CN117535804A - Method and equipment for preparing regenerated cellulose industrial yarn - Google Patents
Method and equipment for preparing regenerated cellulose industrial yarn Download PDFInfo
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- CN117535804A CN117535804A CN202311492886.1A CN202311492886A CN117535804A CN 117535804 A CN117535804 A CN 117535804A CN 202311492886 A CN202311492886 A CN 202311492886A CN 117535804 A CN117535804 A CN 117535804A
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- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims description 31
- 230000001112 coagulating effect Effects 0.000 claims abstract description 158
- 238000009987 spinning Methods 0.000 claims abstract description 116
- 229920002678 cellulose Polymers 0.000 claims abstract description 70
- 239000001913 cellulose Substances 0.000 claims abstract description 70
- 239000002608 ionic liquid Substances 0.000 claims abstract description 59
- 238000007711 solidification Methods 0.000 claims abstract description 50
- 230000008023 solidification Effects 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 238000009998 heat setting Methods 0.000 claims abstract description 14
- 229920000875 Dissolving pulp Polymers 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000011550 stock solution Substances 0.000 claims abstract description 8
- 238000012805 post-processing Methods 0.000 claims abstract description 4
- 230000015271 coagulation Effects 0.000 claims description 137
- 238000005345 coagulation Methods 0.000 claims description 137
- 239000007864 aqueous solution Substances 0.000 claims description 46
- 239000000835 fiber Substances 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 22
- 238000004090 dissolution Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 7
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 5
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 claims description 4
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 claims description 4
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 claims description 3
- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 16
- 229920000297 Rayon Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- -1 1-allyl-3-methylimidazole chloride salt Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
-
- 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- 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
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a preparation method and equipment of regenerated cellulose industrial yarn, wherein the preparation method comprises the following steps: step S1, preparing spinning solution: mixing, dehydrating and dissolving cellulose pulp and ionic liquid to prepare cellulose spinning stock solution with set concentration; s2, a spinning step; extruding the prepared cellulose spinning solution through a spinning cap for spinning; step S3, gradient solidification: sequentially feeding the extruded silk strips into different coagulating baths to carry out graded coagulating treatment after passing through an air section; step S4, a post-processing step: and (3) washing and heat setting the yarn after gradient solidification to obtain regenerated cellulose industrial yarn. The preparation method and the equipment for the regenerated cellulose industrial yarn can ensure the breaking strength and modulus of the regenerated cellulose industrial yarn and improve the breaking elongation of the regenerated cellulose industrial yarn.
Description
Technical Field
The invention belongs to the technical field of chemical materials, relates to an industrial yarn, and in particular relates to a preparation method and equipment of a regenerated cellulose industrial yarn.
Background
The use of cellulose fibers in cords for the rubber industry has been known for many years, with the earliest use of cotton as tire cords; however, the strong yarn is replaced by the later developed viscose strong yarn because of the defects of low strength, high heat emission, slow heat dissipation, easy water absorption and the like of the carcass multi-layer curtain cloth in the use process. The viscose cord has the greatest advantages of heat resistance and form stability, can keep high elastic recovery rate even at high temperature (80 ℃), has good adhesion with rubber and good heat dissipation, and is mainly used for tire meridian of high-speed running sedan; even under the rapid development of high-strength synthetic industrial yarns, viscose cords still occupy a place in the fields of high-performance tires, tires for sports cars, reinforcement of mechanical rubber products (such as brake hoses, cooling hoses, etc.), and the like.
However, with the increasing awareness of global environmental protection and the implementation of related laws, the yield of strong filaments produced by the viscose process tends to be limited. The regenerated cellulose fiber prepared by the new solvent method is dissolved and regenerated as a physical process, no chemical reaction exists, the solvent can be recycled, the recovery rate reaches more than 99.5%, and the clean production of the regenerated cellulose fiber is realized; meanwhile, the high-strength and high-model property of the fiber-reinforced plastic fiber composite material has the potential of developing high-performance products, and is expected to replace viscose strong yarns to be used as a framework material of high-end engineering, airplanes and racing tires.
Patent CN1786301a proposes that a certain proportion (0-50%) of cellulose pulp with high relative molecular weight (polymerization degree 1000-1450) is added into cellulose pulp with medium and high relative molecular weight (polymerization degree 600-850) as raw material, and a specific swelling-dissolving process is adopted to prepare spinning dope with better spinnability, so that the mechanical properties of strength, modulus and the like of the prepared regenerated cellulose cord are greatly improved, but the breaking elongation of the prepared regenerated cellulose fiber is lower than 8%.
In patent EP-A-494851, a technical route of solidification and stretching is provided, namely, the filament is extruded from a spinning nozzle without stress, partial regeneration is completed in a solidification bath, and the filament which is partially regenerated is stretched subsequently, but the mechanical property of the fiber prepared by the method cannot meet the application requirement of a cord.
Patent CN100410430C provides a method for drying and heat-treating, in which the solidified regenerated cellulose fiber is post-stretched at a certain temperature and under a certain tension, which can improve the mechanical strength, especially wet modulus, of the regenerated cellulose fiber to 350CN/tex, but as a regenerated cellulose fiber for a cord, the breaking elongation thereof cannot meet the requirement.
The patent CN101195933B adopts cellulose pulp with moderate relative molecular mass as a raw material, so that the concentration of cellulose in the spinning solution is improved, and inorganic salt is added into a solution system; meanwhile, the mechanical properties of the regenerated cellulose fiber are improved by applying a technical means of moderate stretching and heat setting to the nascent fiber in a wet state in which the fiber structure is not completely formed, but the elongation at break of the fiber is 7.2% -8.5%.
Literature research shows that in the new solvent method regenerated cellulose spinning process, the concentration of the spinning solution, the temperature concentration of the coagulating bath, the length of an air section, the spinning speed and the stretching ratio all have influences on the breaking elongation of the regenerated cellulose fibers. The aim of improving the breaking elongation of the regenerated cellulose fiber can be achieved by adjusting the spinning process conditions, but the strength, the modulus and other performances of the fiber can be influenced, the breaking elongation can not be improved, and the regenerated cellulose fiber with high strength and modulus can be obtained. The elongation at break is also a very important indicator for regenerated cellulose industrial filaments for cords, determining their stability for application to cords.
In summary, the method of improving the mechanical properties of regenerated cellulose fibers for application to cords in the prior art has the following problems:
(1) The use of a high molecular weight raw material, post-stretching of the filaments, heat treatment under tension, and the like have led to the improvement of the breaking strength of regenerated cellulose fibers, mainly by increasing the crystallinity and orientation of the fibers, and the elongation at break of the fibers has not been considered;
(2) The elongation at break of the fiber can be improved by adjusting the spinning process, such as reducing the stretching ratio of a spray nozzle, but the breaking strength of the fiber can be reduced, so that the elongation at break is improved while the strength of the fiber is difficult to ensure.
In view of this, there is an urgent need today to devise a new regenerated cellulose industrial yarn in order to overcome at least part of the above-mentioned drawbacks of the existing regenerated cellulose industrial yarns.
Disclosure of Invention
The invention provides a preparation method and equipment of regenerated cellulose industrial yarn, which can ensure the breaking strength and modulus of the regenerated cellulose industrial yarn and improve the breaking elongation of the regenerated cellulose industrial yarn.
In order to solve the technical problems, according to one aspect of the present invention, the following technical scheme is adopted:
a method of making regenerated cellulose industrial yarn, the method comprising:
step S1, preparing spinning solution:
mixing, dehydrating and dissolving cellulose pulp and ionic liquid to prepare cellulose spinning stock solution with set concentration;
S2, a spinning step;
extruding the prepared cellulose spinning solution through a spinning cap for spinning;
step S3, gradient solidification:
sequentially feeding the extruded yarn into different coagulating baths to carry out graded coagulation treatment after passing through an air section;
step S4, a post-processing step:
and (3) washing and heat setting the yarn after gradient solidification to obtain regenerated cellulose industrial yarn.
In the step S3, the extruded yarn passes through the air section and then sequentially enters the first coagulation bath, the second coagulation bath and the third coagulation bath to be subjected to the fractional coagulation treatment;
wherein, the silk yarn is subjected to first solidification treatment in a first solidification bath, the silk yarn is subjected to second solidification treatment in a second solidification bath, and the silk yarn is subjected to third solidification treatment in a third solidification bath;
the concentration of the ionic liquid aqueous solution adopted by the first coagulating bath is higher than that adopted by the second coagulating bath; the temperature adopted by the first coagulating bath is lower than that adopted by the second coagulating bath and that adopted by the third coagulating bath; the concentration of the ionic liquid aqueous solution adopted by the second coagulating bath is higher than that adopted by the third coagulating bath.
In the step S3, the first coagulation bath is subjected to conditions of higher concentration and lower temperature, so that the forming speed of the filament is slowed down, the difference of the sheath-core structures of the fibers is reduced, the filament is ensured to have higher solvent residues, the intermolecular actions of cellulose are weakened, the movement capacity of cellulose chain segments is improved, and conditions are provided for the adjustment of the structures in the subsequent second and third coagulation baths;
In the second coagulation bath, a relatively moderate concentration and a higher temperature condition are adopted, wherein the higher temperature condition mainly provides thermodynamic conditions for movement of cellulose chain segments in the silk, the relatively moderate concentration is used for reducing the forming speed of the silk, reducing the structural difference along the radial direction of the silk, and simultaneously enabling the structure of the silk to be basically fixed;
the third coagulating bath adopts lower concentration and higher temperature conditions, and simultaneously reduces the stress along the axial direction of the yarn through the adjustment of the stretching conditions and further forms the yarn; the technical route of three-stage coagulation bath gradient coagulation slows down the forming speed of the silk strip, so that the final regenerated cellulose industrial silk skin-core structure difference is reduced, the structure is more uniform, the strength and modulus of the fiber are ensured, and simultaneously, the shrinkage along the axial direction of the silk strip in the second coagulation bath and the smaller stress condition along the axial direction of the silk strip in the third coagulation bath properly reduce the orientation degree of the fiber, and the high elongation at break of the regenerated cellulose industrial silk is ensured.
In the step S1, cellulose pulp with the intrinsic viscosity of 300-1000ml/g and ionic liquid are mixed, dehydrated and dissolved to prepare cellulose spinning dope with the concentration of 5-20%;
The dissolution adopts a wet dissolution process; the intrinsic viscosity of the cellulose pulp is 500-800ml/g;
the ionic liquid is at least one of 1-butyl-3-methylimidazole chloride, 1-allyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole chloride or 1-butyl-3-methylimidazole acetate;
the solid content of cellulose in the spinning solution is 8-15%.
In the step S2, the number of the spinning holes is 100 to 3000 holes; the diameter of the spinneret orifice is 0.04-0.2mm; the spinning temperature is 80-120 ℃.
In the step S3, the length of the air segment is 5-500mm;
the first coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 0-60%, the coagulating bath temperature is 0-30 ℃, the stretching multiplying power is 1-5 times, and the stretching speed is 10-150m/min;
the second coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 10-40%, the coagulating bath temperature is 10-90 ℃, the stretching multiplying power is 0.9-1.2 times, and the stretching speed is 9-180m/min;
the third coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 0-30%, the coagulating bath temperature is 10-90 ℃, the stretching multiplying power is 0.9-1.2 times, and the stretching speed is 8-200m/min.
As one embodiment of the present invention, the first coagulation bath conditions are: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 30-50%, the coagulating bath temperature is 5-20 ℃, the stretching multiplying power is 1-2 times, and the stretching speed is 20-50m/min;
the second coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 20-30%, the coagulating bath temperature is 40-90 ℃, the stretching multiplying power is 0.95-1.05 times, and the stretching speed is 19-55m/min;
the third coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 10-20%, the coagulating bath temperature is 40-90 ℃, the stretching multiplying power is 0.95-1.05 times, and the stretching speed is 18-58m/min.
As an embodiment of the present invention, in the step S4, the obtained regenerated cellulose industrial yarn has a fineness of 500-3500dtex, a dry strength of 4.5-6cN/dtex, a dry modulus of not less than 100cN/dtex, an elongation at break of 8-15%, and a dry heat shrinkage of not more than 0.7% under the conditions of a pre-tension of 0.01cN/dtex at 190 ℃.
As an embodiment of the present invention, in the step S4, the obtained regenerated cellulose industrial yarn has a fineness of 1000-2000dtex, a dry strength of 4.5-5.5cN/dtex, a dry modulus of not less than 120cN/dtex, an elongation at break of 10-13%, and a dry heat shrinkage of not more than 0.6% under the conditions of a pre-tension of 0.01cN/dtex at a temperature of 190 ℃.
According to another aspect of the invention, the following technical scheme is adopted: an apparatus for producing regenerated cellulose industrial yarn, the apparatus comprising: the device comprises a dissolver, a spinning component, a plurality of coagulating baths, a water washing device, a heat setting device and a winding device;
the dissolver is used for mixing, dehydrating and dissolving cellulose pulp and ionic liquid to prepare cellulose spinning solution with set concentration;
the spinning component is used for extruding and spinning the prepared cellulose spinning stock solution; sequentially feeding the extruded yarn into each coagulating bath to carry out graded coagulating treatment after passing through an air section;
and (3) carrying out water washing on the yarn subjected to gradient solidification by the water washing device, carrying out heat setting by the heat setting device, and winding to obtain the regenerated cellulose industrial yarn.
As one embodiment of the present invention, the plurality of coagulation baths includes a first coagulation bath, a second coagulation bath, and a third coagulation bath; sequentially entering the first coagulating bath, the second coagulating bath and the third coagulating bath to carry out graded coagulating treatment after the extruded silk strip passes through the air section;
wherein, the silk yarn is subjected to first solidification treatment in a first solidification bath, the silk yarn is subjected to second solidification treatment in a second solidification bath, and the silk yarn is subjected to third solidification treatment in a third solidification bath;
The preparation apparatus includes a coagulation control module to control parameters of each coagulation bath such that: the concentration of the ionic liquid aqueous solution adopted by the first coagulating bath is higher than that adopted by the second coagulating bath; the temperature adopted by the first coagulating bath is lower than that adopted by the second coagulating bath and that adopted by the third coagulating bath; the concentration of the ionic liquid aqueous solution adopted by the second coagulating bath is higher than that of the ionic liquid aqueous solution adopted by the third coagulating bath;
as one implementation mode of the invention, the first coagulating bath adopts higher concentration and lower temperature conditions, slows down the forming speed of the silk, reduces the difference of the sheath-core structure of the fiber, ensures that the silk has higher solvent residue, weakens the intermolecular action of cellulose, improves the movement capacity of cellulose chain segments, and provides conditions for the adjustment of the structures in the subsequent second coagulating bath and the third coagulating bath;
in the second coagulation bath, a relatively moderate concentration and a higher temperature condition are adopted, wherein the higher temperature condition mainly provides thermodynamic conditions for movement of cellulose chain segments in the silk, the relatively moderate concentration is used for reducing the forming speed of the silk, reducing the structural difference along the radial direction of the silk, and simultaneously enabling the structure of the silk to be basically fixed;
The third coagulating bath adopts lower concentration and higher temperature conditions, and simultaneously reduces the stress along the axial direction of the yarn through the adjustment of the stretching conditions and further forms the yarn; the technical route of three-stage coagulation bath gradient coagulation slows down the forming speed of the silk strip, so that the final regenerated cellulose industrial silk skin-core structure difference is reduced, the structure is more uniform, the strength and modulus of the fiber are ensured, meanwhile, the shrinkage along the axial direction of the silk strip in the second coagulation bath and the smaller stress condition along the axial direction of the silk strip in the third coagulation bath are properly reduced, the orientation degree of the fiber is properly reduced, and the high breaking elongation of the regenerated cellulose industrial silk is ensured.
The invention has the beneficial effects that: the preparation method and the equipment for the regenerated cellulose industrial yarn provided by the invention have the advantages that the prepared regenerated cellulose industrial yarn has higher breaking strength, initial modulus and breaking elongation: the fineness of the regenerated cellulose industrial yarn prepared by the invention is 500-3500dtex, the dry strength is 4.5-6cN/dtex, the dry modulus is more than or equal to 100cN/dtex, the elongation at break is 8-15%, and the dry heat shrinkage rate under the conditions of 190 ℃ and 0.01cN/dtex is less than or equal to 0.7%.
The preparation method can ensure the breaking strength and modulus of the regenerated cellulose industrial yarn and improve the breaking elongation of the regenerated cellulose industrial yarn; the regenerated cellulose industrial yarn prepared by the technical route of the invention can meet the application requirements of the cord.
Drawings
FIG. 1 is a flow chart of a method for producing regenerated cellulose industrial yarn according to an embodiment of the present invention.
FIG. 2 is a schematic diagram showing the constitution of an apparatus for producing regenerated cellulose industrial yarn according to an embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The description of this section is intended to be illustrative of only a few exemplary embodiments and the invention is not to be limited in scope by the description of the embodiments. It is also within the scope of the description and claims of the invention to interchange some of the technical features of the embodiments with other technical features of the same or similar prior art.
The description of the steps in the various embodiments in the specification is merely for convenience of description, and the implementation of the present application is not limited by the order in which the steps are implemented.
The invention discloses a preparation method of regenerated cellulose industrial yarn, and FIG. 1 is a flow chart of the preparation method of regenerated cellulose industrial yarn in an embodiment of the invention; referring to fig. 1, the preparation method includes:
The preparation step of the spinning dope:
and mixing, dehydrating and dissolving cellulose pulp and ionic liquid to prepare cellulose spinning stock solution with set concentration.
In one embodiment of the invention, cellulose pulp with the intrinsic viscosity of 300-1000ml/g and ionic liquid are mixed, dehydrated and dissolved to prepare cellulose spinning dope with the concentration of 5-20%;
in one embodiment of the invention, the dissolution is performed by a wet dissolution process; the intrinsic viscosity of the cellulose pulp is 500-800ml/g;
the ionic liquid is at least one of 1-butyl-3-methylimidazole chloride, 1-allyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole chloride or 1-butyl-3-methylimidazole acetate;
the solid content of cellulose in the spinning solution is 8-15%.
A spinning step (step S2);
and extruding the prepared cellulose spinning solution through a spinning nozzle to spin.
In one embodiment of the present invention, the number of orifices is 100-3000; the diameter of the spinneret orifice is 0.04-0.2mm; the spinning temperature is 80-120 ℃.
Gradient solidification step:
the extruded silk strip passes through the air section and then sequentially enters different coagulating baths to carry out graded coagulation treatment.
In one embodiment of the present invention, the extruded filaments pass through the air section and then sequentially enter the first coagulation bath, the second coagulation bath and the third coagulation bath to be subjected to graded coagulation treatment. Wherein the yarn is subjected to a first coagulation treatment in a first coagulation bath, the yarn is subjected to a second coagulation treatment in a second coagulation bath, and the yarn is subjected to a third coagulation treatment in a third coagulation bath. The concentration of the ionic liquid aqueous solution adopted by the first coagulating bath is higher than that adopted by the second coagulating bath; the temperature adopted by the first coagulating bath is lower than that adopted by the second coagulating bath and that adopted by the third coagulating bath; the concentration of the ionic liquid aqueous solution adopted by the second coagulating bath is higher than that adopted by the third coagulating bath.
In one embodiment, the first coagulation bath adopts higher concentration and lower temperature conditions, so that the forming speed of the yarn is slowed down, the difference of the sheath-core structures of the fibers is reduced, meanwhile, the yarn is ensured to have higher solvent residues, the intermolecular actions of cellulose are weakened, the movement capacity of cellulose chain segments is improved, and conditions are provided for the adjustment of the structures in the subsequent second and third coagulation baths;
in the second coagulation bath, a relatively moderate concentration and a higher temperature condition are adopted, wherein the higher temperature condition mainly provides thermodynamic conditions for movement of cellulose chain segments in the silk, the relatively moderate concentration is used for reducing the forming speed of the silk, reducing the structural difference along the radial direction of the silk, and simultaneously enabling the structure of the silk to be basically fixed;
The third coagulating bath adopts lower concentration and higher temperature conditions, and simultaneously reduces the stress along the axial direction of the yarn through the adjustment of the stretching conditions and further forms the yarn; the technical route of three-stage coagulation bath gradient coagulation slows down the forming speed of the silk strip, so that the final regenerated cellulose industrial silk skin-core structure difference is reduced, the structure is more uniform, the strength and modulus of the fiber are ensured, and simultaneously, the shrinkage along the axial direction of the silk strip in the second coagulation bath and the smaller stress condition along the axial direction of the silk strip in the third coagulation bath properly reduce the orientation degree of the fiber, and the high elongation at break of the regenerated cellulose industrial silk is ensured. The existing primary solidification technology cannot be used for preparing regenerated cellulose industrial yarns which simultaneously meet the requirements of high strength, high modulus and high elongation at break.
In one embodiment of the invention, the length of the air section is 5-500mm;
the first coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 0-60%, the coagulating bath temperature is 0-30 ℃, the stretching multiplying power is 1-5 times, and the stretching speed is 10-150m/min. In one embodiment, the first coagulation bath conditions are: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 30-50%, the coagulating bath temperature is 5-20 ℃, the stretching multiplying power is 1-2 times, and the stretching speed is 20-50m/min.
The second coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 10-40%, the coagulating bath temperature is 10-90 ℃, the stretching multiplying power is 0.9-1.2 times, and the stretching speed is 9-180m/min. In one embodiment, the second coagulation bath conditions are: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 20-30%, the coagulating bath temperature is 40-90 ℃, the stretching multiplying power is 0.95-1.05 times, and the stretching speed is 19-55m/min.
The third coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 0-30%, the coagulating bath temperature is 10-90 ℃, the stretching multiplying power is 0.9-1.2 times, and the stretching speed is 8-200m/min. In one embodiment, the third coagulation bath conditions are: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 10-20%, the coagulating bath temperature is 40-90 ℃, the stretching multiplying power is 0.95-1.05 times, and the stretching speed is 18-58m/min.
Post-processing step (step S4):
and (3) washing and heat setting the yarn after gradient solidification to obtain regenerated cellulose industrial yarn.
In one embodiment of the invention, the regenerated cellulose industrial yarn obtained has a fineness of 500-3500dtex, a dry strength of 4.5-6cN/dtex, a dry modulus of not less than 100cN/dtex, an elongation at break of 8-15% and a dry heat shrinkage of not more than 0.7% at 190 ℃ under a pre-tension of 0.01 cN/dtex. In one embodiment, the regenerated cellulose industrial yarn obtained has a fineness of 1000-2000dtex, a dry strength of 4.5-5.5cN/dtex, a dry modulus of not less than 120cN/dtex, an elongation at break of 10-13% and a dry heat shrinkage of not more than 0.6% at 190℃under a pre-tension of 0.01 cN/dtex.
The invention further discloses a regenerated cellulose industrial yarn preparation device, and FIG. 2 is a schematic diagram of the regenerated cellulose industrial yarn preparation device according to an embodiment of the invention; referring to fig. 2, the preparation apparatus includes: a dissolver 1, a spinning component 2, a plurality of coagulating baths, a water washing device 6, a heat setting device 7 and a winding device 8. The dissolver 1 is used for mixing, dehydrating and dissolving cellulose pulp and ionic liquid to prepare cellulose spinning solution with set concentration. The spinning component 2 is used for extruding and spinning the prepared cellulose spinning stock solution; and (3) sequentially feeding the extruded yarn into each coagulating bath after passing through an air section to carry out graded coagulating treatment. And after the silk strip subjected to gradient solidification is subjected to water washing by the water washing device 6 and heat setting by the heat setting device 7, the silk strip is wound by the winding device 8 to obtain regenerated cellulose industrial silk.
In one embodiment of the invention, the coagulation baths include a first coagulation bath 3, a second coagulation bath 4 and a third coagulation bath 5; the extruded yarn is sequentially fed into a first coagulation bath 3, a second coagulation bath 4 and a third coagulation bath 5 after passing through an air section for carrying out graded coagulation treatment. Wherein, the yarn is subjected to a first coagulation treatment in a first coagulation bath 3, the yarn is subjected to a second coagulation treatment in a second coagulation bath 4, and the yarn is subjected to a third coagulation treatment in a third coagulation bath 5.
The preparation apparatus includes a coagulation control module to control parameters of each coagulation bath such that: the concentration of the ionic liquid aqueous solution adopted by the first coagulating bath 3 is higher than that adopted by the second coagulating bath 4; the temperature of the first coagulation bath 3 is lower than that of the second coagulation bath 4 and the temperature of the third coagulation bath 5; the second coagulation bath 4 employs an ionic liquid aqueous solution having a higher concentration than the ionic liquid aqueous solution employed by the third coagulation bath 5.
In one embodiment, the first coagulation bath adopts higher concentration and lower temperature conditions, so that the forming speed of the yarn is slowed down, the difference of the sheath-core structures of the fibers is reduced, meanwhile, the yarn is ensured to have higher solvent residues, the intermolecular actions of cellulose are weakened, the movement capacity of cellulose chain segments is improved, and conditions are provided for the adjustment of the structures in the subsequent second coagulation bath and the third coagulation bath.
In the second coagulation bath, a relatively moderate concentration and a higher temperature condition are adopted, wherein the higher temperature condition mainly provides thermodynamic conditions for movement of cellulose chain segments in the silk, the relatively moderate concentration is used for reducing the forming speed of the silk, reducing the structural difference along the radial direction of the silk, and simultaneously enabling the structure of the silk to be basically fixed.
The third coagulating bath adopts lower concentration and higher temperature conditions, and simultaneously reduces the stress along the axial direction of the yarn through the adjustment of the stretching conditions and further forms the yarn; the technical route of three-stage coagulation bath gradient coagulation slows down the forming speed of the silk strip, so that the final regenerated cellulose industrial silk skin-core structure difference is reduced, the structure is more uniform, the strength and modulus of the fiber are ensured, meanwhile, the shrinkage along the axial direction of the silk strip in the second coagulation bath and the smaller stress condition along the axial direction of the silk strip in the third coagulation bath are properly reduced, the orientation degree of the fiber is properly reduced, and the high breaking elongation of the regenerated cellulose industrial silk is ensured.
Example 1
In this example, the method for producing the regenerated cellulose industrial yarn with high elongation at break for a cord according to the present invention comprises:
(1) Preparing spinning solution;
and mixing, dehydrating and dissolving cellulose pulp with the intrinsic viscosity of 500ml/g and 1-butyl-3-methylimidazole chloride salt to obtain a cellulose spinning solution.
The dissolution process is a wet dissolution process; the solid content of cellulose in the spinning solution is 10%;
(2) Spinning;
extruding the prepared cellulose spinning solution through a spinning cap for spinning; the number of the spinning holes is 660 holes, the diameter of the spinning holes is 0.06mm, and the spinning temperature is 95 ℃.
(3) Gradient solidification step;
the extruded silk strip passes through an air section and then enters a first coagulating bath, a second coagulating bath and a third coagulating bath;
the length of the air section is 30mm;
the first coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 40%, the coagulating bath temperature is 15 ℃, the stretching multiplying power is 1.5 times, and the stretching speed is 20m/min;
the second coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 25%, the coagulating bath temperature is 80 ℃, the stretching multiplying power is 0.97 times, and the stretching speed is 19.4m/min;
the third coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 15%, the coagulating bath temperature is 80 ℃, the stretching multiplying power is 0.99 times, and the stretching speed is 19.2m/min;
(4) Post-treatment;
the silk yarn after gradient solidification is washed and heat-set to obtain regenerated cellulose industrial yarn, the fineness of the regenerated cellulose industrial yarn is 1650dtex, the dry strength is 4.7cN/dtex, the dry modulus is 170cN/dtex, the elongation at break is 11%, the dry heat shrinkage is 0.5% under the conditions of 190 ℃ (temperature) and 0.01cN/dtex (pre-tension).
Example 2
In this example, the method for producing a regenerated cellulose industrial yarn with high elongation at break for a cord according to the present invention comprises:
(1) Preparing spinning solution;
and mixing, dehydrating and dissolving cellulose pulp with the intrinsic viscosity of 700ml/g and 1-allyl-3-methylimidazole chloride salt to obtain a cellulose spinning solution.
The dissolution process is a wet dissolution process; the solid content of cellulose in the spinning solution is 10%;
(2) Spinning;
extruding the prepared cellulose spinning solution through a spinning cap for spinning; the number of the spinning holes is 1000 holes, the diameter of the spinning holes is 0.06mm, and the spinning temperature is 85 ℃.
(3) Gradient solidification step;
the extruded silk strip passes through an air section and then enters a first coagulating bath, a second coagulating bath and a third coagulating bath;
the length of the air section is 30mm;
the first coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 40%, the coagulating bath temperature is 15 ℃, the stretching multiplying power is 1.9 times, and the stretching speed is 20m/min;
the second coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 25%, the coagulating bath temperature is 80 ℃, the stretching multiplying power is 0.98 times, and the stretching speed is 19.6m/min;
the third coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 15%, the coagulating bath temperature is 80 ℃, the stretching multiplying power is 0.99 times, and the stretching speed is 19.4m/min;
(4) Post-treatment;
the silk yarn after gradient solidification is washed and heat-set to obtain regenerated cellulose industrial yarn, the fineness of the obtained regenerated cellulose industrial yarn is 1900dtex, the dry strength is 4.6cN/dtex, the dry modulus is 150cN/dtex, the elongation at break is 13%, the dry heat shrinkage rate is 190 ℃ (temperature) and 0.01cN/dtex (pre-tension) is 0.4%.
Example 3
In this example, the method for producing a regenerated cellulose industrial yarn with high elongation at break for a cord according to the present invention comprises:
(1) Preparing spinning solution;
and mixing, dehydrating and dissolving cellulose pulp with the intrinsic viscosity of 600ml/g and 1-ethyl-3-methylimidazole acetate to obtain a cellulose spinning solution.
The dissolution process is a wet dissolution process; the solid content of cellulose in the spinning solution is 15%;
(2) Spinning;
extruding the prepared cellulose spinning solution through a spinning cap for spinning; the number of the spinning holes is 660 holes, the diameter of the spinning holes is 0.06mm, and the spinning temperature is 80 ℃.
(3) Gradient solidification step;
the extruded silk strip passes through an air section and then enters a first coagulating bath, a second coagulating bath and a third coagulating bath;
the length of the air section is 30mm;
the first coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 30%, the coagulating bath temperature is 15 ℃, the stretching multiplying power is 1.95 times, and the stretching speed is 18.4m/min;
The second coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 20%, the coagulating bath temperature is 70 ℃, the stretching multiplying power is 0.99 times, and the stretching speed is 18.2m/min;
the third coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 10%, the coagulating bath temperature is 70 ℃, the stretching multiplying power is 0.99 times, and the stretching speed is 18m/min;
(4) Post-treatment;
the silk yarn after gradient solidification is washed and heat-set to obtain regenerated cellulose industrial yarn, the fineness of the regenerated cellulose industrial yarn is 1800dtex, the dry strength is 5.2cN/dtex, the dry modulus is 210cN/dtex, the elongation at break is 10%, the dry heat shrinkage rate is 0.6% under the conditions of 190 ℃ (temperature) and 0.01cN/dtex (pre-tension).
Example 4
In this example, the method for producing a regenerated cellulose industrial yarn with high elongation at break for a cord according to the present invention comprises:
(1) Preparing spinning solution;
and mixing, dehydrating and dissolving cellulose pulp with the intrinsic viscosity of 600ml/g and 1-ethyl-3-methylimidazole chloride salt to obtain a cellulose spinning solution.
The dissolution process is a wet dissolution process
The solid content of cellulose in the spinning solution is 12%
(2) Spinning;
Extruding the prepared cellulose spinning solution through a spinning cap for spinning; the number of the spinning holes is 1000 holes, the diameter of the spinning holes is 0.06mm, and the spinning temperature is 85 ℃.
(3) Gradient solidification step;
the extruded silk strip passes through an air section and then enters a first coagulating bath, a second coagulating bath and a third coagulating bath;
the length of the air section is 30mm;
the first coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 30%, the coagulating bath temperature is 15 ℃, the stretching multiplying power is 1.7 times, and the stretching speed is 18.4m/min;
the second coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 20%, the coagulating bath temperature is 70 ℃, the stretching multiplying power is 0.99 times, and the stretching speed is 18.2m/min;
the third coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 10%, the coagulating bath temperature is 70 ℃, the stretching multiplying power is 0.99 times, and the stretching speed is 18m/min;
(4) Post-treatment;
the silk yarn after gradient solidification is washed and heat-set to obtain regenerated cellulose industrial yarn, the fineness of the regenerated cellulose industrial yarn is 2500dtex, the dry strength is 4.9cN/dtex, the dry modulus is 170cN/dtex, the elongation at break is 10 percent, the temperature is 190 ℃, and the dry heat shrinkage rate under the conditions of 0.01cN/dtex (pre-tension) is 0.5 percent;
Comparative example 1
On the basis of example 1, only the coagulation conditions were changed to prepare regenerated cellulose fibers, and the specific steps were as follows:
(1) Preparing spinning solution;
and mixing, dehydrating and dissolving cellulose pulp with the intrinsic viscosity of 500ml/g and 1-butyl-3-methylimidazole chloride salt to obtain a cellulose spinning solution.
The dissolution process is a wet dissolution process
The solid content of cellulose in the spinning solution is 10 percent
(2) Spinning;
extruding the prepared cellulose spinning solution through a spinning cap for spinning; the number of the spinning holes is 660 holes, the diameter of the spinning holes is 0.06mm, and the spinning temperature is 95 ℃.
(3) A solidification step;
the extruded silk strip enters into a coagulating bath after passing through an air section;
the length of the air section is 30mm;
the coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 20%, the coagulating bath temperature is 15 ℃, the stretching multiplying power is 1.44 times, and the stretching speed is 19.2m/min;
(4) Post-treatment;
the solidified silk strip is washed with water and heat-set to obtain regenerated cellulose industrial silk, the fineness of the regenerated cellulose industrial silk is 1650dtex, the dry strength is 4.9cN/dtex, the dry modulus is 190cN/dtex, the elongation at break is 7%, the dry heat shrinkage is 0.5% under the conditions of 190 ℃ (temperature) and 0.01cN/dtex (pre-tension).
Comparative example 2
On the basis of example 2, regenerated cellulose fibers were prepared by changing only the coagulation conditions, specifically as follows:
(1) Preparing spinning solution;
and mixing, dehydrating and dissolving cellulose pulp with the intrinsic viscosity of 700ml/g and 1-allyl-3-methylimidazole chloride salt to obtain a cellulose spinning solution.
The dissolution process is a wet dissolution process; the solid content of cellulose in the spinning solution is 10%;
(2) Spinning;
extruding the prepared cellulose spinning solution through a spinning cap for spinning; the number of the spinning holes is 1000 holes, the diameter of the spinning holes is 0.06mm, and the spinning temperature is 85 ℃.
(3) A solidification step;
the extruded silk strip enters into a coagulating bath after passing through an air section;
the length of the air section is 30mm;
the coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 20%, the coagulating bath temperature is 15 ℃, the stretching multiplying power is 1.84 times, and the stretching speed is 19.4m/min;
(4) Post-treatment;
the silk yarn after gradient solidification is washed and heat-set to obtain regenerated cellulose industrial yarn, the fineness of the obtained regenerated cellulose industrial yarn is 1900dtex, the dry strength is 5.1cN/dtex, the dry modulus is 210cN/dtex, the elongation at break is 6%, the dry heat shrinkage rate is 0.6% under the conditions of 190 ℃ (temperature) and 0.01cN/dtex (pre-tension).
The regenerated cellulose industrial yarn prepared by the preparation method of the invention is extruded from a cellulose solution through a spinneret orifice, enters a first coagulation bath, a second coagulation bath and a third coagulation bath through an air gap section for gradient coagulation, and is washed and dried to prepare the regenerated cellulose industrial yarn with high strength, high modulus and high elongation at break.
The industrial yarn is prepared by a dry-jet wet spinning process with three-stage gradient coagulation, and compared with the existing primary coagulation process, the industrial yarn is added with a second coagulation bath and a third coagulation bath, and meanwhile, the process conditions of each primary coagulation bath are changed, so that the forming process of regenerated cellulose fibers is more eased. The first coagulation bath adopts higher concentration and lower temperature conditions, so that the forming speed of the silk yarns is slowed down, the difference of skin-core structures of fibers is reduced, meanwhile, the silk yarns are ensured to have higher solvent residues, the intermolecular actions of cellulose are weakened, the movement capacity of cellulose chain segments is improved, and conditions are provided for the adjustment of structures in the subsequent second and third coagulation baths; in the second coagulation bath, a relatively moderate concentration and a higher temperature condition are adopted, wherein the higher temperature condition mainly provides thermodynamic conditions for movement of cellulose chain segments in the silk, the relatively moderate concentration is used for reducing the forming speed of the silk, reducing the structural difference along the radial direction of the silk, and simultaneously enabling the structure of the silk to be basically fixed; the third coagulation bath adopts lower concentration and higher temperature conditions, and simultaneously reduces the stress along the axial direction of the yarn by adjusting the stretching conditions so as to further shape the yarn. The technical route of three-stage coagulation bath gradient coagulation slows down the forming speed of the silk strip, so that the difference of the sheath-core structure of the final regenerated cellulose industrial silk is reduced, the structure is more uniform, the strength and modulus of the fiber are ensured, meanwhile, the shrinkage along the axial direction of the silk strip in the second coagulation bath and the smaller stress condition along the axial direction of the silk strip in the third coagulation bath are properly reduced, the orientation degree of the fiber is properly reduced, and the high elongation at break of the regenerated cellulose industrial silk is ensured. However, the existing primary solidification technology cannot be used for preparing regenerated cellulose industrial yarns which simultaneously meet the requirements of high strength, high modulus and high elongation at break.
In summary, the preparation method and the device for the regenerated cellulose industrial yarn provided by the invention have the advantages that the prepared regenerated cellulose industrial yarn has higher breaking strength, initial modulus and breaking elongation: the regenerated cellulose industrial yarn prepared by the invention has fineness of 500-3500dtex, dry strength of 4.5-6cN/dtex, dry modulus not less than 100cN/dtex, elongation at break of 8-15%, and dry heat shrinkage rate under the conditions of 190 ℃ (temperature) and 0.01cN/dtex (pre-tension) not more than 0.7%.
The preparation method can ensure the breaking strength and modulus of the regenerated cellulose industrial yarn and improve the breaking elongation of the regenerated cellulose industrial yarn; the regenerated cellulose industrial yarn prepared by the technical route of the invention can meet the application requirements of the cord.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The description and applications of the present invention herein are illustrative and are not intended to limit the scope of the invention to the embodiments described above. Effects or advantages referred to in the embodiments may not be embodied in the embodiments due to interference of various factors, and description of the effects or advantages is not intended to limit the embodiments. Variations and modifications of the embodiments disclosed herein are possible, and alternatives and equivalents of the various components of the embodiments are known to those of ordinary skill in the art. It will be clear to those skilled in the art that the present invention may be embodied in other forms, structures, arrangements, proportions, and with other assemblies, materials, and components, without departing from the spirit or essential characteristics thereof. Other variations and modifications of the embodiments disclosed herein may be made without departing from the scope and spirit of the invention.
Claims (10)
1. A method for producing regenerated cellulose industrial yarn, the method comprising:
step S1, preparing spinning solution:
mixing, dehydrating and dissolving cellulose pulp and ionic liquid to prepare cellulose spinning stock solution with set concentration;
s2, a spinning step;
extruding the prepared cellulose spinning solution through a spinning cap for spinning;
step S3, gradient solidification:
sequentially feeding the extruded yarn into different coagulating baths to carry out graded coagulation treatment after passing through an air section;
step S4, a post-processing step:
and (3) washing and heat setting the yarn after gradient solidification to obtain regenerated cellulose industrial yarn.
2. The method for producing regenerated cellulose industrial yarn according to claim 1, wherein:
in the step S3, the extruded silk strip sequentially enters a first coagulating bath, a second coagulating bath and a third coagulating bath for carrying out graded coagulating treatment after passing through an air section;
wherein, the silk yarn is subjected to first solidification treatment in a first solidification bath, the silk yarn is subjected to second solidification treatment in a second solidification bath, and the silk yarn is subjected to third solidification treatment in a third solidification bath;
the concentration of the ionic liquid aqueous solution adopted by the first coagulating bath is higher than that adopted by the second coagulating bath; the temperature adopted by the first coagulating bath is lower than that adopted by the second coagulating bath and that adopted by the third coagulating bath; the concentration of the ionic liquid aqueous solution adopted by the second coagulating bath is higher than that adopted by the third coagulating bath.
3. The method for producing regenerated cellulose industrial yarn according to claim 2, wherein:
in the step S3, the first coagulation bath adopts higher concentration and lower temperature conditions, so as to slow down the forming speed of the filament, reduce the difference of the sheath-core structure of the fiber, ensure that the filament has higher solvent residue, weaken the intermolecular action of cellulose, improve the movement capacity of cellulose chain segments, and provide conditions for the adjustment of the structures in the subsequent second coagulation bath and third coagulation bath;
in the second coagulation bath, a relatively moderate concentration and a higher temperature condition are adopted, wherein the higher temperature condition mainly provides thermodynamic conditions for movement of cellulose chain segments in the silk, the relatively moderate concentration is used for reducing the forming speed of the silk, reducing the structural difference along the radial direction of the silk, and simultaneously enabling the structure of the silk to be basically fixed;
the third coagulating bath adopts lower concentration and higher temperature conditions, and simultaneously reduces the stress along the axial direction of the yarn through the adjustment of the stretching conditions and further forms the yarn; the technical route of three-stage coagulation bath gradient coagulation slows down the forming speed of the silk strip, so that the final regenerated cellulose industrial silk skin-core structure difference is reduced, the structure is more uniform, the strength and modulus of the fiber are ensured, meanwhile, the shrinkage along the axial direction of the silk strip in the second coagulation bath and the smaller stress condition along the axial direction of the silk strip in the third coagulation bath are properly reduced, the orientation degree of the fiber is properly reduced, and the high breaking elongation of the regenerated cellulose industrial silk is ensured.
4. The method for producing regenerated cellulose industrial yarn according to claim 1, wherein:
in the step S1, cellulose pulp with the intrinsic viscosity of 300-1000ml/g and ionic liquid are mixed, dehydrated and dissolved to prepare cellulose spinning stock solution with the concentration of 5-20%;
the dissolution adopts a wet dissolution process; the intrinsic viscosity of the cellulose pulp is 500-800ml/g;
the ionic liquid is at least one of 1-butyl-3-methylimidazole chloride, 1-allyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole acetate, 1-ethyl-3-methylimidazole chloride or 1-butyl-3-methylimidazole acetate;
the solid content of cellulose in the spinning solution is 8-15%;
in the step S2, the number of the spinneret holes is 100-3000 holes; the diameter of the spinneret orifice is 0.04-0.2mm; the spinning temperature is 80-120 ℃.
5. The method for producing regenerated cellulose industrial yarn according to claim 1, wherein:
in the step S3, the length of the air section is 5-500mm;
the first coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 0-60%, the coagulating bath temperature is 0-30 ℃, the stretching multiplying power is 1-5 times, and the stretching speed is 10-150m/min;
the second coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 10-40%, the coagulating bath temperature is 10-90 ℃, the stretching multiplying power is 0.9-1.2 times, and the stretching speed is 9-180m/min;
The third coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 0-30%, the coagulating bath temperature is 10-90 ℃, the stretching multiplying power is 0.9-1.2 times, and the stretching speed is 8-200m/min.
6. The method for producing regenerated cellulose industrial yarn according to claim 5, wherein:
the first coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 30-50%, the coagulating bath temperature is 5-20 ℃, the stretching multiplying power is 1-2 times, and the stretching speed is 20-50m/min;
the second coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 20-30%, the coagulating bath temperature is 40-90 ℃, the stretching multiplying power is 0.95-1.05 times, and the stretching speed is 19-55m/min;
the third coagulation bath conditions were: the coagulating bath is an ionic liquid aqueous solution with the mass fraction of 10-20%, the coagulating bath temperature is 40-90 ℃, the stretching multiplying power is 0.95-1.05 times, and the stretching speed is 18-58m/min.
7. The method for producing regenerated cellulose industrial yarn according to claim 1, wherein:
in the step S4, the obtained regenerated cellulose industrial yarn has fineness of 500-3500dtex, dry strength of 4.5-6cN/dtex, dry modulus not less than 100cN/dtex, elongation at break of 8-15%, and dry heat shrinkage rate under the condition of 190 ℃ and pre-tension of 0.01cN/dtex of not more than 0.7%.
8. A manufacturing apparatus for regenerated cellulose industrial yarn, characterized in that the manufacturing apparatus comprises: the device comprises a dissolver, a spinning component, a plurality of coagulating baths, a water washing device, a heat setting device and a winding device;
the dissolver is used for mixing, dehydrating and dissolving cellulose pulp and ionic liquid to prepare cellulose spinning solution with set concentration;
the spinning component is used for extruding and spinning the prepared cellulose spinning stock solution; sequentially feeding the extruded yarn into each coagulating bath to carry out graded coagulating treatment after passing through an air section;
and after the silk strip subjected to gradient solidification is subjected to water washing by the water washing device and heat setting by the heat setting device, winding by the winding device to obtain regenerated cellulose industrial silk.
9. The production apparatus according to claim 8, wherein:
the plurality of coagulating baths comprise a first coagulating bath, a second coagulating bath and a third coagulating bath; sequentially entering the first coagulating bath, the second coagulating bath and the third coagulating bath to carry out graded coagulating treatment after the extruded silk strip passes through the air section;
wherein, the silk yarn is subjected to first solidification treatment in a first solidification bath, the silk yarn is subjected to second solidification treatment in a second solidification bath, and the silk yarn is subjected to third solidification treatment in a third solidification bath;
The preparation apparatus includes a coagulation control module to control parameters of each coagulation bath such that: the concentration of the ionic liquid aqueous solution adopted by the first coagulating bath is higher than that adopted by the second coagulating bath; the temperature adopted by the first coagulating bath is lower than that adopted by the second coagulating bath and that adopted by the third coagulating bath; the concentration of the ionic liquid aqueous solution adopted by the second coagulating bath is higher than that adopted by the third coagulating bath.
10. The production apparatus according to claim 9, wherein:
the first coagulating bath adopts higher concentration and lower temperature conditions, so that the forming speed of the silk yarns is slowed down, the difference of the sheath-core structures of the fibers is reduced, meanwhile, the silk yarns are ensured to have higher solvent residues, the intermolecular actions of cellulose are weakened, the movement capacity of cellulose chain segments is improved, and conditions are provided for the adjustment of the structures in the subsequent second coagulating bath and the third coagulating bath;
in the second coagulation bath, a relatively moderate concentration and a higher temperature condition are adopted, wherein the higher temperature condition mainly provides thermodynamic conditions for movement of cellulose chain segments in the silk, the relatively moderate concentration is used for reducing the forming speed of the silk, reducing the structural difference along the radial direction of the silk, and simultaneously enabling the structure of the silk to be basically fixed;
The third coagulating bath adopts lower concentration and higher temperature conditions, and simultaneously reduces the stress along the axial direction of the yarn through the adjustment of the stretching conditions and further forms the yarn; the technical route of three-stage coagulation bath gradient coagulation slows down the forming speed of the silk strip, so that the final regenerated cellulose industrial silk skin-core structure difference is reduced, the structure is more uniform, the strength and modulus of the fiber are ensured, meanwhile, the shrinkage along the axial direction of the silk strip in the second coagulation bath and the smaller stress condition along the axial direction of the silk strip in the third coagulation bath are properly reduced, the orientation degree of the fiber is properly reduced, and the high breaking elongation of the regenerated cellulose industrial silk is ensured.
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