CN116288805B - Polyester superfine fiber with titanium-free extinction and cationic dye and easy dyeing under normal pressure and preparation method thereof - Google Patents
Polyester superfine fiber with titanium-free extinction and cationic dye and easy dyeing under normal pressure and preparation method thereof Download PDFInfo
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- CN116288805B CN116288805B CN202310319892.0A CN202310319892A CN116288805B CN 116288805 B CN116288805 B CN 116288805B CN 202310319892 A CN202310319892 A CN 202310319892A CN 116288805 B CN116288805 B CN 116288805B
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- 239000000835 fiber Substances 0.000 title claims abstract description 144
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 37
- 229920000728 polyester Polymers 0.000 title claims abstract description 37
- 238000004043 dyeing Methods 0.000 title claims abstract description 30
- 230000008033 biological extinction Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 238000009987 spinning Methods 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 229920001634 Copolyester Polymers 0.000 claims description 37
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 22
- 239000004088 foaming agent Substances 0.000 claims description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims description 14
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052708 sodium Chemical group 0.000 claims description 9
- 239000011734 sodium Chemical group 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000003361 porogen Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000009835 boiling Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 38
- 239000000975 dye Substances 0.000 description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 27
- 239000000155 melt Substances 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000002788 crimping Methods 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 238000001125 extrusion Methods 0.000 description 16
- 229920001410 Microfiber Polymers 0.000 description 15
- 238000005886 esterification reaction Methods 0.000 description 13
- 238000006068 polycondensation reaction Methods 0.000 description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 13
- 238000005809 transesterification reaction Methods 0.000 description 13
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000009998 heat setting Methods 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 8
- 239000012760 heat stabilizer Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 7
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 7
- 229940035437 1,3-propanediol Drugs 0.000 description 7
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical group COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 5
- 238000011045 prefiltration Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 239000006224 matting agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000000986 disperse dye Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003658 microfiber Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
- D06B23/20—Arrangements of apparatus for treating processing-liquids, -gases or -vapours, e.g. purification, filtration, distillation
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/02—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes
- D06P1/04—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal
- D06P1/08—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes not containing metal cationic azo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8276—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester groups
-
- 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
Abstract
The application discloses a polyester superfine fiber with titanium-free extinction and cationic dye normal-pressure dyeing easiness and a preparation method thereof, and belongs to the technical field of superfine fibers. The preparation method of the polyester superfine fiber comprises the following steps: and (3) blending and melting a matrix CDP and a pore-forming agent UFC, extruding and granulating to obtain pore-forming agent master batches, mixing the pore-forming agent master batches with the CDP to obtain island components, taking the UFC as a sea component, preparing sea-island fibers by melt composite spinning, and carrying out fiber opening treatment on the sea-island fibers in a buffer aqueous solution to obtain the polyester superfine fibers with titanium-free extinction and cationic dye normal-pressure dyeing. The CDP superfine fiber formed by the preparation method has the advantages that microfiber-shaped holes are randomly distributed in the internal structure of the CDP superfine fiber, so that normal-pressure boiling dyeing of cationic dye can be realized, reflection of light can be reduced, a titanium-free extinction effect is achieved, no additional working procedures are required, special requirements on equipment are avoided, and the preparation method is simple.
Description
Technical Field
The application belongs to the technical field of superfine fibers, and particularly relates to a polyester superfine fiber with titanium-free extinction and cationic dye normal-pressure dyeing easiness and a preparation method thereof.
Background
The sea-island type composite fiber method is a relatively mature production process for producing superfine fiber, and the sea-island fiber belongs to one of the varieties of composite superfine fiber, and adopts a composite spinning technology to take 2 fiber-forming polymers as island components and sea components respectively, and melt-spin the island components and the sea components according to different proportions, and then uses the different solubility or decomposability of the 2 components to certain chemical solvents to remove the sea components and leave the island components so as to obtain the superfine fiber.
In CN202010644577, CN202010644587, CN202010644732 and CN202010644747, a modified copolyester is used as sea component to prepare sea-island fiber, and because it has the characteristics of being insoluble in boiling water but soluble in aqueous solution at lower temperature under specific conditions, when used as sea component of sea-island fiber, it can be effectively removed by mild process and means, and damage of island component in sea-island fiber can be effectively avoided, so as to form superfine fiber only with island component, so that the modified copolyester is a more ideal fixed-island superfine fiber carrier (Ultrafine Fiber Carrier, hereinafter abbreviated as UFC). Therefore, the CN202010644575 further takes polyethylene terephthalate (PET) as an island component and UFC as a sea component, adopts a melt composite spinning technology to prepare sea-island fibers taking PET as the island component, and obtains the PET superfine fibers after fiber opening. The PET superfine fiber has good mechanical property, but the disperse dye is adopted to dye under the dyeing condition of high temperature and high pressure, so that the requirement on equipment is high, and the energy consumption is high; in addition, the disperse dye is combined with PET superfine fiber by Van der Waals force or hydrogen bond, is easy to migrate and change in color, and limits the application of the disperse dye in the field of high-end microfiber suede leather.
In order to solve the problems of color migration and color change of the superfine fiber, cationic dye dyeable Copolyester (CDP) and cationic dye normal pressure dyeable copolyester (ECDP) are respectively adopted as island components, when UFC is adopted as sea component, a melt composite spinning technology is adopted to respectively prepare sea-island fiber with CDP and ECDP as island components, and the CDP superfine fiber and the ECDP superfine fiber are obtained after fiber opening, so that the following problems still exist in the prepared superfine fiber: (1) When ECDP is adopted as an island component for the fixed island type sea-island composite fiber, the spinnability is affected due to poor heat resistance, the phenomena of floating yarn and broken ends exist, and the service life of the component is short; (2) When CDP is adopted as an island component of the fixed island type sea-island composite fiber, although the spinnability is good, the prepared CDP superfine fiber has strong light, the extinction effect comfortable for vision cannot be achieved, on one hand, the cost is increased, and on the other hand, the sea-island fiber composite spinneret orifice is easily blocked by adding the inorganic powder titanium dioxide extinction agent, so that the spinnability is poor. Therefore, the technical problem to be solved is how to prepare the copolyester superfine fiber which has no titanium extinction and is easy to dye with cationic dye at normal pressure.
Disclosure of Invention
In order to solve the technical problems, the application provides a polyester superfine fiber with titanium-free extinction and cationic dye normal-pressure dyeing easiness and a preparation method thereof.
In order to achieve the above object, the present application provides the following solutions:
the application provides a polyester superfine fiber which has no titanium extinction and cation dye normal pressure dyeing easiness, wherein the diameter of the cation dye normal pressure dyeing easiness polyester superfine fiber is less than or equal to 5 mu m, and microfibrous holes are distributed on the cross section of the fiber. Under the condition of normal pressure boiling dyeing, cationic dye can be used for normal pressure dyeing at the temperature of 95-100 ℃, and the dyeing rate is more than 90%; the polyester superfine fiber still has a matting effect without the titanium dioxide matting agent.
The application also provides a preparation method of the polyester superfine fiber with titanium-free extinction and cationic dye and easy dyeing under normal pressure, which comprises the following steps:
(1) Blending and melting a matrix and a pore-foaming agent, extruding and granulating to obtain pore-foaming agent master batches, wherein the matrix is CDP (cationic dye dyeable copolyester), the pore-foaming agent is UFC, and holes can be left after dissolution and removal in a fiber opening bath;
(2) Mixing the pore-forming agent master batch with CDP to obtain an island component, taking UFC as a sea component, and carrying out melt composite spinning on the island component and the sea component to obtain sea-island fibers;
(3) And (3) carrying out fiber opening treatment on the sea-island fiber in a buffer aqueous solution, wherein the sea component UFC and the pore-forming agent UFC of the sea-island fiber are completely dissolved, and the polyester superfine fiber (CDP superfine fiber) which has the functions of titanium-free extinction and cationic dye and is easy to dye at normal pressure can be obtained.
Further, the cationic dye dyeable copolyester CDP is obtained by copolymerizing 5-sodium sulfonate-isophthalic acid components in a conventional polyester PET molecular structure chain segment.
Further, in the step (1), the amount of the matrix in the pore-foaming agent master batch is (70-80) wt%, and the amount of the pore-foaming agent is (20-30) wt%.
Further, in the step (2), the amount of the pore-forming agent master batch in the island component is (5-10) wt%, and the amount of the CDP is (90-95) wt%.
Further, in the step (2), the mass ratio of the sea component to the island component is (20-35): 65-80.
Further, in the step (2), the melt composite spinning specifically includes: feeding the island component into a first screw extruder for melt extrusion, feeding the sea component into a second screw extruder for melt extrusion, feeding the two melt after melt extrusion into a sea-island fiber composite spinning box body, respectively metering by a metering pump, spraying by a composite spinning spinneret plate to obtain primary fibers, and then bundling, stretching, heat setting, crimping and cutting to obtain the sea-island fibers taking CDP as the island component.
Further, the temperature of five zones in the first screw extruder is 275 ℃ to 280 ℃, 280 ℃ to 285 ℃, 285 ℃ to 290 ℃ and 290 ℃ to 295 ℃; the temperature of five areas in the second screw extruder is 250-265 ℃, 265-275 ℃, 260-270 ℃ and 260-280 ℃.
Further, in the step (3), the pH value of the buffer aqueous solution is 7.9-8.1, and the temperature is 70-80 ℃.
Further, in step (3), the pH of the buffered aqueous solution is adjusted with citric acid and disodium hydrogen phosphate.
Further, in the step (3), the buffer aqueous solution contains sulfolane and sodium sulfate, and the concentration of the sulfolane and the concentration of the sodium sulfate in the buffer aqueous solution are respectively (8-10) wt%.
Further, in the step (3), the specific preparation method of the buffer aqueous solution comprises the following steps: 0.2mol/L disodium hydrogen phosphate aqueous solution and 0.1mol/L citric acid aqueous solution are mixed according to the volume ratio (97.0-97.5): (2.5-3.0) and adding (8-10) weight percent sulfolane and (8-10) weight percent sodium sulfate respectively.
Further, in the step (3), the bath ratio of the sea-island fiber to the buffer aqueous solution is 1: (10-30).
Further, in the step (3), the time of the fiber opening treatment is (30-60) min.
The pore-forming agent master batch preparation process of the application aims at two: firstly, UFC is uniformly dispersed in CDP matrix in advance, so that difficulty in uniform dispersion in a spinning melting stage is reduced; secondly, the high-concentration master batch is added into the spinning raw material again in a certain proportion, so that the metering of the raw material proportion is facilitated, and the overall manufacturing cost is reduced.
The application discloses the following technical effects:
according to the technical scheme, the pore-forming agent UFC and the sea component UFC in the sea-island fiber are the same substance, in the fiber opening process, the sea-island fiber taking CDP as the island component is in a swelling state in a weak alkaline aqueous solution (pH is more than or equal to 7.9 and less than or equal to 8.1), so that the pore-forming agent UFC in the island component CDP and the sea component UFC outside the island component CDP can be dissolved and removed, microfiber-shaped holes are randomly distributed in the formed CDP superfine fiber inner structure, the dye molecules are favorably adsorbed and diffused by the fiber, the diffusion channel of the dye molecules is increased, the diffusion difficulty of the dye molecules from a dye bath to the inside of the CDP is reduced, normal-pressure boiling dyeing of cationic dye is realized, the heterogeneous interface between the microfiber-shaped holes and a CDP matrix increases the diffuse reflection and scattering of light, and the titanium-free extinction effect is generated.
Aiming at the technical problems that the dyeing condition of the CDP superfine fiber obtained from the sea-island composite fiber is harsh and the extinction effect cannot be achieved, the method adopts the method that the pore-forming agent and the sea component are selected from the same substance and are dissolved and removed in the fiber opening process, the dyeing rate of the CDP superfine fiber obtained by the preparation method under the normal-pressure boiling dyeing condition can reach more than 90 percent, the extinction purpose is achieved on the basis of no inorganic powder titanium dioxide extinction agent, the process is not additionally added, no special requirement is caused on equipment, the preparation method is simple, and the microfiber suede leather product in the subsequent process has the advantage of soft luster.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 is a schematic cross-sectional structure of a CDP ultrafine fiber prepared in example 1 of the present application, wherein the pore-forming agent UFC in the 1-pore-forming agent master batch, the 2-island component CDP, the 3-sea component UFC;
FIG. 2 is a schematic cross-sectional structure of CDP ultrafine fibers prepared in example 1 of the application, wherein 4-randomly distributed fibrous pores are shown.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The application provides a polyester superfine fiber which has no titanium extinction and cation dye normal pressure dyeing easiness, wherein the diameter of the cation dye normal pressure dyeing easiness polyester superfine fiber is less than or equal to 5 mu m, and microfibrous holes are distributed on the cross section of the fiber. Under the condition of normal pressure boiling dyeing, cationic dye can be used for normal pressure dyeing at the temperature of 95-100 ℃, and the dyeing rate is more than 90%; the polyester superfine fiber can still have a matting effect without containing a titanium dioxide matting agent.
The application also provides a preparation method of the polyester superfine fiber with titanium-free extinction and cationic dye and easy dyeing under normal pressure, which comprises the following steps:
(1) Blending and melting a matrix and a pore-foaming agent, extruding and granulating to obtain pore-foaming agent master batches, wherein the matrix is CDP, the pore-foaming agent is UFC, and the pore-foaming agent UFC can be dissolved and removed in a fiber opening bath to leave holes;
(2) Mixing the pore-forming agent master batch with CDP to obtain an island component, taking UFC as a sea component, and carrying out melt composite spinning on the island component and the sea component to obtain sea-island fibers;
(3) And (3) carrying out fiber opening treatment on the sea-island fiber in a buffer water solution to obtain the polyester superfine fiber (CDP superfine fiber) which has the functions of titanium-free extinction and cationic dye and is easy to dye at normal pressure.
Further, the cationic dye dyeable copolyester CDP is obtained by copolymerization modification of a third monomer containing a sulfonic acid group in a molecular structure chain segment of conventional polyester PET, is purchased through a commercial way, meets the standard of qualified products of cationic dye dyeable polyester Chips (CDP) of China textile industry standard FZ/T51003-2011, and the raw material CDP in the embodiment and the comparative example is a conventional polyester modification technology and a product in the field, and is not an important point of the application and is not repeated herein.
Further, in the step (1), the amount of the matrix in the pore-foaming agent master batch is (70-80) wt%, and the amount of the pore-foaming agent is (20-30) wt%.
Further, in the step (2), the amount of the pore-forming agent master batch in the island component is (5-10) wt%, and the amount of the CDP is (90-95) wt%.
Further, in the step (2), the mass ratio of the sea component to the island component is (20-35): 65-80.
Further, in the step (2), the melt composite spinning specifically includes: feeding the island component into a first screw extruder for melt extrusion, feeding the sea component into a second screw extruder for melt extrusion, feeding the two melt after melt extrusion into a sea-island fiber composite spinning box body, respectively metering by a metering pump, spraying by a composite spinning spinneret plate to obtain primary fibers, and then bundling, stretching, heat setting, crimping and cutting to obtain the sea-island fibers taking CDP as the island component.
Further, in the step (2), the temperature of five zones in the first screw extruder is 275 ℃ to 280 ℃, 280 ℃ to 285 ℃, 285 ℃ to 290 ℃ and 290 ℃ to 295 ℃; the temperature of five areas in the second screw extruder is 250-265 ℃, 265-275 ℃, 260-270 ℃ and 260-280 ℃.
Further, in the step (3), the pH value of the buffer aqueous solution is 7.9-8.1, and the temperature is 70-80 ℃.
Further, in the step (3), the pH of the buffered aqueous solution is adjusted with citric acid and sodium citrate.
Further, in the step (3), the buffer aqueous solution contains sulfolane and sodium sulfate, and the concentration of the sulfolane and the concentration of the sodium sulfate in the buffer aqueous solution are respectively (8-10) wt%.
Further, in the step (3), the specific preparation method of the buffer aqueous solution comprises the following steps: 0.2mol/L disodium hydrogen phosphate aqueous solution and 0.1mol/L citric acid aqueous solution are mixed according to the volume ratio (97.0-97.5): (3.0-2.5) and adding (8-10) weight percent sulfolane and (8-10) weight percent sodium sulfate respectively.
Further, in the step (3), the bath ratio of the sea-island fiber to the buffer aqueous solution is 1: (10-30).
Further, in the step (3), the time of the fiber opening treatment is (30-60) min.
Embodiments of the applicationThe pore-forming agent UFC and the sea component UFC are the same substance and are all modified copolyester, the modified copolyester is the modified copolyester disclosed by CN 111621875A, and the structural formula is as follows:wherein the repeating unit->Randomly selected from
M is potassium or sodium; n is more than or equal to 95.
More specifically, the modified copolyester has the structure
The molar ratio of (2) is 1: (1.1-2.4): (0.015-0.07): (0.04-0.20): (0.02-0.10).
More specifically, the preparation method of the modified polyester comprises the following steps:
1) Esterification reaction is carried out on ethylene glycol and terephthalic acid; the temperature of the esterification reaction is 240-270 ℃; the esterification reaction time is 2-4 h;
2) Adding sodium meta-benzene dibasic acid dibasic ester-5-sulfonate or potassium meta-benzene dibasic acid dibasic ester-5-sulfonate, and adding 2-methyl-1, 3-propanediol and 1, 3-propanediol for transesterification; the temperature of the transesterification reaction is 240-270 ℃; the time of the transesterification reaction is 1-3 h;
3) Adding a catalyst and a heat stabilizer to perform polycondensation reaction; the temperature of the polycondensation reaction is 270-300 ℃; the polycondensation reaction time is 2-4 h; wherein the catalyst is antimony trioxide; the heat stabilizer is trimethyl phosphate or triphenyl phosphate; the addition amount of the heat stabilizer is 0.02-0.06% of the mass of terephthalic acid; the addition amount of the catalyst is not more than 0.08% of the mass of terephthalic acid.
Further, the molar ratio of terephthalic acid, ethylene glycol, isophthalic dibasic acid dibasic ester-5-sodium or potassium sulfonate, 2-methyl-1, 3-propanediol and 1, 3-propanediol is 1: (1.1-2.4): (0.015-0.07): (0.04-0.20): (0.02-0.10).
The modified copolyester UFC obtained through the reaction is obtained through granulating and drying after discharging, and the UFC used in the embodiment and the comparative example of the application are prepared according to the method.
The other raw materials in the examples and comparative examples of the present application are commercially available.
The technical scheme of the application is further described by examples and comparative examples.
Example 1
(1) Preparation of UFC and CDP
In the embodiment, the pore-forming agent UFC and the sea component UFC are the same substance and are both modified copolyesters, wherein the modified copolyesters are the modified copolyesters disclosed by CN 111621875A, and the mole ratio of raw materials terephthalic acid, ethylene glycol, isophthalate dibasic ester-5-sodium sulfonate, 2-methyl-1, 3-propanediol and 1, 3-propanediol is 1:2.0:0.05:0.10:0.08, wherein the esterification reaction temperature is 250 ℃, and the esterification reaction time is 3 hours; the temperature of the transesterification reaction is 260 ℃, and the time of the transesterification reaction is 2 hours; the polycondensation reaction temperature is 275 ℃; the polycondensation reaction time is 3h, the adding amount of the catalyst antimony trioxide is 0.05wt% of the mass of terephthalic acid, the adding amount of the heat stabilizer trimethyl phosphate is 0.04wt% of the mass of terephthalic acid, the modified copolyester is prepared by the method as a pore-forming agent UFC and a sea component UFC in the embodiment, the intrinsic viscosity is 0.645dL/g measured by a capillary viscosimetry, and the melting point is 228 ℃;
in the embodiment, the CDP is purchased through a commercial way and is obtained by copolymerization modification of a third monomer containing sulfonic acid groups in a conventional polyester PET molecular structure chain segment, and meets the standard of qualified products of cationic dye dyeable polyester Chips (CDP) in China textile industry standard FZ/T51003-2011, the intrinsic viscosity is 0.695dL/g measured by a capillary viscosimetry, and the melting point is 246 ℃;
(2) Blending and melting 70wt% of matrix CDP and 30wt% of pore-forming agent UFC through a double-screw granulator, extruding and granulating to obtain pore-forming agent master batch, wherein the temperature of five areas in the double-screw extruder is 250 ℃, 265 ℃, 260 ℃ and 260 ℃;
(3) Mixing 10wt% of pore-forming agent master batch and 90wt% of CDP to obtain island components of sea-island fibers, feeding the island components into a first screw extruder for melt extrusion by adopting a melt composite spinning technology by taking UFC as the sea components, and simultaneously feeding the sea components into a second screw extruder for melt extrusion, wherein the five-zone temperature in the first screw extruder is 275 ℃, 280 ℃, 285 ℃, 290 ℃, and the five-zone temperature in the second screw extruder is 250 ℃, 265 ℃, 260 ℃; after passing through a prefilter, conveying the melt into a composite spinning box body respectively, metering the melt by a metering pump (the mass ratio of sea component to island component is 30:70), spraying the melt by a sea-island fiber composite spinning spinneret plate to obtain nascent fiber, and then bundling, stretching, heat setting, crimping and cutting the nascent fiber to obtain sea-island fiber with CDP as island component of 4.2dtex and 37 islands, wherein the temperature of the filter is 265 ℃, the temperature of the spinning box body is 270 ℃, the temperature of the annular blowing is 25 ℃, the wind speed is 0.30m/min, the relative humidity is 78%, the winding speed is 1000m/min, the temperature of an oil bath drafting tank is 60 ℃, the temperature of a steam heating box is 100 ℃, the first stretching ratio is 1.02, the second stretching ratio is 2.80, the third stretching ratio is 1.02, the stretching speed is 150m/min, the tension heat setting temperature is 150 ℃, the crimping temperature is 100 ℃, the main pressure of a crimping wheel is 0.35MPa, and the back pressure is 0.2MPa;
(4) The sea-island fiber is subjected to fiber opening treatment for 40min at 70 ℃ in a buffer aqueous solution with pH value of pH=8.0 (the buffer aqueous solution is specifically prepared by mixing 0.2mol/L of disodium hydrogen phosphate aqueous solution and 0.1mol/L of citric acid aqueous solution according to a volume ratio of 97.25:2.75, 10wt% of sulfolane and 8wt% of sodium sulfate are respectively added, the bath ratio is 1:20, and sea component UFC of the sea-island fiber and pore-forming agent UFC are completely dissolved (fiber-shaped holes which are randomly distributed are formed after the pore-forming agent UFC is dissolved), so as to obtain the CDP ultrafine fiber.
FIG. 1 is a schematic cross-sectional structure of a CDP ultrafine fiber prepared in example 1 of the present application, wherein the pore-forming agent UFC in the 1-pore-forming agent master batch, the 2-island component CDP, the 3-sea component UFC; FIG. 2 is a schematic cross-sectional structure of CDP ultrafine fibers prepared in example 1 of the application, wherein 4-randomly distributed fibrous pores are shown.
Example 2
(1) Preparation of UFC and CDP
In the embodiment, the pore-forming agent UFC and the sea component UFC are the same substance and are both modified copolyesters, wherein the modified copolyesters are the modified copolyesters disclosed by CN 111621875A, and the mole ratio of raw materials terephthalic acid, ethylene glycol, isophthalate dibasic ester-5-sodium sulfonate, 2-methyl-1, 3-propanediol and 1, 3-propanediol is 1:1.1:0.015:0.04:0.02, wherein the esterification reaction temperature is 240 ℃ and the esterification reaction time is 2h; the temperature of the transesterification reaction is 240 ℃, and the time of the transesterification reaction is 1h; the polycondensation reaction temperature is 270 ℃; the polycondensation reaction time is 2 hours, the adding amount of the catalyst antimony trioxide is 0.08 weight percent of the mass of terephthalic acid, the adding amount of the heat stabilizer trimethyl phosphate is 0.06 weight percent of the mass of terephthalic acid, the modified copolyester is prepared by the method and used as the pore-forming agent UFC and the sea component UFC in the embodiment, the intrinsic viscosity is 0.590dL/g measured by a capillary viscosimetry, and the melting point is 220 ℃;
in the embodiment, the CDP is purchased through a commercial way and is obtained by copolymerization modification of a third monomer containing sulfonic acid groups in a conventional polyester PET molecular structure chain segment, and meets the standard of qualified products of cationic dye dyeable polyester Chips (CDP) in China textile industry standard FZ/T51003-2011, the intrinsic viscosity is 0.695dL/g measured by a capillary viscosimetry, and the melting point is 246 ℃;
(2) Blending and melting 80wt% of matrix CDP and 20wt% of pore-forming agent UFC through a double-screw granulator, extruding and granulating to obtain pore-forming agent master batch, wherein the temperature of five areas in the double-screw extruder is 265 ℃, 275 ℃, 270 ℃ and 280 ℃;
(3) Mixing 5wt% of pore-forming agent master batch and 95wt% of CDP to obtain island components of sea-island fibers, taking UFC as sea components, adopting a melt composite spinning technology, feeding the island components into a first screw extruder for melt extrusion, simultaneously feeding the sea components into a second screw extruder for melt extrusion, wherein the five-zone temperature in the first screw extruder is 280 ℃, 285 ℃, 290 ℃, 295 ℃, and the five-zone temperature in the second screw extruder is 265 ℃, 275 ℃, 270 ℃, 280 ℃; after passing through a prefilter, conveying the melt into a composite spinning box body respectively, metering the melt by a metering pump (the mass ratio of sea component to island component is 20:80), spraying the melt by a sea-island fiber composite spinning spinneret plate to obtain nascent fiber, and then bundling, stretching, heat setting, crimping and cutting the nascent fiber to obtain sea-island fiber with 3.8dtex and 37 island with CDP as island component, wherein the temperature of the filter is 265 ℃, the temperature of the spinning box body is 270 ℃, the temperature of the annular blowing is 25 ℃, the wind speed is 0.30m/min, the relative humidity is 78%, the winding speed is 1000m/min, the temperature of an oil bath drafting tank is 60 ℃, the temperature of a steam heating box is 100 ℃, the first stretching ratio is 1.02, the second stretching ratio is 2.80, the third stretching ratio is 1.02, the stretching speed is 150m/min, the tension heat setting temperature is 150 ℃, the crimping temperature is 100 ℃, the main pressure of a crimping wheel is 0.35MPa, and the back pressure is 0.2MPa;
(4) The sea-island fiber is subjected to fiber opening treatment for 30min at 80 ℃ in a buffer aqueous solution with pH value of pH=7.9 (the buffer aqueous solution is specifically prepared by mixing 0.2mol/L of disodium hydrogen phosphate aqueous solution and 0.1mol/L of citric acid aqueous solution according to a volume ratio of 97.5:2.5, 8wt% of sulfolane and 10wt% of sodium sulfate are respectively added, the bath ratio is 1:10, and the sea component UFC and the pore-forming agent UFC of the sea-island fiber are completely dissolved to obtain the CDP ultrafine fiber.
Example 3
(1) Preparation of UFC and CDP
In the embodiment, the pore-forming agent UFC and the sea component UFC are the same substance and are both modified copolyesters, wherein the modified copolyesters are the modified copolyesters disclosed by CN 111621875A, and the mole ratio of raw materials terephthalic acid, ethylene glycol, isophthalate dibasic ester-5-sodium sulfonate, 2-methyl-1, 3-propanediol and 1, 3-propanediol is 1:2.4:0.07:0.20:0.10, wherein the esterification reaction temperature is 270 ℃ and the esterification reaction time is 4 hours; the temperature of the transesterification reaction is 270 ℃, and the time of the transesterification reaction is 3 hours; the polycondensation reaction temperature is 300 ℃; the polycondensation reaction time is 4 hours, the adding amount of the catalyst antimony trioxide is 0.06wt% of the mass of terephthalic acid, the adding amount of the heat stabilizer trimethyl phosphate is 0.04wt% of the mass of terephthalic acid, the modified copolyester is formed by the method as a pore-forming agent UFC and a sea component UFC in the embodiment, the intrinsic viscosity is 0.685dL/g measured by a capillary viscosimetry, and the melting point is 235 ℃;
in the embodiment, the CDP is purchased through a commercial way and is obtained by copolymerization modification of a third monomer containing sulfonic acid groups in a conventional polyester PET molecular structure chain segment, and meets the standard of qualified products of cationic dye dyeable polyester Chips (CDP) in China textile industry standard FZ/T51003-2011, the intrinsic viscosity is 0.695dL/g measured by a capillary viscosimetry, and the melting point is 246 ℃;
(2) Blending and melting 75wt% of matrix CDP and 25wt% of pore-forming agent UFC through a double-screw granulator, extruding and granulating to obtain pore-forming agent master batch, wherein the temperature of five areas in the double-screw extruder is 250 ℃, 265 ℃, 260 ℃ and 260 ℃;
(3) Mixing 10wt% of pore-forming agent master batch and 90wt% of CDP to obtain island components of sea-island fibers, taking UFC as sea components, adopting a melt composite spinning technology, feeding the island components into a first screw extruder for melt extrusion, simultaneously feeding the sea components into a second screw extruder for melt extrusion, wherein the five-zone temperature in the first screw extruder is 280 ℃, 285 ℃, 290 ℃, 295 ℃, and the five-zone temperature in the second screw extruder is 265 ℃, 275 ℃, 270 ℃, 280 ℃; after passing through a prefilter, conveying the melt into a composite spinning box body respectively, metering the melt by a metering pump (the mass ratio of sea component to island component is 35:65), spraying the melt by a sea-island fiber composite spinning spinneret plate to obtain nascent fiber, and then bundling, stretching, heat setting, crimping and cutting the nascent fiber to obtain sea-island fiber with CDP as island component of 4.4dtex and 37 islands, wherein the temperature of the filter is 265 ℃, the temperature of the spinning box body is 270 ℃, the temperature of the annular blowing is 25 ℃, the wind speed is 0.30m/min, the relative humidity is 78%, the winding speed is 1000m/min, the temperature of an oil bath drafting tank is 60 ℃, the temperature of a steam heating box is 100 ℃, the first stretching ratio is 1.02, the second stretching ratio is 2.80, the third stretching ratio is 1.02, the stretching speed is 150m/min, the tension heat setting temperature is 150 ℃, the crimping temperature is 100 ℃, the main pressure of a crimping wheel is 0.35MPa, and the back pressure is 0.2MPa;
(4) The sea-island fiber is subjected to fiber opening treatment for 40min at 75 ℃ in a buffer aqueous solution with pH value of pH=8.1 (the buffer aqueous solution is specifically prepared by mixing 0.2mol/L of disodium hydrogen phosphate aqueous solution and 0.1mol/L of citric acid aqueous solution according to a volume ratio of 96.5:3.5, and respectively adding 9wt% of sulfolane and 9wt% of sodium sulfate), wherein the bath ratio is 1:20, and the sea component UFC and the pore-forming agent UFC of the sea-island fiber are completely dissolved to obtain the CDP ultrafine fiber.
Example 4
(1) Preparation of UFC and CDP
In the embodiment, the pore-forming agent UFC and the sea component UFC are the same substance and are both modified copolyesters, wherein the modified copolyesters are the modified copolyesters disclosed by CN 111621875A, and the mole ratio of raw materials of terephthalic acid, ethylene glycol, isophthalate dibasic ester-5-potassium sulfonate, 2-methyl-1, 3-propanediol and 1, 3-propanediol is 1:2.0:0.05:0.10:0.08, wherein the esterification reaction temperature is 250 ℃, and the esterification reaction time is 3 hours; the temperature of the transesterification reaction is 260 ℃, and the time of the transesterification reaction is 2 hours; the polycondensation reaction temperature is 275 ℃; the polycondensation reaction time is 3h, the adding amount of the catalyst antimony trioxide is 0.05wt% of the mass of terephthalic acid, the adding amount of the heat stabilizer trimethyl phosphate is 0.04wt% of the mass of terephthalic acid, the modified copolyester is formed by the method as a pore-forming agent UFC and a sea component UFC in the embodiment, the intrinsic viscosity is 0.645dL/g measured by a capillary viscosimetry, and the melting point is 228 ℃;
in the embodiment, the CDP is purchased through a commercial way and is obtained by copolymerization modification of a third monomer containing sulfonic acid groups in a conventional polyester PET molecular structure chain segment, and meets the standard of qualified products of cationic dye dyeable polyester Chips (CDP) in China textile industry standard FZ/T51003-2011, the intrinsic viscosity is 0.695dL/g measured by a capillary viscosimetry, and the melting point is 246 ℃;
(1) Blending and melting 80wt% of matrix CDP and 20wt% of pore-foaming agent UFC through a double-screw granulator, and extruding and granulating to obtain pore-foaming agent master batch;
(2) Mixing 6wt% of pore-forming agent master batch and 94wt% of CDP to obtain island components of sea-island fibers, feeding the island components into a first screw extruder for melt extrusion by adopting a melt composite spinning technology by taking UFC as the sea components, and simultaneously feeding the sea components into a second screw extruder for melt extrusion, wherein the five-zone temperature in the first screw extruder is 275 ℃, 280 ℃, 285 ℃, 290 ℃, and the five-zone temperature in the second screw extruder is 250 ℃, 265 ℃, 260 ℃; after passing through a prefilter, conveying the melt into a composite spinning box body respectively, metering the melt by a metering pump (the mass ratio of sea component to island component is 30:70), spraying the melt by a sea-island fiber composite spinning spinneret plate to obtain nascent fiber, and then bundling, stretching, heat setting, crimping and cutting the nascent fiber to obtain sea-island fiber with CDP as island component of 4.0dtex and 37 islands, wherein the temperature of the filter is 265 ℃, the temperature of the spinning box body is 270 ℃, the temperature of the annular blowing is 25 ℃, the wind speed is 0.30m/min, the relative humidity is 78%, the winding speed is 1000m/min, the temperature of an oil bath drafting tank is 60 ℃, the temperature of a steam heating box is 100 ℃, the first stretching ratio is 1.02, the second stretching ratio is 2.80, the third stretching ratio is 1.02, the stretching speed is 150m/min, the tension heat setting temperature is 150 ℃, the crimping temperature is 100 ℃, the main pressure of a crimping wheel is 0.35MPa, and the back pressure is 0.2MPa;
(4) The sea-island fiber is subjected to fiber opening treatment for 60min at 70 ℃ in a buffer aqueous solution with pH value of pH=8.0 (the buffer aqueous solution is specifically prepared by mixing 0.2mol/L of disodium hydrogen phosphate aqueous solution and 0.1mol/L of citric acid aqueous solution according to a volume ratio of 97.25:2.75, 8wt% of sulfolane and 8wt% of sodium sulfate are respectively added, the bath ratio is 1:30, and the sea component UFC and the pore-forming agent UFC of the sea-island fiber are completely dissolved to obtain the CDP ultrafine fiber.
Comparative example 1
The difference from example 1 is that the sea-island fiber of 4.2dtex and 37 islands, in which the mass ratio of sea component to island component is 30:70, is obtained by using CDP as the island component of the sea-island fiber (i.e., no pore-forming agent master batch is added to the island component) and UFC as the sea component and adopting the melt composite spinning technique.
Comparative example 2
The difference from example 1 is that the sea-island fiber was subjected to a fiber opening treatment at 70℃in an aqueous solution having a pH value of pH=7.0 (the aqueous solution is specifically prepared by directly adding 10% by weight of sulfolane and 8% by weight of sodium sulfate to water for dissolution) for 40 minutes at a bath ratio of 1:20, the sea component UFC of the sea-island fiber is completely dissolved, and the CDP superfine fiber is obtained.
Comparative example 3
(1) Preparation of UFC and CDP
In the comparative example, the pore-forming agent UFC and the sea component UFC are the same substances and are all modified copolyesters, wherein the modified copolyesters are the modified copolyesters disclosed by CN 111621875A, and the mole ratio of raw materials of terephthalic acid, ethylene glycol, isophthalate dibasic ester-5-sodium sulfonate, 2-methyl-1, 3-propanediol and 1, 3-propanediol is 1:2.0:0.05:0.10:0.08, wherein the esterification reaction temperature is 250 ℃, and the esterification reaction time is 3 hours; the temperature of the transesterification reaction is 260 ℃, and the time of the transesterification reaction is 2 hours; the polycondensation reaction temperature is 275 ℃; the polycondensation reaction time is 3h, the adding amount of the catalyst antimony trioxide is 0.05wt% of the mass of the terephthalic acid, the adding amount of the heat stabilizer trimethyl phosphate is 0.04wt% of the mass of the terephthalic acid, the modified copolyester is formed by the method as the pore-forming agent UFC and the sea component UFC in the embodiment, the intrinsic viscosity is 0.645dL/g measured by a capillary viscosimetry, and the melting point is 228 ℃;
in the comparative example, the CDP is purchased through a commercial way and is obtained by copolymerization modification of a third monomer containing sulfonic acid groups in a conventional polyester PET molecular structure chain segment, and meets the standard of a Chinese textile industry standard FZ/T51003-2011 cationic dye dyeable polyester Chip (CDP) qualification product, and the intrinsic viscosity is 0.695dL/g and the melting point is 246 ℃ measured by a capillary viscosimetry;
(2) The commercial titanium dioxide extinction polyester master batch (the titanium dioxide content is 50 wt%) and CDP are mixed according to the mass ratio of 5wt%:90wt% of island components of sea-island fibers are obtained by mixing, UFC is used as a sea component, a melt composite spinning technology is adopted, the island components are fed into a first screw extruder for melt extrusion, meanwhile, the sea components are fed into a second screw extruder for melt extrusion, the five-zone temperature in the first screw extruder is 275 ℃, 280 ℃, 285 ℃, 290 ℃, and the five-zone temperature in the second screw extruder is 250 ℃, 265 ℃, 260 ℃;
(3) After passing through a prefilter, conveying the melt into a composite spinning box body respectively, metering the melt by a metering pump (the mass ratio of sea component to island component is 30:70), spraying the melt by a sea-island fiber composite spinning spinneret plate to obtain nascent fiber (the phenomenon of broken filaments caused by spinneret blockage is observed during spinning), and then bundling, stretching, heat setting, crimping and cutting the nascent fiber with CDP as island component of 4.2dtex and 37 islands, wherein the temperature of the filter is 265 ℃, the temperature of the spinning box body is 270 ℃, the annular blowing temperature is 25 ℃, the wind speed is 0.30m/min, the relative humidity is 78%, the winding speed is 1000m/min, the temperature of an oil bath drafting tank is 60 ℃, the temperature of a steam heating box is 100 ℃, the first stretching ratio is 1.02, the second stretching ratio is 2.80, the third stretching speed is 150m/min, the tension heat setting temperature is 150 ℃, the crimping temperature is 100 ℃, and the main pressure of a crimping wheel is 0.35MPa, and the back pressure is 0.2MPa;
(4) Sea-island fiber was subjected to a fiber opening treatment at 70℃in a buffer aqueous solution having a pH value of pH=8.0 (the buffer aqueous solution is specifically prepared by mixing 0.2mol/L of an aqueous solution of disodium hydrogen phosphate and 0.1mol/L of an aqueous solution of citric acid in a volume ratio of 97.25:2.75, and adding 10wt% of sulfolane and 8wt% of sodium sulfate, respectively) for 40 minutes in a bath ratio of 1:20, the sea component UFC of the sea-island fiber is completely dissolved, and the CDP superfine fiber containing the titanium dioxide matting agent is obtained.
Effect verification example
Washing the CDP superfine fibers prepared in the examples 1-4 and the comparative examples 1-3 with water, then drying, weighing, calculating the weight loss rate, observing the dried CDP superfine fibers under an optical fiber mirror, randomly selecting 30 fibers to measure the diameter of the monofilament fibers, and calculating the average diameter as the diameter of the monofilament fibers; and then the dried CDP superfine fiber is dyed by adopting cationic dye, and the cationic red M-RL, the cationic yellow M-4GL and the cationic blue M-RL are respectively adopted, wherein the dyeing concentration is 4%, the pH is 5-6 (regulated by acetic acid), the bath ratio is 1:20, the dyeing is carried out at 100 ℃ for 60min, and the result of calculating the coloring rate according to the industrial standard FZ/T50020-2013 cationic dye dyeable modified polyester coloring rate test method is shown in the table 1 and the table 2.
TABLE 1 weight loss and color loss of CDP ultrafine fibers of examples
TABLE 2 weight loss and color loss of comparative CDP microfibers
As can be seen from the data and the observation of the phenomena in the table 1 and the table 2, the CDP superfine fiber prepared by the technical scheme of the application has the coloring rate of more than 90 percent under the normal pressure boiling dyeing condition and has better dyeing performance for cationic dye; the matting effect of the CDP ultrafine fibers in some examples (example 1 and example 3) was consistent with that of the CDP ultrafine fibers added with the titanium dioxide matting agent in comparative example 3, and the aim of titanium-free matting was achieved.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (7)
1. The preparation method of the polyester superfine fiber with the functions of titanium-free extinction and cationic dye normal-pressure dyeing is characterized by comprising the following steps of:
(1) Blending and melting a matrix and a pore-foaming agent, extruding and granulating to obtain pore-foaming agent master batches, wherein the matrix is CDP, and the pore-foaming agent is UFC;
(2) Mixing the pore-forming agent master batch with CDP to obtain an island component, taking UFC as a sea component, and carrying out melt composite spinning on the island component and the sea component to obtain sea-island fibers;
(3) Carrying out fiber opening treatment on the sea-island fiber in a buffer water solution to obtain the polyester superfine fiber which has the functions of titanium-free extinction and cationic dye normal-pressure dyeing;
in the step (3), the pH value of the buffer aqueous solution is 7.9-8.1, and the temperature is (70-80);
in the step (3), the buffer aqueous solution contains sulfolane and sodium sulfate, wherein the concentration of the sulfolane and the concentration of the sodium sulfate in the buffer aqueous solution are respectively 8-10 wt%;
the CDP is cationic dye dyeable copolyester;
the UFC is modified copolyester, and the structural formula of the modified copolyester is as follows:wherein the repeating unitRandomly selected from-> M is potassium or sodium; n is more than or equal to 95.
2. The preparation method of claim 1, wherein the diameter of the cationic dye dyeable copolyester superfine fiber monofilament in the polyester superfine fiber which is prepared by the preparation method and has no titanium extinction and is easy to dye with cationic dye under normal pressure is less than or equal to 5 μm, and microfibrous holes are distributed on the fiber section.
3. The method of claim 1, wherein in step (1), the matrix is used in an amount of (70-80 wt%) and the porogen is used in an amount of (20-30 wt%).
4. The method of claim 1, wherein in step (2), the porogen master batch is used in an amount of (5-10) wt% and the CDP is used in an amount of (90-95) wt%.
5. The method of claim 1, wherein in step (2), the mass ratio of the sea component to the island component is (20-35): 65-80.
6. The method according to claim 1, wherein in the step (3), the bath ratio of the sea-island fiber to the buffer aqueous solution is 1: (10-30).
7. The method according to claim 1, wherein in the step (3), the time for the opening treatment is (30-60) min.
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