CN116163025A - Method for coagulating and forming solution containing natural polymer and method for spinning long fiber - Google Patents
Method for coagulating and forming solution containing natural polymer and method for spinning long fiber Download PDFInfo
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- CN116163025A CN116163025A CN202310301287.0A CN202310301287A CN116163025A CN 116163025 A CN116163025 A CN 116163025A CN 202310301287 A CN202310301287 A CN 202310301287A CN 116163025 A CN116163025 A CN 116163025A
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- 239000000835 fiber Substances 0.000 title claims abstract description 85
- 230000001112 coagulating effect Effects 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229920005615 natural polymer Polymers 0.000 title claims abstract description 42
- 238000009987 spinning Methods 0.000 title claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000004202 carbamide Substances 0.000 claims abstract description 37
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007711 solidification Methods 0.000 claims abstract description 29
- 230000008023 solidification Effects 0.000 claims abstract description 29
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002166 wet spinning Methods 0.000 claims abstract description 11
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 6
- 239000011787 zinc oxide Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000005345 coagulation Methods 0.000 claims description 39
- 230000015271 coagulation Effects 0.000 claims description 39
- 229920002678 cellulose Polymers 0.000 claims description 20
- 239000001913 cellulose Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 229920002101 Chitin Polymers 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000002861 polymer material Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 47
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 4
- 239000012266 salt solution Substances 0.000 abstract description 2
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000004627 regenerated cellulose Substances 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- 229920000875 Dissolving pulp Polymers 0.000 description 6
- 229920003043 Cellulose fiber Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229940079826 hydrogen sulfite Drugs 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000467 phytic acid Substances 0.000 description 2
- 229940068041 phytic acid Drugs 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WTHDKMILWLGDKL-UHFFFAOYSA-N urea;hydrate Chemical compound O.NC(N)=O WTHDKMILWLGDKL-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- -1 zinc oxide) Chemical class 0.000 description 1
Images
Classifications
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
-
- 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
- D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
- D01F13/02—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of cellulose, cellulose derivatives or proteins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a solution solidification forming method containing natural polymer, which is characterized in that fiber trickle obtained by wet spinning of the solution containing natural polymer is formed by at least 1 coagulating bath, the solution containing natural polymer contains metal hydroxide and auxiliary agent, and the auxiliary agent is at least one selected from urea, zinc oxide and thiourea; the bicarbonate or the bisulphite or the combination of the bicarbonate and the carbonate or the combination of the bisulphite and the sulfite is used as a coagulating bath component, and the long fiber with round section and excellent mechanical property can be prepared by adopting low-cost, green, high-efficiency, nontoxic, harmless and cheap inorganic salt solution without strong acid and organic solvent, and has smooth, soft and glossy surface. And in the coagulating bath, bicarbonate and carbonate or bisulphite and sulfite are easy to separate and recycle.
Description
Technical Field
The invention relates to the technical field of natural polymer solution solidification forming, in particular to a solution solidification forming method containing natural polymers and a long fiber spinning method.
Background
Natural polymers mainly comprise cellulose, chitin, chitosan and the like, and have extremely strong hydrogen bonding action among natural polymers and in molecules, so that the natural polymers are insoluble in common solvents and are difficult to directly use. At present, the solvent for dissolving natural polymers mainly comprises NaOH/CS 2 LiCl/DMAc, ionic liquids, N-methylmorpholine-N-oxide and aqueous alkali/urea solvent systems, etc. The alkali solution is a natural polymer solvent system with great development prospect at present, such as sodium hydroxide, sodium hydroxide/urea water, lithium hydroxide/urea, potassium hydroxide/urea and the like, and then the natural polymer solution is formed in an acidic coagulation bath. The coagulation forming is a key step of precipitating spinning solution from homogeneous trickle, the composition of coagulation bath not only directly influences and determines the product performance and cost, but also needs to consider the problems of salt separation and recovery and three-waste treatment caused by the reaction of the coagulation bath and solvent.
Patent application 200410013689. X discloses a preparation method of regenerated cellulose fibers, cellulose is dissolved in mixed aqueous solution of 5-12 wt% of sodium hydroxide and 8-20wt% of urea, and the mixed aqueous solution is fully stirred to prepare cellulose concentrated solution, natural polymers mainly comprise cellulose, chitin, chitosan and the like, and natural polymers have extremely strong hydrogen bonding action between molecules and in molecules, so that the cellulose is insoluble in common solvents and is difficult to directly use. At present, the solvent for dissolving natural polymers mainly comprises NaOH/CS 2 LiCl/DMAc, ionic liquids, N-methylmorpholine-N-oxide and aqueous alkali/urea solvent systems, etc. The alkali solution is a natural polymer with great development prospect at presentSolvent systems such as sodium hydroxide, sodium hydroxide/aqueous urea, lithium hydroxide/urea, potassium hydroxide/urea, etc., after which the natural polymer solution is shaped in an acidic coagulation bath. The coagulation forming is a key step of precipitating spinning solution from homogeneous trickle, the composition of coagulation bath not only directly influences and determines the product performance and cost, but also needs to consider the problems of salt separation and recovery and three-waste treatment caused by the reaction of the coagulation bath and solvent.
Patent application 200410013689. X discloses a preparation method of regenerated cellulose fibers, which comprises the steps of dissolving cellulose in a mixed aqueous solution of 5-12 wt% of sodium hydroxide and 8-20wt% of urea, fully stirring to obtain a cellulose concentrated solution, spinning on a spinning machine by adopting a wet spinning method, and regenerating and solidifying in a coagulating bath, wherein the coagulating bath comprises 3-25 wt% of sulfuric acid aqueous solution, 3-25 wt% of sulfuric acid/5-30 wt% of sodium sulfate aqueous solution, 3-25 wt% of sulfuric acid/5-30 wt% of ammonium sulfate aqueous solution and the like. In the method for preparing regenerated cellulose fibers by the two-step coagulation bath method disclosed in patent application 200510018799.8, the composition of the coagulation bath is 5-20wt% sulfuric acid/10-25wt% sodium sulfate mixed aqueous solution. CN103757720a discloses a coagulating bath for forming cellulose solution by alkali/urea/water system solvent method, the primary coagulating bath and the secondary coagulating bath are aqueous solutions containing phosphoric acid and/or phosphate, the cellulose fiber is thoroughly coagulated, and the prepared fiber interface is round, the fiber is soft and has high strength. CN110042488A discloses a solvent system of sodium hydroxide/urea/zinc oxide, which is prepared by spinning and solidifying in a mixed solution of citric acid, sodium citrate, ethylene glycol and water (5-35 wt%, 2-20 wt%, 5-60wt% and 10-70 wt%) and then preliminary stretching orientation, washing with water and drying. The coagulating bath composed of the strong acid or the weak acid reacts with alkali/urea thin flow to generate various salts or mixed aqueous solutions of various salts and urea and the like, so that the solvent or the salts are difficult to recycle, and the difficulty and the cost of separating and recycling the salts and treating three wastes are directly increased. CN107653502a adopts phytic acid as coagulating bath to prepare high-strength fiber yarn based on nanofiber construction. But the phytic acid has higher price, and the production cost is greatly increased. CN102443869a discloses a method for solidifying and forming cellulose solution, (1) cellulose pulp is dissolved in urea or thiourea, alkali metal hydroxide and a mixed aqueous solution of the components to obtain cellulose solution; (2) Solidifying the cellulose solution in the step (1) in a non-acidic first coagulating bath at a temperature of 50-100 ℃ and with concentrations of urea/thiourea and alkali metal hydroxide lower than those used for the corresponding components in the step (1); and (3) obtaining the cellulose fiber through subsequent treatment. But the solidification speed is slow, the reaction is incomplete, and the high-temperature solidification leads to phase separation and low strength of the fiber.
Disclosure of Invention
In order to solve the problems of poor product performance, high recovery and treatment cost of coagulating bath salt and the like in the prior art, the invention provides a solution coagulating and forming method and a spinning method containing natural polymers.
The first aspect of the invention provides a method for solidifying and forming a solution containing natural polymers, which comprises the steps of carrying out at least 1-channel coagulating bath forming on a fiber trickle obtained by wet spinning of the solution containing the natural polymers, wherein the solution containing the natural polymers contains metal hydroxide and an auxiliary agent, and the auxiliary agent is at least one selected from urea, zinc oxide and thiourea;
the coagulating bath is a first coagulating bath containing XHCO 3 And/or XHSO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein X is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); in the coagulation bath, XHCO 3 And/or XHSO 3 The mass concentration of (2) is 0.5-30wt%; or (b)
The coagulating bath is a second coagulating bath containing XHCO 3 And Y 2 CO 3 Or XHSO 3 And Y 2 SO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein Y is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); XHCO 3 Or XHSO 3 The mass concentration of (2) is 0.5-30wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (C) is 0.5-30wt% respectively.
In a second aspect, the present invention provides a method for spinning long fibers, comprising:
the primary fiber is obtained by the solidification molding method, and the primary fiber is washed, oiled and dried to obtain the long fiber.
Compared with the prior art, the solution solidification forming method of the natural polymer, provided by the invention, takes bicarbonate or a composition of bicarbonate and carbonate or bisulphite and sulfite as a solidification bath component to serve as a moderate solidification solution, is favorable for forming fiber trickle yarns into uniform solidification and forming, is favorable for fully solidifying and stretching in a solidification bath and subsequent drafting due to the fact that the fiber trickle yarns do not completely form a cellulose intermolecular hydrogen bond network in the process, and further obtains fibers with round cross sections and excellent performance (the strength can be up to 2.4 cN/dtex), and the fibers are smooth in surface, soft and glossy, compact in cross section, uniform in structure and free of obvious skin-core structures.
In the coagulating bath, the main component of the salt solution is alkalescent bicarbonate, the salt reacts with strong alkali, the auxiliary agent is urea and/or thiourea which are accumulated in the coagulating bath to be beneficial to improving the performance of products, when the auxiliary agent is metal salt (such as zinc oxide), corresponding precipitate is generated in the coagulating bath, and the precipitate can be filtered and removed without influencing the regeneration of weak acid bicarbonate or bisulphite; the hydrogen carbonate or the hydrogen sulfite is regenerated by acidification of carbon dioxide or sulfur dioxide, so that urea and/or thiourea can be recycled, and the hydrogen carbonate, the hydrogen sulfite and the sulfite are easy to separate and recycle, so that the consumption of chemical materials is equivalent to or even lower than that of a viscose process, the recycling and treatment problems of high-concentration salt are solved, the production difficulty and the cost are reduced, and the application prospect is wide.
Drawings
FIG. 1 is a drawing of a long fiber Scanning Electron Microscope (SEM) of the preparation of example 1;
FIG. 2 is a drawing of a long fiber Scanning Electron Microscope (SEM) of the preparation of example 1;
FIG. 3 is a long fiber Scanning Electron Microscope (SEM) image of the preparation of comparative example 1;
fig. 4 is a long fiber Scanning Electron Microscope (SEM) image of the preparation of comparative example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a method for solidifying and forming a solution containing natural polymers, which comprises the steps of carrying out at least 1-channel coagulating bath forming on a fiber trickle obtained by wet spinning of the solution containing the natural polymers, wherein the solution containing the natural polymers contains metal hydroxide and an auxiliary agent, and the auxiliary agent is at least one selected from urea, zinc oxide and thiourea;
the coagulating bath is a first coagulating bath containing XHCO 3 And/or XHSO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein X is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); in the coagulation bath, XHCO 3 And/or XHSO 3 The mass concentration of (2) is 0.5-30wt%; or (b)
The coagulating bath is a second coagulating bath containing XHCO 3 And Y 2 CO 3 Or XHSO 3 And Y 2 SO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein Y is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); XHCO 3 Or XHSO 3 The mass concentration of (2) is 0.5-30wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (C) is 0.5-30wt% respectively.
The solution solidification forming method of natural polymer-containing solution, provided by the invention, takes bicarbonate or a combination of bicarbonate and carbonate or bisulphite and sulfite as a solidification bath component to serve as a moderate solidification solution, is favorable for forming fiber trickle yarns into uniform solidification and forming, is favorable for fully solidifying and stretching in a solidification bath and subsequent drafting due to the fact that the fiber trickle yarns do not completely form a cellulose intermolecular hydrogen bond network in the process, and further obtains fibers with round cross sections and excellent performance (the strength can be higher than 2.4 cN/dtex), and the fibers are smooth in surface, soft and glossy, compact in cross section, uniform in structure and free of obvious skin-core structures.
In the present invention, the optional range of the molding conditions is broad, and according to a preferred embodiment of the present invention, the molding conditions include: the temperature is 10-80℃and preferably 20-40 ℃.
In the present invention, the accumulation of urea and/or thiourea in the coagulation bath, which contributes to the improvement of the properties of the product, according to a preferred embodiment of the present invention, the coagulation bath further contains urea and/or thiourea, preferably in a mass concentration of 5-60wt%, for example 10wt%, 15wt%, 18wt%, 20wt%, 25wt%, 28wt%, 30wt%, 32wt%, 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%, 45wt%.
In the invention, the mass concentration of the natural polymer material in the solution containing the natural polymer is wide in optional range, and according to a preferred embodiment of the invention, the mass concentration of the natural polymer material in the solution containing the natural polymer is 5-9 wt%; preferably, the natural polymer material has a polymerization degree of 200 to 800.
In the invention, the mass concentration of the auxiliary agent in the natural polymer-containing solution is in a wider range, and according to a preferred embodiment of the invention, the mass concentration of the auxiliary agent in the natural polymer-containing solution is 0.01-15 wt%.
In the present invention, the type of the natural polymer material is selected from at least one of cellulose, chitin, chitosan and sodium alginate, according to a preferred embodiment of the present invention.
According to a preferred embodiment of the present invention, the metal hydroxide is selected from at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.
In the present invention, the fiber trickle is subjected to at least 1 coagulation bath, for example, may be subjected to 1, 2, 3, 4 coagulation baths, and according to a preferred embodiment of the present invention, the fiber trickle is subjected to 2 coagulation baths; is beneficial to improving the performance of the fiber.
According to a preferred embodiment of the present invention, in the 1 st coagulation bath, XHCO when the coagulation bath is the first coagulation bath 3 Or XHSO 3 The mass concentration of (2) is 0.5-30wt%;
when the coagulating bath is a second coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 0.5-30wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (C) is 0.5-30wt% respectively.
According to a preferred embodiment of the invention, in the coagulation bath of lane 2, XHCO when the coagulation bath is the first coagulation bath 3 Or XHSO 3 The mass concentration of (2) is 5-15wt%;
when the coagulating bath is a second coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 5-15wt%; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (2) is 1-10wt%.
According to a preferred embodiment of the invention, in the coagulation bath 1 st,
when the coagulating bath is a first coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 8-20wt% respectively;
when the coagulating bath is a second coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (C) is 8-20wt%, Y 2 CO 3 Or Y 2 SO 3 The mass concentrations of (2) to (6) wt.% each.
According to a preferred embodiment of the invention, in the coagulation bath 1, the coagulation bath is a second coagulation bath, wherein XHCO 3 Or XHSO 3 The mass concentration of (2) is 8-15wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of urea and/or thiourea is respectively 2-6wt% and the mass concentration of urea and/or thiourea is 20-40wt%.
According to a preferred embodiment of the present invention, the solidification molding method further includes drawing the molded fiber at a drawing ratio of-50% to 100%.
According to a preferred embodiment of the invention, the drawing ratio of the 1 st to the coagulation bath is-50% to 100%, and the drawing ratio of the 2 nd coagulation bath is 0% to 100%.
According to a preferred embodiment of the invention, the shaping temperature in the coagulation bath 1 is 20-40 ℃; in the 2 nd coagulating bath, the molding temperature is 40-60 ℃.
In a second aspect, the present invention provides a method for spinning long fibers, comprising:
the primary fiber is obtained by the solidification molding method, and the primary fiber is washed, oiled and dried to obtain the long fiber.
In the present invention, long fibers refer to continuous filaments processed by fibers, and the continuous filaments are not subjected to a cutting process.
In the present invention, the water washing conditions are not particularly limited, and the salt may be washed clean.
In the invention, the oiling is used for improving the softness; for example, the primary fiber obtained after washing with water may be coated with silicone oil.
In the present invention, the drying conditions are not particularly limited, and preferably include: the temperature is 80-130 ℃ and the time is 2-5h.
The present invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention in any way.
In the following examples, the regenerated fiber filament density, dry elongation, average strength, etc. were tested according to the bamboo pulp viscose filament yarn standard (FZ-T54012-2007).
Example 1
(i) Dissolving cellulose with DP of 400 into a sodium hydroxide/urea/water (mass ratio of 7:12:81) system, and filtering and defoaming to obtain a solution containing 7.5wt% cellulose;
(ii) Wet spinning the solution obtained in the step (i) to obtain a fiber trickle, wherein the fiber trickle passes through a coagulating bath (the temperature of the coagulating bath is 50 ℃) containing 14 weight percent of sodium bicarbonate and 2 weight percent of sodium carbonate, and is subjected to 30 percent of forward drawing to obtain nascent fibers;
(iii) The nascent fiber is sequentially subjected to hot water washing at 65 ℃, oiling (silicone oil) and drying at 110 ℃ to obtain regenerated cellulose long fiber. The regenerated fiber has a linear density of 133dtex, a dry elongation of 12.1% and an average strength of 1.7cN/dtex.
The long fiber Scanning Electron Microscope (SEM) images are shown in fig. 1 and 2, the fiber has a round section, smooth surface, compact section and uniform structure, and no obvious sheath-core structure.
Example 2
(i) Dissolving cellulose with DP of 250 into a sodium hydroxide/urea/water (mass ratio of 7:5:87) system, and defoaming to obtain a solution containing 8wt% cellulose;
(ii) Wet spinning the solution obtained in the step (i) to obtain a fiber trickle, wherein the fiber trickle passes through a coagulating bath (the temperature of the coagulating bath is 20 ℃) which comprises 15 weight percent of sodium bisulphite and 15 weight percent of sodium sulfite, and is subjected to 30 percent of forward drawing to obtain nascent fibers;
(iii) The nascent fiber is sequentially washed by water at 65 ℃ and oiled (silicone oil), and dried at 130 ℃ to obtain the regenerated cellulose long fiber. The regenerated fiber has a linear density of 133dtex, a dry elongation of 15.6% and an average strength of 1.9cN/dtex.
Example 3
The procedure of preparation 1 was followed, except that in step (ii), the coagulation bath composition was: 9wt% of sodium bicarbonate, 2wt% of sodium carbonate and 20wt% of urea (the temperature of the coagulating bath is 20 ℃); the other conditions were the same as in preparation example 1.
The regenerated fiber has a linear density of 133dtex, a dry elongation of 16% and an average strength of 2.2cN/dtex.
Example 4
(i) Dissolving chitin with DP of 250 into a potassium hydroxide/urea/water (mass ratio of 12.7:5.7:81.6) system, and defoaming to obtain a solution containing 7wt% of chitin;
(ii) Wet spinning the solution obtained in the step (i) to obtain a fiber trickle, wherein the fiber trickle passes through a coagulating bath (the temperature of the coagulating bath is 10 ℃) which comprises 20 weight percent of potassium bicarbonate, 15 weight percent of potassium carbonate and 30 weight percent of urea, and 20 percent of forward drawing is carried out to obtain nascent fibers;
(iii) The nascent fiber is sequentially washed by water at 65 ℃ and oiled (silicone oil), and dried at 130 ℃ to obtain the regenerated chitin fiber. The dry elongation of the regenerated chitin fiber is 12.3%, and the average strength is 1.7cN/dtex.
Example 5
(i) Dissolving cellulose with DP of 400 into a sodium hydroxide/urea/water (mass ratio of 7:12:81) system, and defoaming to obtain a solution containing 7.5wt% cellulose;
(ii) Wet spinning the solution in step (i) to obtain a fiber trickle, wherein the fiber trickle passes through a 1 st coagulating bath (containing 8wt% of sodium bicarbonate and 2wt% of sodium carbonate), the temperature of the coagulating bath is 20 ℃, and 30% forward drawing is carried out;
then passing through a coagulating bath (containing 5wt% of sodium bicarbonate and 2wt% of sodium carbonate) with the temperature of 50 ℃ and carrying out 50% positive draft;
(iii) The nascent fiber is sequentially subjected to hot water washing at 65 ℃, oiling (silicone oil) and drying at 110 ℃ to obtain regenerated cellulose long fiber.
The regenerated fiber has a linear density of 133dtex, a dry elongation of 16.0% and an average strength of 2.2cN/dtex.
Example 6
(i) Dissolving cellulose with DP of 400 into a sodium hydroxide/urea/water (mass ratio of 7:12:81) system, and defoaming to obtain a solution containing 7.5wt% cellulose;
(ii) Wet spinning the solution in the step (i) to obtain a fiber trickle, wherein the fiber trickle passes through a 1 st coagulating bath (8 wt% of sodium bicarbonate, 2wt% of sodium carbonate and 20wt% of urea), the coagulating bath temperature is 20 ℃, and 30% forward drawing is carried out;
then passing through a coagulating bath (containing 5wt% of sodium bicarbonate and 2wt% of sodium carbonate) with the temperature of 50 ℃ and carrying out 50% positive draft;
(iii) The nascent fiber is sequentially subjected to hot water washing at 65 ℃, oiling (silicone oil) and drying at 110 ℃ to obtain regenerated cellulose long fiber.
The regenerated fiber has a linear density of 133dtex, a dry elongation of 16.1% and an average strength of 2.4cN/dtex.
Example 7
The procedure of preparation 1 was followed except that in step (2), the coagulation bath had the following composition: 16wt% sodium bicarbonate (temperature of coagulation bath 60 ℃); the other conditions were the same as in preparation example 1.
The regenerated fiber has a linear density of 133dtex, a dry elongation of 12.2% and an average strength of 1.7cN/dtex.
Example 8
(i) Dissolving cellulose with DP of 400 into a sodium hydroxide/urea/water (mass ratio of 7:12:81) system, and defoaming to obtain a solution containing 7.5wt% cellulose;
(ii) Wet spinning the solution in the step (1) to obtain a fiber trickle, wherein the fiber trickle passes through a 1 st coagulating bath (containing 7wt% of sodium bicarbonate and 1wt% of sodium carbonate), the temperature of the coagulating bath is 20 ℃, and 20% forward drawing is carried out;
then passing through a coagulating bath (containing 5wt% of sodium bicarbonate and 2wt% of sodium carbonate) with the temperature of 50 ℃ and carrying out 30% positive draft;
(iii) The nascent fiber is sequentially subjected to hot water washing at 65 ℃, oiling (silicone oil) and drying at 110 ℃ to obtain regenerated cellulose long fiber.
The regenerated fiber has a linear density of 133dtex, a dry elongation of 15.2% and an average strength of 1.9cN/dtex.
Comparative example 1
The procedure of example 1 was followed except that the coagulation bath was a sulfuric acid coagulation bath system (concrete composition: 110g/L of sulfuric acid and 150g/L of sodium sulfate), and the other conditions were the same as in example 1.
The regenerated fiber has a linear density of 133dtex, a dry elongation of 8.0% and an average strength of 1.1cN/dtex.
The Scanning Electron Microscope (SEM) pictures of the regenerated fiber are shown in fig. 3 and 4, the fiber has irregular cross section and more surface wrinkles, a large number of irregular holes are distributed, and the sheath-core structure is obvious.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A solution solidification forming method containing natural polymer, wet spinning the solution containing natural polymer to obtain fiber trickle, and forming through at least 1 coagulating bath, wherein the solution containing natural polymer contains metal hydroxide and auxiliary agent, the auxiliary agent is selected from at least one of urea, zinc oxide and thiourea;
the coagulating bath is a first coagulating bath containing XHCO 3 And/or XHSO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein X is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); in the coagulation bath, XHCO 3 And/or XHSO 3 The mass concentration of (2) is 0.5-30wt%; or (b)
The coagulating bath is a second coagulating bath containing XHCO 3 And Y 2 CO 3 Or XHSO 3 And Y 2 SO 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein Y is selected from Li, na, K, rb, cs, fr and NH 4 At least one of (a) and (b); XHCO 3 Or XHSO 3 The mass concentration of (2) is 0.5-30wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (C) is 0.5-30wt% respectively.
2. The solidification method according to claim 1, wherein,
the molding conditions include: the temperature is 10-80 ℃, preferably 20-40 ℃; and/or
The coagulation bath also contains urea and/or thiourea, preferably in a mass concentration of 5-60wt%.
3. The solidification method according to claim 1 or 2, wherein,
in the solution containing the natural polymer, the mass concentration of the natural polymer material is 5-9 wt%; preferably, the polymerization degree of the natural high molecular material is 200-800; and/or
In the solution containing natural polymer, the mass concentration of the auxiliary agent is 0.01-15 wt%.
4. The solidification method according to claim 1 or 2, wherein,
the natural polymer material is at least one of cellulose, chitin, chitosan and sodium alginate; and/or
The metal hydroxide is selected from at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.
5. The solidification method according to any one of claims 1 to 4, wherein,
the fiber trickle is passed through 2 coagulation baths;
in the 1 st coagulating bath, XHCO when the coagulating bath is the first coagulating bath 3 Or XHSO 3 The mass concentration of (2) is 0.5-30wt%;
when the coagulating bath is a second coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 0.5-30wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (2) is 0.5-30wt% respectively;
in the 2 nd coagulating bath, when the coagulating bath is the first coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 5-15wt%;
when the coagulating bath is a second coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 5-15wt%; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of (2) is 1-10wt%.
6. The solidification method of claim 5, wherein,
in the coagulation bath of the 1 st path,
when the coagulating bath is a first coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (2) is 8-20wt% respectively;
when the coagulating bath is a second coagulating bath, XHCO 3 Or XHSO 3 The mass concentration of (C) is 8-20wt%, Y 2 CO 3 Or Y 2 SO 3 The mass concentrations of (2) to (6) wt.% each.
7. The solidification method of claim 6, wherein,
in the 1 st coagulating bath, the coagulating bath is a second coagulating bath, wherein XHCO 3 Or XHSO 3 The mass concentration of (2) is 8-15wt% respectively; y is Y 2 CO 3 Or Y 2 SO 3 The mass concentration of urea and/or thiourea is respectively 2-6wt% and the mass concentration of urea and/or thiourea is 20-40wt%.
8. The solidification process according to any one of claims 1 to 7, wherein,
the solidification forming method also comprises the steps of drafting the formed fiber, wherein the drafting rate is-50% -100%.
9. The solidification method of claim 7, wherein,
the drawing ratio of the 1 st to the coagulating bath is-50% -100%, and the drawing ratio of the 2 nd coagulating bath is 0-100%.
10. A method of spinning long fibers, the method comprising:
the primary fiber obtained by the solidification process according to any one of claims 1 to 9, which is subjected to water washing, oiling, and drying to obtain a long fiber.
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