xanthate with the dithiocarbonic anhydride reaction under the highly basic effect, it is dissolved in diluted alkaline and becomes viscose.The Mierocrystalline cellulose viscose is regenerated in dilute acid soln after spray silk or curtain coating, makes viscose yarn or glassine paper.This method relates to chemical reagent such as formaldehyde, sulphite, sodium sulphite, zinc sulfate in process of production, and discharges a large amount of poisonous dithiocarbonic anhydride and hydrogen sulfide, not only damages HUMAN HEALTH, and serious environment pollution.Producing copper rayon with cuprammonium process also exists environmental pollution, costs an arm and a leg and solution recovery problem.
Alternative method as viscose process, reported serial of methods this year, wherein Mierocrystalline cellulose is dissolved under the situation that does not generate derivative in the aqueous solution of the mixture of organic solvent, organic solvent and inorganic salt or salt, the cellulosic fibre of formulations prepared from solutions obtains generic name Lyocell from BISFA (regenerated fiber stdn international office) thus.BISFA is defined as Lyocell the cellulosic fibre that is obtained by spinning processes by organic solvent.Having only at present unique a kind of generic name of making on the commodity scale so far is that the method for the cellulosic fibre of Lyocell has realized industrialization.In this method, N-methylmorpholine-(U.S.patent 2179181,1939 for N-oxide compound (NMMO) in application; Brit.1144048,1967; U.S.patent 4246221,1981) as solvent.This method provide have high-tensile, the fiber of high wet modulus and high hook strength performance.Yet,, thereby limited practicality widely with this fiber because above-mentioned fiber has tangible tendency for fibrillation under dampness.Adopt Special Equipments such as expensive thin-film evaporator, twin screw to carry out cellulosic dissolving in the production process mostly, though these Special Equipments can satisfy certain industrial scale, the plain silk of at present existing small amount of fibers product comes into the market, but because investment is huge, technical qualification are harsh, suitability for industrialized production is made slow progress.In addition, ionic liquid at room temperature is widely used in electrochemistry, organic synthesis, catalysis as a kind of green solvent and the field such as separates, and also is the good solvent of many macromolecular polymerization reactions and processing simultaneously.But only there is a few ionic liquid that fiber is have dissolving power preferably, still has a lot of defectives, still be in conceptual phase at present.In addition, Mierocrystalline cellulose and urea at high temperature react the generation cellulose carbamate, directly are dissolved in then and obtain spinning solution (Finnish Patent61003 in the sig water; Finnish Patent 62318; U.S.Patent 4404369), but the amount of urea height, by product is arranged, also be difficult to industrialization.Japan has reported that Mierocrystalline cellulose is at 2.5molL
-1Dissolving in the aqueous sodium hydroxide solution, but must use the wood pulp cellulose of handling through steam explosion (polymerization degree is lower than 250), then there is not effect for the cotton pulp dregs of rice, and extremely low (the Japan Patent 1777283,1983 of obtained fiber yarn intensity; U.S.Patent 4634470).
Interpolation urea or thiocarbamide can obviously improve cellulosic dissolving in aqueous sodium hydroxide solution.Sodium hydroxide/(ZL 00114486.3 for the 4wt% aqueous solution of urea to use 6wt%; Polym.J.2000,32,866-870) with 1.5M sodium hydroxide/0.65M thiourea solution (ZL00128162.3; J.Polym.Sci.Polym.Phys.2002,40,1521-1529) dissolved cellulose, but Mierocrystalline cellulose and solvent mixture under freezing conditions must be frozen into ice, the ability of thawing then dissolving cellulos, especially these two kinds of solvent compositions only are about 30% to the cotton pulp dregs of rice solubleness of the polymerization degree 500, do not possess practicality substantially.Chinese patent ZL 03128386.1, ZL 200310111447.8, ZL 200310111567.8 and ZL 200410012682.4 disclose respectively and have utilized sodium hydroxide/urea, sodium hydroxide/thiocarbamide, lithium hydroxide/urea and lithium hydroxide/thiourea solution, at room temperature direct dissolving cellulos after cooling, wherein sodium hydroxide/urea, sodium hydroxide/thiourea solution solubilized molecular weight are lower than 10.110
4Natural cellulose and molecular weight be lower than 1210
4Regenerated cellulose.But cellulosic solid content is lower in the gained solution (is 600 the cotton pulp dregs of rice to the polymerization degree, solid content is higher than at 4.3% o'clock and is difficult to carry out deaeration with general method, and stability of solution is low, and spinning property is poor, even can not dissolve fully), relatively poor to the polymerization degree greater than 600 cotton pulp dregs of rice dissolving power.And the molecular weight of lithium hydroxide/urea and lithium hydroxide/thiourea solution dissolved cellulose is also more limited, institute can dissolved the high-polymerization degree of Mierocrystalline cellulose be 2300.Chinese patent publication number 200710051867.X and 200710052532.X disclose the method for dissolving cellulos respectively, Mierocrystalline cellulose is dispersed in the sodium hydroxide of high density or the lithium hydroxide aqueous solution forms soda cellulose, add aqueous solution of urea then and make cellulose dissolution, Mierocrystalline cellulose, sodium hydroxide or lithium hydroxide are identical with ZL 200310111567.8 with Chinese patent ZL03128386.1 with urea concentration in the final solution.This method is not better than Chinese patent ZL 03128386.1 and the disclosed method of ZL200310111567.8, and they are also relatively limited to cellulosic dissolving power, and the cellulose solution stability that obtains is low, and spinning property is poor.Utilize sodium hydroxide among the Chinese patent ZL 200510027217.2, thiocarbamide, the quaternary system dissolving cellulos of urea and water, the cellulose solution stability of gained is lower (to be 500 the cotton pulp dregs of rice for the polymerization degree, solid content is higher than 5.5% cellulose solution and is difficult to use the general method deaeration equally, and solution is easy to gel in the deaeration process, spinning property is poor), the intensity of resulting regenerated cellulose film and silk is lower, and (tensile strength of film is lower than 100MPa, the intensity of regenerated cellulose fibre only is 1.04cN/dtex), can be up to 1400 by the dissolved cellulosic degree of polymerization.The shortcoming of above method is: cellulose solution that can only viscosity is relatively low carries out spinning, and the Mierocrystalline cellulose quality concentration that it had in addition is less relatively.From economic angle, this low cellulose concentration is unsafty, because this causes that product performance are low, throughput is little and to the evaporation expense height of the processing of exhausted peptizer.
Summary of the invention
Technical problem to be solved by this invention is to disclose a kind of inexpensive, pollution-free, easy cellosolve, overcoming the defective that prior art exists, and provide the method for utilizing the quick dissolving cellulos of this solvent and processability fiber with excellent cellulose fiber, film, porous material and carbon material.
Compare with existing technology, solvent compositions can obtain the high density cellulose solution at-15～5 ℃ of rapidly complete dissolving cellulos.And this cellulose solution good spinnability can be preserved gel not taken place more than January yet, and the processing process is efficient more simple, and the product performance that obtain are good, have extensive use, are particularly suitable for suitability for industrialized production.Therefore, the present invention has significant innovation and technical progress, meets the social benefit and the economic interests of Sustainable development.
This water solvent consist of lithium hydroxide, sodium hydroxide, thiocarbamide, water quaternary system, wherein the content of lithium hydroxide is 0.1～7wt%, the content of sodium hydroxide is 0.1～12wt%, the content of thiocarbamide is 0.1～6wt%, all the other are water.Also can contain the urea that content is 0.1～25wt% simultaneously.
The present invention also provides the preparation method of above-mentioned water solvent, in the said ratio scope, lithium hydroxide, sodium hydroxide, thiocarbamide and water is mixed in proportion.Can be earlier with one or both or three kinds of medicine wiring solution-formings (addition sequence in no particular order) in three kinds of solid medicines, and then add other two kinds or a kind of medicine (addition sequence is in no particular order), make its dissolving.Also lithium hydroxide, sodium hydroxide, thiocarbamide, urea and water can be mixed in proportion.Can be earlier with one or both or three kinds or four kinds of medicine wiring solution-formings (addition sequence in no particular order) in four kinds of solid medicines, and then add other three kinds or two kinds or a kind of medicine (addition sequence is in no particular order), make its dissolving.
The present invention also provides the method for utilizing above-mentioned water solvent dissolving cellulos: 100 gram solvents are chilled to-15～5 ℃ in advance, 1～22 gram Mierocrystalline cellulose is scattered in the solvent, the powerful stirring 2～10 minutes, obtain transparent Mierocrystalline cellulose strong solution, wherein content of cellulose is 1～18wt%, and the gained cellulose solution can be stablized and not form gel more than preserving January.Used Mierocrystalline cellulose comprises natural cellulose and regenerated cellulose, as straw pulp, bagasse pulp, bamboo pulp, wood pulp, paper pulp, cotton pulp, bacteria cellulose, non-woven fabrics etc.
The present invention also provides the method for utilizing above-mentioned cellulose solution to prepare cellulose membrane, fiber, porous material and carbon material.Cellulose solution can adopt the following step: the solution of Mierocrystalline cellulose in solvent is extruded by the spray silk groove or the hole of spinning jet, thus extruded film or fiber with common wet method system film, fiber and porous material in this complete processing; Make the film extruded or fiber enter precipitation bath and draw, install drawing-off film or fiber thus by towing mechanism; The film or the fiber of drawing-off are continued to be processed into regenerated cellulose film, fiber and porous material.These cellulose prods obtain corresponding carbon material through high temperature cabonization.
The also available so-called dry-jet wet-spinning legal system film of cellulose solution, fiber, porous material have adopted the following step: the solution of Mierocrystalline cellulose in solvent is extruded by the spray silk groove or the hole of spinning jet, thus extruded film or fiber in this complete processing; The film extruded or long filament are drawn by air gap, precipitation bath and by towing mechanism, install drawing-off film or fiber thus; The film or the fiber of drawing-off are continued to be processed into regenerated cellulose film, fiber and porous material.These cellulose prods obtain corresponding carbon material through high temperature cabonization.
This section gaseous space between " air gap " refers to from the spinning jet to the precipitation bath, it can be an air, also can be any gas of spinning process or mixture of gas of not disturbing.As above-mentioned, fatty alcohol must exist with " gas phase state ".Experiment shows that following alcohol especially is fit to be used as the gas of " air gap ": methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol and the trimethyl carbinol.Also can use these pure mixtures.
Solidification liquid can be that water content is lower than 50wt%, preferably is lower than the nonpolar organic liquid of lower boiling of 10wt%.In a preferable preparation technique, solidification liquid is anhydrous (being that liquid water content is lower than 5wt%).The example of the suitable peptizer of this class comprises alcohol, ketone, ester or its mixture.It is preferred using methyl alcohol, ethanol and acetone to do peptizer.Optionally water is added peptizer so that obtain the peptizer that water content is lower than 50wt%.But preferably use water content to be lower than the peptizer of 10wt%, more especially substantially anhydrous peptizer.
Solidification liquid also can be to have added cationic water, preferably contains for example H of monovalent cation
+, NH
4 +, Li
+, Na
+Or K
+The aqueous solution, such solution is can be for example water-soluble and make with hydrochloric acid, sulfuric acid, nitric acid, acetic acid, ammonium sulfate, ammonium acetate, lithium chloride, sodium sulfate, vitriolate of tartar etc.As long as the gasiform fatty alcohol is provided,, still can produce film or fiber with satisfactory performance even adopt water as peptizer in air gap.
After solidifying, can be with film, fiber and the porous material washing that forms.Washings is optional freely as the low boiling point organic solvent on the same group of peptizer or the mixture of these solvents, but preferred washings is a water.
The cellulose membrane that produces, fiber, porous material can obtain corresponding carbon material through high temperature cabonization under inert atmosphere protection.Inert atmosphere does not refer to and reacts with Mierocrystalline cellulose, prevents cellulose materials at high temperature incendiary gas or gaseous mixture.Experiment shows that following gas especially is fit to be used as inert atmosphere: nitrogen, carbonic acid gas, helium, neon and argon gas.Also can use the mixture of these gases.
Except water, sodium hydroxide, lithium hydroxide, thiocarbamide and/or urea, Mierocrystalline cellulose and/or solvent composition and cellulosic reaction product, in solution, may there be other materials." other materials " can be the material that helps the cellulose solution processing characteristics, with lithium hydroxide, sodium hydroxide, thiocarbamide, different other solvents or auxiliary (additive), for example water glass, silicon-dioxide, titanium dioxide, carbon black, the dyestuffs etc. of urea.
The purpose of this invention is to provide a kind of inexpensive, pollution-free, easy method and obtain high-quality cellulose solution, and utilize this cellulose solution to adopt corresponding apparatus system film, spinning, granulation etc., the regenerated cellulose film that production performance is good, fiber, non-woven fabrics, porous material and various functional regenerated cellulose product and carbon material thereof thus.The invention has the advantages that: the solvent that is adopted is lithium hydroxide, sodium hydroxide, thiocarbamide (and/or urea) and water, and production process is nontoxic, pollution-free, helps environment protection and operator ' s health; Shorten the preparation time of Mierocrystalline cellulose stoste, both improved the concentration of cellulose solution, also guaranteed the stability and the workability of cellulose solution, saved the resource and the energy; Cellulose prods and the carbon material produced have good performance and function.The not only production technique environmental protection of this novel method, cost are low, and excellent product performance, and it is the important breakthrough to prior art, is suitable for suitability for industrialized production and practical application, has broad application prospects.
Description of drawings
Fig. 1 shows that cellulose solution of the present invention preserves after 1 month state in beaker;
Fig. 2 illustrates the photo of porous material of regenerated cellulose;
Fig. 3 illustrates the stereoscan photograph of porous material of regenerated cellulose;
Fig. 4 shows the stereoscan photograph of regenerated cellulose fibre;
Fig. 5 illustrates the stereoscan photograph of porous carbon materials.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
Embodiment 1
Get the 17.5 gram cotton pulp dregs of rice (polymerization degree 500), add in 200 gram 4wt% lithium hydroxide/1wt% sodium hydroxide/3wt% thiourea solutions (being chilled to-6 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 8wt%.Fig. 1 illustrates this solution and preserves 1 month later photo at 4 ℃, and gelation does not take place cellulose solution, and leaves standstill natural deaeration in the process, illustrates that solution quality is very good.
Embodiment 2
Get the 13 gram cotton pulp dregs of rice (polymerization degree 500), add in 200 gram 7wt% lithium hydroxide/0.1wt% sodium hydroxide/6wt% thiourea solutions (being chilled to 5 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 6.1wt%.
Embodiment 3
Get the 8.4 gram cotton pulp dregs of rice (polymerization degree 500), add in 200 gram 0.1wt% lithium hydroxide/12wt% sodium hydroxide/0.1wt% thiourea solutions (being chilled to-15 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 4wt%.
Embodiment 4
Get the 20 gram cotton pulp dregs of rice (polymerization degree 400), add in 200 gram 3.2wt% lithium hydroxide/2.6wt% sodium hydroxide/5wt% thiourea solutions (being chilled to-5 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 9.1wt%.
Embodiment 5
Get the 30 gram cotton pulp dregs of rice (polymerization degree 300), add in 200 gram 4.2wt% lithium hydroxide/8wt% sodium hydroxide/4wt% thiourea solutions (being chilled to 0 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 13wt%.
Embodiment 6
Get the 44 gram cotton pulp dregs of rice (polymerization degree 200), add in 200 gram 2.5wt% lithium hydroxide/2wt% sodium hydroxide/4.5wt% thiourea solutions (being chilled to-10 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 18wt%.
Embodiment 7
Get 2 gram bacteria celluloses (polymerization degree 4000), add in 200 gram 0.5wt% lithium hydroxide/3wt% sodium hydroxide/2wt% thiourea solutions (being chilled to-12 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, bacteria cellulose dissolves fully and obtains clarifying cellulose solution, and cellulose concentration is 1wt%.
Embodiment 8
Get the 13 gram cotton pulp dregs of rice (polymerization degree 500), add in 200 gram 1.5wt% lithium hydroxide/6.8wt% sodium hydroxide/1wt% thiocarbamide/6wt% aqueous solution of urea (being chilled to-6 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 6.1wt%.This solution is preserved at 4 ℃ and gelation was not taken place in 1 month, and leaves standstill natural deaeration in the process.
Embodiment 9
Get 10.5 gram wood pulps (polymerization degree 1200), add in 200 gram 5.5wt% lithium hydroxide/4wt% sodium hydroxide/3wt% thiocarbamide/25wt% aqueous solution of urea (being chilled to-15 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, wood pulp dissolves fully and obtains clarifying cellulose solution, and cellulose concentration is 5wt%.
Embodiment 10
Get the 8.4 gram cotton pulp dregs of rice (polymerization degree 400), add in 200 gram 6wt% lithium hydroxide/10wt% sodium hydroxide/6wt% thiocarbamide/0.1wt% aqueous solution of urea (being chilled to-5 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 4wt%.
Embodiment 11
Get the 44 gram cotton pulp dregs of rice (polymerization degree 200), add in 200 gram 0.1wt% lithium hydroxide/12wt% sodium hydroxide/0.1wt% thiocarbamide/15wt% aqueous solution of urea (being chilled to-10 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 18wt%.
Embodiment 12
Get the 23 gram cotton pulp dregs of rice (polymerization degree 400), add in 200 gram 4.5wt% lithium hydroxide/10wt% sodium hydroxide/1.5wt% thiocarbamide/0.1wt% aqueous solution of urea (being chilled to-8 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 10wt%.
Embodiment 13
Get 2 gram tunicate Mierocrystalline celluloses (polymerization degree 3200), add in 200 gram 7wt% lithium hydroxide/8wt% sodium hydroxide/2.5wt% thiocarbamide/2.5wt% aqueous solution of urea (being chilled to-7 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the tunicate Mierocrystalline cellulose dissolves fully and obtains clarifying cellulose solution, and cellulose concentration is 2wt%.
Embodiment 14
Get the 32 gram cotton pulp dregs of rice (polymerization degree 200), add in 200 gram 6.1wt% lithium hydroxide/5wt% sodium hydroxide/4wt% thiocarbamide/10wt% aqueous solution of urea (being chilled to-5 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, regenerated cellulose dissolves fully and obtains clarifying cellulose solution, and cellulose concentration is 17.8wt%.
Embodiment 15
Get 10.5 gram regenerated celluloses (polymerization degree 1300), add in 200 gram 5.5wt% lithium hydroxide/0.1wt% sodium hydroxide/6wt% thiocarbamide/5wt% aqueous solution of urea (being chilled to-6 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 4wt%.
Embodiment 16
Get the 17.5 gram cotton pulp dregs of rice (polymerization degree 500), add in 200 gram 4.5wt% lithium hydroxide/2wt% sodium hydroxide/4wt% thiourea solutions (being chilled to-8 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 8wt%.At 4000 rev/mins, 10 ℃ were descended centrifugal 10 minutes, and were not changed before cellulose solution is more centrifugal with ultracentrifuge.Pour out cellulose solution, the no micelle precipitation in concentrator bowl bottom.Behind knifing on the sheet glass, put into precipitation bath, soak after 5 minutes and take out, rinse well with deionized water.Be fixed at last to dry naturally on the polyfluortetraethylene plate and obtain transparent regenerated cellulose film.Tensile strength, elongation at break and the Young's modulus of the regenerated cellulose film that is recorded by electronics pulling experiment machine is respectively 148MPa, 12% and 6198MPa.Recording 800nm place transmittance by ultraviolet-visible spectrophotometer is 90%.
Embodiment 17
Get the 17.5 gram cotton pulp dregs of rice (polymerization degree 500), add in 200 gram 4.1wt% lithium hydroxide/2.5wt% sodium hydroxide/4.3wt% thiourea solutions (being chilled to-10 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 8wt%.At 4000 rev/mins, 10 ℃ were descended centrifugal 10 minutes, and were not changed before cellulose solution is more centrifugal with ultracentrifuge.Pour out cellulose solution, the no micelle precipitation in concentrator bowl bottom.Behind knifing on the sheet glass, put into precipitation bath, soak after 5 minutes and take out, rinse well with deionized water.Obtain the porous material of regenerated cellulose through after the lyophilize at last.The porous material of regenerated cellulose specific surface area that is recorded by the nitrogen adsorption experiment is 427m
2/ g, porosity is 92%.Recording 800nm place transmittance by ultraviolet-visible spectrophotometer is 86%.Fig. 2 illustrates the photo of porous material of regenerated cellulose, illustrates that the porous material that obtains has good optical transmission.Fig. 3 illustrates the stereoscan photograph of porous material of regenerated cellulose, illustrates that this material has uniform vesicular structure.
Embodiment 18
Get the 17.5 gram cotton pulp dregs of rice (polymerization degree 500), add in 200 gram 4wt% lithium hydroxide/2wt% sodium hydroxide/3wt% thiocarbamide/8wt% aqueous solution of urea (being chilled to-6 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 8wt%.At 4000 rev/mins, 10 ℃ were descended centrifugal 10 minutes, and were not changed before cellulose solution is more centrifugal with ultracentrifuge.Pour out cellulose solution, the no micelle precipitation in concentrator bowl bottom.Behind knifing on the sheet glass, put into precipitation bath, soak after 5 minutes and take out, rinse well with deionized water.Be fixed at last to dry naturally on the polyfluortetraethylene plate and obtain transparent regenerated cellulose film.Tensile strength, elongation at break and the Young's modulus of the regenerated cellulose film that is recorded by electronics pulling experiment machine is respectively 132MPa, 13% and 5362MPa.Recording 800nm place transmittance by ultraviolet-visible spectrophotometer is 88%.
Embodiment 19
Get the 17.5 gram cotton pulp dregs of rice (polymerization degree 500), add in 200 gram 4wt% lithium hydroxide/2wt% sodium hydroxide/4wt% thiocarbamide/10wt% aqueous solution of urea (being chilled to-6 ℃ in advance), then 0 ℃ (by brine bath temperature control) powerful stirring 10 minutes, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 8wt%.At 4000 rev/mins, 10 ℃ were descended centrifugal 10 minutes, and were not changed before cellulose solution is more centrifugal with ultracentrifuge.Pour out cellulose solution, the no micelle precipitation in concentrator bowl bottom.Behind knifing on the sheet glass, put into precipitation bath, soak after 5 minutes and take out, rinse well with deionized water.Obtain the porous material of regenerated cellulose through after the lyophilize at last.The porous material of regenerated cellulose specific surface area that is recorded by the nitrogen adsorption experiment is 392m
2/ g, porosity is 90%.Recording 800nm place transmittance by ultraviolet-visible spectrophotometer is 82%.
Embodiment 20-39
1000 gram 5.5wt% lithium hydroxide/2.4wt% sodium hydroxide/4.6wt% thiourea solutions are chilled to-8 ℃ in advance, add the 87.5 gram exsiccant cotton pulp dregs of rice (polymerization degree 500) immediately, stirring 10 minutes in 0 ℃ (by brine bath temperature control) brute force, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 8wt%.Under 1 normal atmosphere, filter, made it de-bubbled in 6 hours 4 ℃ of quiet deaerations of following vacuum then, obtain transparent cellulose spin dope with 200 eye mesh screens.Extrude with spinning jet at 10 ℃, spinning jet has 30 orifices, and the aperture is 100 4. m.Spinning solution enters precipitation bath after spinning jet is extruded, and draws by godet roller, with this godet roller long filament is applied tension force, and long filament is drafted at air gap thus.Behind godet roller, long filament cuts off at once, cleans solvent then, and aftertreatment and dry oils.Change employed precipitation bath and carried out extrusion test altogether 20 times.Fig. 4 shows the stereoscan photograph of regenerated cellulose fibre, and fiber surface is smooth, even structure.Intensity, the elongation at break result of the regenerated cellulose fibre that is recorded by electronics pulling experiment machine are stated from table 1.
Table 1
Embodiment 40-54
1000 gram 6wt% lithium hydroxide/1.6wt% sodium hydroxide/3.8wt% thiourea solutions are chilled to-8 ℃ in advance, add the 87.5 gram exsiccant cotton pulp dregs of rice (polymerization degree 500) immediately, stirring 10 minutes in 0 ℃ (by brine bath temperature control) brute force, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 8wt%.Under 1 normal atmosphere, filter, made it de-bubbled in 6 hours 4 ℃ of quiet deaerations of following vacuum then, obtain transparent cellulose spin dope with 200 eye mesh screens.Extrude with spinning jet at 10 ℃, spinning jet has 30 orifices, and the aperture is 120 4. m.Spinning solution is extruded the back from spinning jet and is entered precipitation bath by air gap, and draws by godet roller, with this godet roller long filament is applied tension force, and long filament is drafted at air gap thus.Behind godet roller, long filament cuts off at once, cleans solvent then, and aftertreatment and dry oils.Change air gap and precipitation bath and carried out 15 experiments.Intensity, the elongation at break of the regenerated cellulose fibre that is recorded by electronics pulling experiment machine are stated from table 2 respectively.
Table 2
Embodiment 55
1000 gram 5.5wt% lithium hydroxide/1.4wt% sodium hydroxide/4wt% thiourea solutions are chilled to-8 ℃ in advance, add 52.5 gram exsiccant wood pulps (polymerization degree 1200) immediately, stirring 10 minutes in 0 ℃ (by brine bath temperature control) brute force, wood pulp dissolves fully and obtains clarifying cellulose solution, and cellulose concentration is 5wt%.Under 1 normal atmosphere, filter, made it de-bubbled in 6 hours 4 ℃ of quiet deaerations of following vacuum then, obtain transparent cellulose spin dope with 200 eye mesh screens.Extrude with spinning jet at 10 ℃, spinning jet has 30 orifices, and the aperture is 100 4. m.Spinning solution is extruded the back from spinning jet and is entered precipitation bath by air gap, and draws by godet roller, with this godet roller long filament is applied tension force, and long filament is drafted at air gap thus.Behind godet roller, long filament cuts off at once, cleans solvent then, and aftertreatment and dry oils.Intensity, the elongation at break of the regenerated cellulose fibre that is recorded by electronics pulling experiment machine are respectively 2.3cN/dtex and 15%.
Embodiment 56
1000 gram 4wt% lithium hydroxide/2wt% sodium hydroxide/4wt% thiocarbamide/8wt% aqueous solution of urea are chilled to-8 ℃ in advance, add the 87.5 gram exsiccant cotton pulp dregs of rice (polymerization degree 600) immediately, stirring 10 minutes in 0 ℃ (by brine bath temperature control) brute force, the cotton pulp dregs of rice dissolve fully and obtain clarifying cellulose solution, and cellulose concentration is 8wt%.Under 1 normal atmosphere, filter, made it de-bubbled in 6 hours 4 ℃ of quiet deaerations of following vacuum then, obtain transparent cellulose spin dope with 200 eye mesh screens.Extrude with spinning jet at 10 ℃, spinning jet has 30 orifices, and the aperture is 120 4. m.Spinning solution enters precipitation bath after spinning jet is extruded, and draws by godet roller, with this godet roller long filament is applied tension force, and long filament is drafted at air gap thus.Behind godet roller, long filament cuts off at once, cleans solvent then, and aftertreatment and dry oils.Intensity, the elongation at break of the regenerated cellulose fibre that is recorded by electronics pulling experiment machine are respectively 2.6cN/dtex and 13%.
Embodiment 57
Each 10 gram of regenerated cellulose film, fiber and porous material are heated to 250～1200 degree in process furnace, nitrogen is as shielding gas.Cellulose membrane, fiber, porous material obtain black carbon film, fiber, porous carbon materials through high temperature pyrolysis.The carbon productive rate is 14%～27%.Recording the porous carbon materials specific surface area that is obtained by the carbonization of Mierocrystalline cellulose porous material by the nitrogen adsorption experiment is 800～1800m2/g.Fig. 5 illustrates the stereoscan photograph of porous carbon materials, illustrates that this carbon material has uniform vesicular structure.
Claims (18)
1. the water solvent of a dissolving cellulos, it is characterized in that: this solvent comprises lithium hydroxide, sodium hydroxide, thiocarbamide, and wherein the content of lithium hydroxide is 0.1～7wt%, and the content of sodium hydroxide is 0.1～12wt%, and the content of thiocarbamide is 0.1～6wt%.
2. water solvent according to claim 1 is characterized in that: the urea that also comprises 0.1～25wt%.
3. method of utilizing claim 1 or 2 each described water solvent dissolving cellulos, it is characterized in that: 100 parts of (weight unit) water solvents are chilled to-15～5 ℃ in advance, 1～22 part of (weight unit) Mierocrystalline cellulose is scattered in the water solvent, stirred 2～10 minutes, obtain transparent Mierocrystalline cellulose strong solution, wherein content of cellulose is 1～18wt%, and the described cellulosic polymerization degree is between 200～4000.
4. method of utilizing claim 1 or 2 described water solvents to prepare the carbon material of cellulose membrane, fiber or porous material, it is characterized in that: 100 parts of (weight unit) water solvents are chilled to-15～5 ℃ in advance, 1～22 part of (weight unit) Mierocrystalline cellulose is scattered in the water solvent, stirred 2～10 minutes, obtain transparent Mierocrystalline cellulose strong solution, wherein content of cellulose is 1～18wt%; Then with cellulose solution through filtration, deaeration, casting film-forming or through after extruding, in precipitation bath, regenerate, after make regenerated cellulose film, fiber or porous material after the washing, drying; Again with the regenerated cellulose film, fiber or the porous material that make through 250 ℃ to 1200 ℃ carbonizations under inert atmosphere protection, obtain corresponding carbon material.
5. method according to claim 4 is characterized in that: described precipitation bath is the aqua that is added with monovalent cation therein, or is lower than the nonpolar organic liquid of lower boiling of 50wt% at water ratio.
6. method of utilizing claim 1 or 2 described water solvents to prepare the carbon material of cellulose membrane, fiber or porous material, it is characterized in that: 100 parts of (weight unit) water solvents are chilled to-15～5 ℃ in advance, 1～22 part of (weight unit) Mierocrystalline cellulose is scattered in the water solvent, stirred 2～10 minutes, obtain transparent Mierocrystalline cellulose strong solution, wherein content of cellulose is 1～18wt%; Then with cellulose solution through filtration, deaeration, casting film-forming or through after extruding, by air gap, in precipitation bath, regenerate, after make regenerated cellulose film, fiber or porous material after the washing, drying; Again with the regenerated cellulose film, fiber or the porous material that make through 250 to 1200 ℃ of carbonizations under inert atmosphere protection, obtain corresponding carbon material.
7. method according to claim 6 is characterized in that: described precipitation bath is the aqua that is added with monovalent cation therein, or is lower than the nonpolar organic liquid of lower boiling of 50wt% at water ratio.
8. according to the method for claim 6, it is characterized in that: described film of extruding or fiber are exposed in the air-flow that contains the fatty alcohol that is gas phase state in described air gap, and contact with fatty alcohol.
9. according to the method for claim 8, it is characterized in that: described fatty alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol or the trimethyl carbinol, or the mixture of aforementioned various alcohol.
10. method of utilizing claim 1 or 2 described water solvents to prepare cellulose membrane, fiber or porous material, it is characterized in that: 100 parts of (weight unit) water solvents are chilled to-15～5 ℃ in advance, 1～22 part of (weight unit) Mierocrystalline cellulose is scattered in the water solvent, stirred 2～10 minutes, obtain transparent Mierocrystalline cellulose strong solution, wherein content of cellulose is 1～18wt%; The solution of Mierocrystalline cellulose in water solvent is extruded by the spray silk groove or the hole of spinning jet, thus extruded film or fiber; Make the film extruded or fiber enter precipitation bath and draw, install drawing-off film or fiber thus by towing mechanism; The film or the fiber of drawing-off are continued to be processed into regenerated cellulose film, fiber or porous material.
11. method according to claim 10 is characterized in that: described precipitation bath is the aqua that is added with monovalent cation therein, or is lower than the nonpolar organic liquid of lower boiling of 50wt% at water ratio.
12. method of utilizing claim 1 or 2 described water solvents to prepare cellulose membrane, fiber or porous material, it is characterized in that: 100 parts of (weight unit) water solvents are chilled to-15～5 ℃ in advance, 1～22 part of (weight unit) Mierocrystalline cellulose is scattered in the water solvent, stirred 2～10 minutes, obtain transparent Mierocrystalline cellulose strong solution, wherein content of cellulose is that 1～18wt% extrudes the solution of Mierocrystalline cellulose in water solvent by the spray silk groove or the hole of spinning jet, thus extruded film or fiber; The film extruded or fiber are drawn by air gap, precipitation bath and by towing mechanism, install drawing-off film or fiber thus; The film or the fiber of drawing-off are continued to be processed into regenerated cellulose film, fiber or porous material.
13. the method according to claim 12 is characterized in that: described film of extruding or fiber are exposed in the air-flow that contains the fatty alcohol that is gas phase state in described air gap, and contact with fatty alcohol.
14. the method according to claim 13 is characterized in that: described fatty alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol or the trimethyl carbinol, or the mixture of aforementioned various alcohol.
15. method according to claim 12 is characterized in that: described precipitation bath is the aqua that is added with monovalent cation therein, or is lower than the nonpolar organic liquid of lower boiling of 50wt% at water ratio.
16. according to claim 5,7,11 or 15 described methods, it is characterized in that: the nonpolar organic liquid of described lower boiling is alcohol, ketone, ester or its mixture.
17. method according to claim 16 is characterized in that: described alcohol is methyl alcohol, ethanol; Described ketone is acetone.
18. utilize claim 1 or 2 described water solvents at dissolving cellulos and carry out spinning, system film or system porous material, or make the application of carbon material by prepared cellulose membrane, fiber or porous material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102443868A (en) * | 2010-09-30 | 2012-05-09 | 中国纺织科学研究院 | Method for manufacturing regenerated cellulose fibers |
| CN107586395A (en) * | 2017-10-11 | 2018-01-16 | 盐城工学院 | A kind of cellulose potassium titanate composite membrane, its preparation method and application |
| CN107653502A (en) * | 2017-10-13 | 2018-02-02 | 武汉大学 | A kind of preparation method of high strength regenerative cellulose fiber |
| CN109879282A (en) * | 2019-04-11 | 2019-06-14 | 合肥工业大学 | A kind of method that thermal field argon-arc plasma field double-field coupled prepares biomass-based active carbon |
| CN111499883A (en) * | 2020-05-19 | 2020-08-07 | 武汉水木弘新材料有限公司 | Low-temperature dissolving method adopting cellulose combined raw materials and application thereof |
| CN115959648A (en) * | 2022-12-21 | 2023-04-14 | 北方民族大学 | Simple preparation method of high-defect carbon film and application of high-defect carbon film in CO2 reduction flow cell |
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2008
- 2008-04-09 CN CNA2008100666178A patent/CN101555321A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443868A (en) * | 2010-09-30 | 2012-05-09 | 中国纺织科学研究院 | Method for manufacturing regenerated cellulose fibers |
| CN102443868B (en) * | 2010-09-30 | 2014-10-15 | 中国纺织科学研究院 | Method for manufacturing regenerated cellulose fibers |
| CN107586395A (en) * | 2017-10-11 | 2018-01-16 | 盐城工学院 | A kind of cellulose potassium titanate composite membrane, its preparation method and application |
| CN107586395B (en) * | 2017-10-11 | 2020-11-17 | 盐城工学院 | Cellulose-potassium titanate composite membrane, preparation method and application thereof |
| CN107653502A (en) * | 2017-10-13 | 2018-02-02 | 武汉大学 | A kind of preparation method of high strength regenerative cellulose fiber |
| CN107653502B (en) * | 2017-10-13 | 2020-05-22 | 武汉大学 | Preparation method of high-strength regenerated cellulose fibers |
| CN109879282A (en) * | 2019-04-11 | 2019-06-14 | 合肥工业大学 | A kind of method that thermal field argon-arc plasma field double-field coupled prepares biomass-based active carbon |
| CN111499883A (en) * | 2020-05-19 | 2020-08-07 | 武汉水木弘新材料有限公司 | Low-temperature dissolving method adopting cellulose combined raw materials and application thereof |
| CN115959648A (en) * | 2022-12-21 | 2023-04-14 | 北方民族大学 | Simple preparation method of high-defect carbon film and application of high-defect carbon film in CO2 reduction flow cell |
| CN115959648B (en) * | 2022-12-21 | 2024-05-28 | 北方民族大学 | Simple preparation method of high-defect carbon film and application of high-defect carbon film in CO2 reduction flow cell |
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