CN107304246A - A kind of solvent for dissolving cellulose and application thereof - Google Patents
A kind of solvent for dissolving cellulose and application thereof Download PDFInfo
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- CN107304246A CN107304246A CN201610255183.0A CN201610255183A CN107304246A CN 107304246 A CN107304246 A CN 107304246A CN 201610255183 A CN201610255183 A CN 201610255183A CN 107304246 A CN107304246 A CN 107304246A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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Abstract
The present invention relates to a kind of quick solvent for directly dissolving cellulose, it is made up of the aqueous solution of sodium hydroxide and thiocarbamide, sodium hydroxide accounts for the 8.1~12.0% of aqueous solution gross weight in the solvent, and thiocarbamide accounts for the 3.0~6.0% of aqueous solution gross weight.Present invention also offers a kind of method of directly quick dissolving cellulose, native cellulose or regenerated cellulose are scattered in above-mentioned solvent, stirring obtains transparent cellulose concentrated solution.By this cellulose solution by filtering, deaerating, after casting film-forming or spinning, by film or fiber in solidification liquid solidification regeneration, clean and regenerated cellulose film or fiber can be made in drying.The present invention using solvent due to directly being dissolved, and condition is wide in range, it is possible to use the technique and equipment of existing viscose production are realized by simple reformation, and waste liquid can be used for chemical fertilizer production.It is expected to replace industrial viscose process and cuprammonium process, thus is with a wide range of applications.
Description
Technical field
The present invention relates to a kind of solvent of use sodium hydroxide and thiocarbamide mixed aqueous solution as cellulose, and dissolve cellulose with it and prepare the new method of regenerated celulose fibre and film, belong to natural polymer subdomains, fall within chemistry, agricultural, field of environment engineering.
Background technology
Plant cellulose is renewable resource most abundant on the earth, belongs to environment-friendly material, makes full use of cellulose not only can be with environmental protection, and can save limited petroleum resources.Because cellulose can not be melted with very strong intramolecular and intermolecular hydrogen bonding, therefore indissoluble solution, so as to greatly limit its extensive use.The traditional handicraft of production regenerated cellulose fiber and film is still viscose process technique, and its principle is cellulose (NaOH concentration 18wt%) and CS under highly basic effect2Reaction generates cellulose xanthate and is dissolved in dilute alkaline soln, and then regeneration prepares viscose rayon or glassine paper (cellophane) in dilute acid soln.A large amount of CS are used in its production process2And discharge H2S, SO2And severe contamination environment.(J.Macromol.Sci.-Rev.Macromol.
Chem., 1980, C18 (1), 1).Cuprammonium process is once used to produce cuprammonium staple fibre, but reclaims problem there is also environmental pollution and solution.In the late two decades, various organic or inorganic novel solvents have achieved greater advance, wherein having dimethyl sulfoxide (DMF)-nitrogen oxides (U.S.pattent 3236669,1966), NH3/NH3The SCN aqueous solution (J.Polym.Sci.
Polym.Chem.Ed.1980,18,3469), Ca (SCN)2With the NaSCN aqueous solution (Polymer J.1998,30,43；30,49), ZnCl2The aqueous solution (U.S.Patent 5290349,1994), trichloroacetaldehyde-dimethyl sulfoxide (DMF)-pyridine mixed liquor (Polym.J 1980,12,521), LiCl/DMAc (U.S.Patent 4302252,1981), NaOH/ urea prepares cellulose carbamate dissolving spinning technique, N- methyl-N- morpholine oxides (NMMO) (J.Polym.Sci.：Polym.Lett. Ed.1979,17,219) and the NaOH aqueous solution (Japan Patent 1777283,1983；Polym.J 1984,12,857) etc..N- methyl-N- morpholine oxides are most strong cellulose solvents so far, and a small amount of cellulose products (Lyocell) prepared with it have been enter into market.But because its is expensive, spinning temperature is higher, industrialized production slower development.The NaOH aqueous solution is to dissolve the generally the least expensive solvent of cellulose, when the hydrogen bond of native cellulose is corrupted to a certain degree, in the NaOH aqueous solution that 7-9wt% is may be dissolved at 4 DEG C or so.But this solvent is only capable of dissolving after Steam explosion treatment, and the degree of polymerization is less than 250 wood pulp cellulose, it is impossible to dissolve cotton linter pulp.And obtained filament intensity is relatively low, be not suitable for industrialization spinning or film.We dissolve cellulose and successfully prepare the regenerated cellulose film of good strength with 6%NaOH/5% thiourea solutions as characteristics among new solvents of cellulose.But the dicyandiamide solution must could dissolve cellulose for 3-5 hours under freezing conditions prepares transparent cellulose concentrated solution, therefore, it is difficult to realize industrialization.
The content of the invention
The new method of cellulose solution is prepared it is an object of the invention to provide a kind of novel solvent of quick directly dissolving cellulose and with it.
To achieve the above object, the technical solution adopted in the present invention is as follows：
A kind of solvent for dissolving cellulose, is made up of the aqueous solution of sodium hydroxide and thiocarbamide, it is characterised in that：Sodium hydroxide accounts for 8.1~12.0wt% of aqueous solution gross weight in the solvent, and the concentration that thiocarbamide accounts for aqueous solution gross weight is to equal to 6.0 wt% more than 4.0wt%.
Above-mentioned solvent can be prepared by laxative remedy：After sodium hydroxide and thiocarbamide are mixed, add water and obtain required solvent；Or sodium hydroxide is first made into the aqueous solution, then add thiocarbamide and obtain required solvent；Also sodium hydroxide and thiocarbamide can be made into the aqueous solution respectively, is then mixed to get required solvent.Be stored in less than 20 DEG C it is standby.
A kind of method that cellulose is directly quickly dissolved using above-mentioned solvent, native cellulose or regenerated cellulose are scattered in -10 DEG C~5 DEG C of 8.1~12.0wt% sodium hydroxides and more than 4.0wt% into equal to the mixed aqueous solution of 6.0wt% thiocarbamides, native cellulose or regenerated cellulose are being sufficiently stirred in the time of 10~15 minutes dissolving rapidly and are forming transparent cellulose concentrated solution, and wherein content of cellulose is 2-10wt%.
Present invention also offers a kind of method for preparing regenerated cellulose film or fiber using above-mentioned solvent, native cellulose or regenerated cellulose are dissolved in 8.1~12.0wt% sodium hydroxides and containing cellulose 2-10wt% transparency cellulose concentrated solution is made into equal to the mixed aqueous solution of 6.0wt% thiocarbamides more than 4.0wt%, again by this cellulose solution by filtering, degassing, after casting film-forming or spinning, by film or fiber in solidification liquid solidification regeneration, clean and dry obtained regenerated cellulose film or fiber.
Above-mentioned solidification liquid is 3-10wt% dilute acid solutions, or 5-15wt% ammonium salt aqueous solutions, or diluted acid containing 3-10wt% and 5-15wt% sodium sulphate the aqueous solution.
Compared with conventional technology, the present invention has marked improvement, and sodium hydroxide/thiourea solution therein can be adapted to the various cellulose fibres of industrialized production, film, non-woven fabrics and chromatographic column porous aggregate in -10 DEG C~5 DEG C or so quick dissolving celluloses.The main innovation of the present invention is as follows：
Sodium hydroxide and thiocarbamide mixed aqueous solution concentration used in the present invention be respectively 8.1-12.0% and more than 4.0% to equal to 6.0% (weight ratio), wherein NaOH concentration is lower than the impregnation concentrations (15-18%) of viscose process.And for various native celluloses (such as cotton linter pulp, wood pulp cellulose etc.), wood pulp cellulose and regenerated cellulose (such as non-woven fabrics, glassine paper, short rayon fiber) after steaming is quick-fried, directly can quickly dissolve and have larger solubility；Especially for cotton linter pulp (the I fiber types element, M of high-crystallinityη＜ 10.2 × 104), it is not necessary to by switching to the refrigerating process just directly dissolving of solid phase by liquid phase, its reason be primarily due to improve NaOH consumptions and thiocarbamide cooperative effect can effectively destroy between poly- polysaccharide molecule and intramolecular hydrogen bond and accelerate it to dissolve.
This method is with cheap and free of contamination sodium hydroxide and thiocarbamide [(CS (NH2)2)] it is solvent, pass through 10 to 15 minutes quick dissolving celluloses under the conditions of -10 DEG C~5 DEG C.Thus transparent cellulose concentrated solution is obtained, the mouldability of good fiber spinnability and film is maintained, available for spinning or film；There is difference substantially with the derivatization dissolution process such as viscose process and cellulose carbamate method, the present invention is using native cellulose as raw material, whole process occurs without chemical reaction, and the techniques such as alkalization, experienced, sulphur ortho acid and maturation are reduced than traditional viscose rayon technique；Consumption of raw materials is few simultaneously, and with short production cycle, technological process is simple.Its feature is not needing, and with short production cycle, technological process is short, in favor of industrialized production.
Due to directly being dissolved using solvent, condition is wide in range, it is possible to use the technique and equipment of existing viscose production are realized by simple reformation, and waste liquid can be used for chemical fertilizer production.It is expected to replace industrial viscose process and cuprammonium process, thus is with a wide range of applications.
Embodiment
Technical scheme is described further below in conjunction with specific example：
Embodiment 1
Take quick-fried wood pulp cellulose (the viscosity average molecular weigh M of steamingη=4.5 × 104) 9 grams, add and be sufficiently stirred for 5 minutes in 200 grams of 9.5wt%NaOH/4.5wt% thiocarbamide mixed aqueous solutions, ice-water bath (0-5 DEG C), obtain transparent cellulose solution, filtered under 0.1~0.2MPa pressure with 200 mesh filter screens, acquisition settled solution.
Embodiment 2
Take non-woven fabrics (viscosity average molecular weigh Mη=12.0 × 104) 10 grams, 200 grams of 9.5wt%NaOH/4.5wt% thiocarbamide mixed aqueous solutions that precooling temperature is -5 DEG C are added, are sufficiently stirred for, are dissolved in 10 minutes, are filtered under 1~2 atmospheric pressure with 200 mesh filter screens, acquisition settled solution.
Embodiment 3
15 grams of regenerated cellulose (short rayon fiber) is taken, 185 grams of 8wt%NaOH/4wt% thiocarbamide mixed aqueous solutions are added, is stirred 5 minutes in 5 DEG C, obtains transparent cellulose solution.With ultracentrifuge at 8,000 revs/min, centrifuged 30 minutes at 15 DEG C, cellulose solution does not change before relatively centrifuging.Cellulose solution is poured out, concentrator bowl bottom is precipitated without micelle, fiber presence is visible by naked eyes in resulting solution.Regenerated cellulose (short rayon fiber) is completely dissolved.One week still stabilization is preserved at 7-10 DEG C.
Embodiment 4
Take wood pulp cellulose (viscosity average molecular weigh Mη=10.0 × 104) 8.4 grams, add and be sufficiently stirred in 200 grams of 9.5wt%NaOH/4.5wt% thiocarbamide mixed aqueous solutions, ice salt bath (- 4 DEG C), dissolved in 10 minutes, filtered under 1~2 atmospheric pressure with 200 mesh filter screens, acquisition settled solution.
Embodiment 5
Take cotton linter pulp cellulose (viscosity average molecular weigh Mη=10.2 × 104) 8.4 grams, add and be sufficiently stirred in 200 grams of 9.5wt%NaOH/4.5wt % thiocarbamide mixed aqueous solutions, ice-water bath (0-5 DEG C), dissolved in 10 minutes, filtered under 0.1~0.2MPa pressure with 200 mesh filter screens, acquisition settled solution.It is immediately placed on a glass after knifing in 5wt% aqueous sulfuric acids, or 5wt% aqueous hydrochloric acid solutions, or 1-2mol/L aqueous acetic acids, immersion is taken out after 2-5 minutes, is rinsed well with water.Finally it is attached to dry naturally on poly (methyl methacrylate) plate and obtains regenerated cellulose film.The tensile strength σ of the regenerated cellulose film solidified by 5wt% sulfuric acid is measured by electronics tension testerb, elongation at break εbAnd modulus of elasticity is respectively 88MPa, 11% and 4679MPa.Light transmittance is 85% (800nm).
Embodiment 6
Take cotton linter pulp cellulose (viscosity average molecular weigh Mη=8.5 × 104) 10 grams, add 200 grams of 10wt%NaOH/5wt% thiocarbamide mixed aqueous solutions that temperature is 0 DEG C, it is sufficiently stirred for, dissolving obtains colourless transparent solution in 10 minutes, with ultracentrifuge 8,000 rev/min, centrifuged at 15 DEG C and remove within 30 minutes after a small amount of non-fibrinolysin knifing on a glass, be immediately placed in 5-20wt% ammonium sulfate solutions, or 5-15wt% aqueous ammonium chloride solutions, immersion is taken out after 3-4 minutes, is rinsed well with water.Finally it is attached to dry naturally on poly (methyl methacrylate) plate and obtains regenerated cellulose film.The tensile strength σ of the cellulose membrane by 5wt% ammonium sulfate solution solidification regenerations is measured by electronics tension testerb, elongation at break εbAnd modulus of elasticity is respectively 83MPa, 9.5% and 3923MPa.Light transmittance is 84% (800nm)
Embodiment 7
Take cotton linter pulp (viscosity average molecular weigh Mη=8.5 × 104) 8.4 grams, 200 grams of 9.5wt%NaOH/4wt% thiocarbamide mixed aqueous solutions that precooling temperature is -8 DEG C are added, are sufficiently stirred for, it is completely dissolved in 10 minutes, with ultracentrifuge at 8,000 revs/min, centrifuged 30 minutes at 15 DEG C, cellulose solution does not change before relatively centrifuging.Cellulose solution is poured out, concentrator bowl bottom is precipitated without micelle.Syringe, which prepares cellulose silk and enters solidification regeneration in 5wt% aqueous sulfuric acids, obtains cellulose silk, rinses nature well with water and dries.Its tensile strength σ is measured by electronics tension testerbFor 8.74CN/dtex, elongation at break εbFor 10.4%.
Embodiment 8
Take cotton linter pulp (viscosity average molecular weigh Mη=8.5 × 104) 10 grams, 200 grams of 9.5wt%NaOH/4.5wt% thiocarbamide mixed aqueous solutions that precooling temperature is -8 DEG C are added, are sufficiently stirred for, it is completely dissolved in 10 minutes, with ultracentrifuge at 8,000 revs/min, centrifuged 30 minutes at 15 DEG C, cellulose solution does not change before relatively centrifuging.Cellulose solution is poured out, concentrator bowl bottom is precipitated without micelle.With 5wt% sulfuric acid/10wt% aqueous sodium persulfate solutions, or 12wt% aqueous ammonium chloride solutions are coagulating bath, and 25-30 DEG C of coagulation bath temperature prepares regenerated celulose fibre by simple spinning-drawing machine.
Claims (5)
1. a kind of solvent for dissolving cellulose, is made up of the aqueous solution of sodium hydroxide and thiocarbamide, it is characterised in that：Sodium hydroxide accounts for 8.1~12.0wt% of aqueous solution gross weight in the solvent, and the concentration that thiocarbamide accounts for aqueous solution gross weight is to equal to 6.0wt% more than 4.0wt%.
2. the method that the solvent described in a kind of utilization claim 1 directly quickly dissolves cellulose, it is characterised in that：Native cellulose or regenerated cellulose are scattered in -10 DEG C~5 DEG C of 8.1~12.0wt% sodium hydroxides and more than 4.0wt% to being equal in the mixed aqueous solution of 6.0wt% thiocarbamides, native cellulose or regenerated cellulose were sufficiently stirred in the time of 10~15 minutes
Dissolve rapidly and form transparent cellulose concentrated solution, wherein content of cellulose is 2-10 wt%.
3. the method that the solvent described in a kind of utilization claim 1 prepares regenerated cellulose film or fiber, it is characterised in that：Native cellulose or regenerated cellulose are dissolved in 8.1~12.0wt% sodium hydroxides and containing cellulose 2-10wt% transparency cellulose concentrated solution is made into equal to the mixed aqueous solution of 6.0wt% thiocarbamides more than 4.0wt%, again by this cellulose solution by filtering, degassing, after casting film-forming or spinning, by film or fiber in solidification liquid solidification regeneration, clean and dry obtained regenerated cellulose film or fiber.
4. according to the method described in claim 3, it is characterised in that：Described solidification liquid is 3-10wt% dilute acid solutions, or 5-15wt% ammonium salt aqueous solutions, or diluted acid containing 3-10wt% and 5-15wt% sodium sulphate the aqueous solution.
5. application of the solvent described in claim 1 in dissolving native cellulose or regenerated cellulose and carrying out spinning or film forming industry.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108178982A (en) * | 2017-12-26 | 2018-06-19 | 天长市金陵电子有限责任公司 | A kind of excellent LED light heat radiation coating of adhesive force |
| CN112552539A (en) * | 2020-12-10 | 2021-03-26 | 四川三联新材料有限公司 | Low-adsorption hydrophobic cellulose membrane and preparation method and application thereof |
-
2016
- 2016-04-25 CN CN201610255183.0A patent/CN107304246A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108178982A (en) * | 2017-12-26 | 2018-06-19 | 天长市金陵电子有限责任公司 | A kind of excellent LED light heat radiation coating of adhesive force |
| CN112552539A (en) * | 2020-12-10 | 2021-03-26 | 四川三联新材料有限公司 | Low-adsorption hydrophobic cellulose membrane and preparation method and application thereof |
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