CN112962166A - Preparation method of disperse dye normal-pressure low-temperature easy-to-dye superfine fiber - Google Patents
Preparation method of disperse dye normal-pressure low-temperature easy-to-dye superfine fiber Download PDFInfo
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- CN112962166A CN112962166A CN202110281941.7A CN202110281941A CN112962166A CN 112962166 A CN112962166 A CN 112962166A CN 202110281941 A CN202110281941 A CN 202110281941A CN 112962166 A CN112962166 A CN 112962166A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a preparation method of a disperse dye normal-pressure low-temperature easy-to-dye superfine fiber, which relates to the technical field of modified copolyester and comprises the following preparation methods: (1) preparing low-temperature easy-dyeing modified copolyester; (2) sea-island composite spinning: carrying out pre-crystallization and drying on alkali-soluble polyester and low-temperature dyeable modified copolyester, then taking the alkali-soluble polyester as a sea part and the low-temperature dyeable modified copolyester as an island part, and spinning and winding to prepare the sea-island composite fiber; (3) alkali dissolution treatment: treating the sea-island composite fiber with an alkali solution to remove sea parts to prepare the disperse dye normal-pressure low-temperature easy-to-dye superfine fiber; the addition of the dihydric alcohol and the polyester polyol destroys the regularity of the original PET molecular chain, increases the amorphous region of the polyester, enables dye molecules to enter more easily, improves the dyeability, and can improve the water absorption performance of the polyester fiber while not influencing the stability of the polyester.
Description
Technical Field
The invention relates to a preparation method of modified copolyester, in particular to a preparation method of disperse dye normal-pressure low-temperature easy-to-dye superfine fiber.
Background
The conventional polyester fiber is a symmetrical straight-chain macromolecular structure and is tightly arranged, and the rigidity of the fiber structure is higher due to the existence of a conjugated system, so that the disperse dye can only be dyed at high temperature and high pressure. In order to improve the dyeing performance of polyester fibers, the molecular structure of polyester fibers is usually modified by chemical or physical modification methods, such as introducing groups capable of accepting dye molecules onto a macromolecular chain, increasing amorphous regions to make dyes more easily enter, or improving the dyeing performance by adding color master batches. The total of dyeable polyesters falls into two broad categories: cationic dyes polyester dyeable at normal pressure and low temperature (ECDP) and disperse dyes polyester dyeable at normal pressure and low temperature. The cationic dye is easy to dye polyester at normal pressure and low temperature, and the dyeing performance of polyester fiber is improved by introducing a third component containing a sulfonate structure and a fourth component for improving the flowability to a polyester macromolecular structure in an ester exchange mode. The ECDP fiber has good color fastness and bright color, is easy for industrial production, but is not easy to dye dark color, so that the application of the ECDP fiber is limited.
For example, a chinese patent publication discloses "a hydrophilic easy-to-dye cotton-like composite yarn and a method for manufacturing the same", which publication No. CN110184699A discloses a hydrophilic easy-to-dye cotton-like composite yarn, which is formed by combining two different filament bundles one by one, wherein the two different filament bundles are respectively: FDY adopts hydrophilic easy-dyeing cotton-like polyester spinning, POY adopts hydrophilic easy-dyeing cotton-like polyester spinning, and the hydrophilic easy-dyeing cotton-like polyester is generated by chemical reaction of polypropylene glycol, 5-sodium sulfoisophthalate, ethylene glycol antimony, cobalt acetate, a stabilizer Irganox1010, triphenyl phosphite, titanium dioxide, refined terephthalic acid and ethylene glycol. However, the low-temperature dyeing by adopting the cation is not easy to dye deep color, so that the application of the dye is limited.
Disclosure of Invention
The invention provides a preparation method of a disperse dye normal-pressure low-temperature easy-to-dye superfine fiber in order to overcome the problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a disperse dye normal-pressure low-temperature easy-to-dye superfine fiber comprises the following preparation methods:
(1) preparing low-temperature easy-dyeing modified copolyester:
(1.1) mixing terephthalic acid, ethylene glycol and a catalyst for esterification reaction to obtain an esterified substance;
(1.2) adding dihydric alcohol and polyester polyol into an esterified substance, then carrying out pre-polycondensation and final polycondensation, and discharging to prepare low-temperature easy-dyeing modified copolyester;
(2) sea-island composite spinning: carrying out pre-crystallization and drying on alkali-soluble polyester and low-temperature dyeable modified copolyester, then taking the alkali-soluble polyester as a sea part and the low-temperature dyeable modified copolyester as an island part, and spinning and winding to prepare the sea-island composite fiber;
(3) alkali dissolution treatment: the sea-island composite fiber is treated by alkali solution to remove sea part, and the disperse dye normal-pressure low-temperature easy-to-dye superfine fiber is prepared.
In the invention, when the low-temperature dyeable modified copolyester is prepared, firstly terephthalic acid and ethylene glycol are adopted for preliminary esterification to obtain an esterified substance, then a mixture of dihydric alcohol and polyester polyol is added into the esterified substance for polycondensation reaction, wherein the addition of the dihydric alcohol and the polyester polyol destroys the regularity of the original PET molecular chain, and simultaneously, an amorphous region of the polyester is increased, so that dye molecules can enter more easily.
Preferably, the alcohol-acid ratio of the ethylene glycol to the diol to the terephthalic acid in the step (1) is 1.2 to 1.6.
Preferably, the esterification reaction in the step (1.1) is carried out at 225-235 ℃ and 0.1-0.3Mpa for 1.5-2.5h, and the esterification rate is controlled to be more than 85%.
Preferably, the catalyst in the step (1.1) is a titanium catalyst, the addition amount is 5ppm based on the mass of Ti atoms in the theoretical polyester production amount, and the titanium catalyst comprises the following preparation steps:
s1: mixing the pseudo-boehmite slurry with 10-15 wt% of nitric acid solution, and adjusting the pH to 2-4 to obtain pseudo-boehmite sol with the solid content of 30-45%;
s2: mixing pseudo-boehmite sol and 8-10 wt% of p-azidobenzoic acid aqueous solution according to the mass ratio of 1:5-10, standing for adsorption for 2-5h, drying, and performing ion adsorption at 1000 ℃ and 5000mW/cm2After being irradiated for 15-30min under ultraviolet light, the alumina carrier is prepared by calcining for 4-6h at the temperature of 700-850 ℃ and grinding;
s3: soaking an alumina carrier to absorb water, and drying the surface of the alumina carrier to obtain a water-carrying alumina carrier with water carrying capacity of 1-1.5 wt%;
s4: placing tetrabutyl titanate, 2-hydroxycarboxylic acid compounds and phosphorus-containing compounds in isopropanol in a mol ratio of 1:1-10:1-10 to obtain an organic mixed solution;
s5: and (3) putting the water-carrying alumina carrier into the mixed solution, reacting for 1-3h at 50-80 ℃, and separating to prepare the titanium catalyst.
In the invention, firstly, a porous alumina carrier is prepared by using azidobenzoic acid as a pore-forming agent, and then the alumina carrier is adopted to carry out titanium loading, thus preparing the titanium catalyst.
In the preparation process of the alumina carrier, the pH value of the pseudo-boehmite slurry is adjusted to 2-4 to obtain pseudo-boehmite sol, the-OH on the surface of the pseudo-boehmite in the pseudo-boehmite sol acts with hydrogen ions, so that the pseudo-boehmite sol has positive charges, after the pseudo-boehmite sol is mixed with aqueous solution of azidobenzoic acid, the azidobenzoic acid has negative charges on the surface, so that the azidobenzoic acid can be electrostatically attracted with the pseudo-boehmite, the azidobenzoic acid can be firmly adsorbed on the surface of the pseudo-boehmite, the dispersibility and the loading stability of the pore-forming agent to the azidobenzoic acid are improved, so that pore channels generated by subsequent decomposition are more uniform, then in the ultraviolet irradiation process, the azidobenzoic acid on the azidobenzoic acid can be decomposed to generate nitrogen to form primary pore channels, in the subsequent calcination process to form alumina, the residual benzene rings can also be decomposed, and the formation of the pore channels is further expanded, the prepared alumina carrier with the pore size distribution of 15-25 nm.
And then, when the alumina carrier is used for carrying titanium, firstly carrying water in the alumina carrier, then soaking the water-carrying alumina carrier in an organic mixed solution containing tetrabutyl titanate, wherein an organic phase and a water phase are mutually diffused in a pore channel of the water-carrying alumina carrier, and when the tetrabutyl titanate is contacted with the water in the pore channel, hydrolyzing to obtain titanium dioxide, and carrying the titanium dioxide in the pore channel to prepare the titanium catalyst.
Because the titanium dioxide in the titanium catalyst prepared by the method is loaded in the pore channel, and the titanium dioxide is almost not present outside the pore channel, in the polyester catalysis process, a polymerization monomer needs to enter the pore channel and can be catalyzed after contacting with the titanium dioxide, so that a long-chain polyester molecular chain obtained by polymerization cannot continuously enter the pore channel for reaction under the restriction action of the pore channel, the molecular weight of a final product can be more concentrated, the catalysis control effect is achieved, and the spinning stability is improved.
Preferably, the dihydric alcohol in step (1.2) comprises one or more of 1, 2-propylene glycol, 1, 2-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, and is used in an amount of 2-8wt% of the low temperature dyeable modified copolyester.
Preferably, the polyester polyol in the step (1.2) comprises one or more of polyethylene glycol adipate, polypropylene glycol adipate and polybutylene adipate, and the amount of the polyester polyol is 1-5wt% of the low-temperature dyeable modified copolyester.
The dyeability is influenced by the amount of polyester polyol used.
Preferably, the precondensation in step (1.2) is carried out at 255-265 ℃ and 50-150Pa for 40-60 min; the final polycondensation is carried out at 265 ℃ and 275 ℃ and at 100Pa and 120Pa for 1.5-2.5 h.
Preferably, the pre-crystallization in the step (2) is carried out at the temperature of 120-140 ℃ for 25-30min, and the water content after drying is less than or equal to 30 ppm.
Preferably, a cross-shaped section spinneret plate is adopted during spinning in the step (2), the box temperature of the sea part is 265-272 ℃, and the box temperature of the island part is 275-285 ℃; the winding speed during winding is 4000-4500 m/min.
Preferably, the mass ratio of the sea part alkali-soluble polyester to the island part low-temperature dyeable modified copolyester in the step (2) is 15-35: 85-65.
Preferably, the alkali solution treatment in step (3) is carried out by using 1-4wt% NaOH solution at 115-130 deg.C for 30-60 min.
Therefore, the invention has the following beneficial effects: the addition of the dihydric alcohol and the polyester polyol destroys the regularity of the original PET molecular chain, increases the amorphous region of the polyester, enables dye molecules to enter more easily, improves the dyeability, and can improve the water absorption performance of the polyester fiber while not influencing the stability of the polyester.
Detailed Description
The invention is further described with reference to specific embodiments.
General example:
a preparation method of a disperse dye normal-pressure low-temperature easy-to-dye superfine fiber comprises the following preparation methods:
(1) preparing low-temperature easy-dyeing modified copolyester:
(1.1) mixing terephthalic acid, ethylene glycol and a titanium catalyst, and carrying out an esterification reaction for 1.5-2.5h at the temperature of 225 ℃ and 235 ℃ and under the pressure of 0.1-0.3Mpa, wherein the esterification rate is controlled to be more than 85 percent, so as to obtain an esterified substance; the addition of the titanium catalyst is 5ppm based on the theoretical polyester generation amount of Ti atom mass;
(1.2) adding dihydric alcohol and polyester polyol into the esterified substance, then reacting for 40-60min at the temperature of 255-265 ℃ and the pressure of 50-150pa for pre-polycondensation, reacting for 1.5-2.5h at the temperature of 265-275 ℃ and the pressure of 100-120pa for final polycondensation, discharging, and preparing the low-temperature dyeable modified copolyester; the alcohol-acid ratio of the ethylene glycol to the dihydric alcohol to the terephthalic acid is 1.2-1.6; the dihydric alcohol comprises one or more of 1, 2-propylene glycol, 1, 2-butanediol, 1, 3-butanediol and 2-methyl-1, 3-propanediol, and the dosage of the dihydric alcohol is 2-8wt% of the low-temperature dyeable modified copolyester; the polyester polyol comprises one or more of polyethylene glycol adipate, polypropylene glycol adipate and polybutylene glycol adipate, and the dosage of the polyester polyol is 1-5wt% of the low-temperature dyeable modified copolyester;
(2) sea-island composite spinning: performing heat preservation on alkali-soluble polyester and low-temperature easy-dyeing modified copolyester at the temperature of 120-140 ℃ for 25-30min for pre-crystallization, drying until the water content is less than or equal to 30ppm, then using the alkali-soluble polyester as a sea part and the low-temperature easy-dyeing modified copolyester as an island part, spinning by using a cross-shaped cross-section spinneret plate, wherein the box temperature of the sea part is 265-fold 272 ℃, the box temperature of the sea part is 275-fold 285 ℃, then performing ring cooling heating, side blowing and oiling, and winding at the speed of 4000-fold 4500m/min to obtain the sea-island composite fiber; wherein the mass ratio of the sea part alkali-soluble polyester to the island part low-temperature easy-dyeing modified copolyester is 15-35: 85-65;
(3) alkali dissolution treatment: treating the sea-island composite fiber with 1-4wt% NaOH solution at 115-130 ℃ for 30-60min to remove sea part, and preparing the disperse dye normal-pressure low-temperature dyeable superfine fiber;
the titanium catalyst comprises the following preparation steps:
s1: mixing the pseudo-boehmite slurry with 10-15 wt% of nitric acid solution, and adjusting the pH to 2-4 to obtain pseudo-boehmite sol with the solid content of 30-45%;
s2: mixing pseudo-boehmite sol and 8-10 wt% of p-azidobenzoic acid aqueous solution according to the mass ratio of 1:5-10, standing for adsorption for 2-5h, drying, and performing ion adsorption at 1000 ℃ and 5000mW/cm2After being irradiated for 15-30min under ultraviolet light, the alumina carrier is prepared by calcining for 4-6h at the temperature of 700-850 ℃ and grinding;
s3: soaking an alumina carrier to absorb water, and drying the surface of the alumina carrier to obtain a water-carrying alumina carrier with water carrying capacity of 1-1.5 wt%;
s4: placing tetrabutyl titanate, 2-hydroxycarboxylic acid compounds and phosphorus-containing compounds in isopropanol in a mol ratio of 1:1-10:1-10 to obtain an organic mixed solution;
s5: and (3) putting the water-carrying alumina carrier into the mixed solution, reacting for 1-3h at 50-80 ℃, and separating to prepare the titanium catalyst.
Example 1:
a preparation method of a disperse dye normal-pressure low-temperature easy-to-dye superfine fiber comprises the following preparation methods:
(1) preparing low-temperature easy-dyeing modified copolyester:
(1.1) mixing terephthalic acid, ethylene glycol and a commercial titanium polyester catalyst, and carrying out esterification reaction for 2 hours at 230 ℃ and under the pressure of 0.2Mpa, wherein the esterification rate is controlled to be more than 85 percent, so as to obtain an esterified substance; the addition of the titanium catalyst is 5ppm based on the theoretical polyester generation amount of Ti atom mass;
(1.2) adding 4wt% of 2-methyl-1, 3-propylene glycol and 2 wt% of polyethylene glycol adipate (PEA-2000) of the low-temperature dyeable modified copolyester into an esterified substance, then reacting for 50min at 260 ℃ and 100pa pressure for pre-polycondensation, reacting for 2h at 270 ℃ and 110pa pressure for final polycondensation, discharging, and preparing the low-temperature dyeable modified copolyester; wherein the alcohol-acid ratio of the ethylene glycol to the dihydric alcohol to the terephthalic acid is 1.4;
(2) sea-island composite spinning: carrying out heat preservation on alkali-soluble polyester and low-temperature easy-dyeing modified copolyester at 130 ℃ for 30min for pre-crystallization, drying until the water content is less than or equal to 30ppm, then taking the alkali-soluble polyester as a sea part and the low-temperature easy-dyeing modified copolyester as an island part, spinning by adopting a cross-shaped section spinneret plate, wherein the box temperature of the sea part is 270 ℃, the box temperature of the island part is 280 ℃, then carrying out ring cooling heating, cross air blowing and oiling, and then winding at 4200m/min to prepare the sea-island composite fiber; wherein the mass ratio of the sea part alkali-soluble polyester to the island part low-temperature easy-dyeing modified copolyester is 30: 70;
(3) alkali dissolution treatment: the sea-island composite fiber is treated by 2 wt% NaOH solution at 120 ℃ for 40min to remove sea parts, and the disperse dye normal-pressure low-temperature easy-to-dye superfine fiber is prepared.
Example 2:
a preparation method of a disperse dye normal-pressure low-temperature easy-to-dye superfine fiber comprises the following preparation methods:
(1) preparing low-temperature easy-dyeing modified copolyester:
(1.1) mixing terephthalic acid, ethylene glycol and a commercial titanium polyester catalyst, and carrying out esterification reaction for 1.5h at 235 ℃ and 0.3Mpa, wherein the esterification rate is controlled to be more than 85%, so as to obtain an esterified substance; the addition of the titanium catalyst is 5ppm based on the theoretical polyester generation amount of Ti atom mass;
(1.2) adding 4wt% of 2-methyl-1, 3-propylene glycol and 2 wt% of polyethylene glycol adipate (PEA-2000) of the low-temperature dyeable modified copolyester into an esterified substance, then reacting for 40min at 265 ℃ and 150pa pressure for pre-polycondensation, reacting for 1.5h at 275 ℃ and 120pa pressure for final polycondensation, discharging, and preparing the low-temperature dyeable modified copolyester; the alcohol-acid ratio of the ethylene glycol to the dihydric alcohol to the terephthalic acid is 1.4;
(2) sea-island composite spinning: carrying out heat preservation on alkali-soluble polyester and low-temperature easy-dyeing modified copolyester at 140 ℃ for 30min for pre-crystallization, drying until the water content is less than or equal to 30ppm, then taking the alkali-soluble polyester as a sea part and the low-temperature easy-dyeing modified copolyester as an island part, spinning by adopting a cross-shaped section spinneret plate, wherein the box body temperature of the sea part is 272 ℃, the box body temperature of the sea part is 285 ℃, then carrying out ring cooling heating, cross air blowing and oiling, and winding at 4500m/min to obtain the sea-island composite fiber; wherein the mass ratio of the sea part alkali-soluble polyester to the island part low-temperature easy-dyeing modified copolyester is 20: 80;
(3) alkali dissolution treatment: the sea-island composite fiber is treated by 4wt% NaOH solution at 130 ℃ for 30min to remove sea part, and the disperse dye normal-pressure low-temperature easy-to-dye superfine fiber is prepared.
Example 3:
a preparation method of a disperse dye normal-pressure low-temperature easy-to-dye superfine fiber comprises the following preparation methods:
(1) preparing low-temperature easy-dyeing modified copolyester:
(1.1) mixing terephthalic acid, ethylene glycol and a commercial titanium polyester catalyst, and carrying out esterification reaction for 1.5h at 225 ℃ and under the pressure of 0.1Mpa, wherein the esterification rate is controlled to be more than 85%, so as to obtain an esterified substance; the addition of the titanium catalyst is 5ppm based on the theoretical polyester generation amount of Ti atom mass;
(1.2) adding 2 wt% of 2-methyl-1, 3-propylene glycol and 5wt% of polyethylene glycol adipate (PEA-2000) of the low-temperature dyeable modified copolyester into an esterified substance, then reacting for 60min at 255 ℃ and 50pa pressure for pre-polycondensation, reacting for 2.5h at 265 ℃ and 100pa pressure for final polycondensation, discharging, and preparing the low-temperature dyeable modified copolyester; the alcohol-acid ratio of the ethylene glycol to the dihydric alcohol to the terephthalic acid is 1.4;
(2) sea-island composite spinning: carrying out heat preservation on alkali-soluble polyester and low-temperature easy-dyeing modified copolyester at 120 ℃ for 30min for pre-crystallization, drying until the water content is less than or equal to 30ppm, then taking the alkali-soluble polyester as a sea part and the low-temperature easy-dyeing modified copolyester as an island part, spinning by adopting a cross-shaped section spinneret plate, wherein the box temperature of the sea part is 265 ℃, the box temperature of the sea part is 275 ℃, then carrying out ring cooling heating, cross air blowing and oiling, and winding at 4000m/min to obtain the sea-island composite fiber; wherein the mass ratio of the sea part alkali-soluble polyester to the island part low-temperature easy-dyeing modified copolyester is 15: 85;
(3) alkali dissolution treatment: the sea-island composite fiber is treated by 1 wt% NaOH solution at 115 ℃ for 60min to remove sea parts, and the disperse dye normal-pressure low-temperature easy-to-dye superfine fiber is prepared.
Example 4:
a preparation method of a disperse dye normal-pressure low-temperature easy-to-dye superfine fiber comprises the following preparation methods:
(1) preparing low-temperature easy-dyeing modified copolyester:
(1.1) mixing terephthalic acid, ethylene glycol and a commercial titanium polyester catalyst, and carrying out esterification reaction for 2 hours at 230 ℃ and under the pressure of 0.2Mpa, wherein the esterification rate is controlled to be more than 85 percent, so as to obtain an esterified substance; the addition of the titanium catalyst is 5ppm based on the theoretical polyester generation amount of Ti atom mass;
(1.2) adding 8wt% of 1, 3-butanediol and 1 wt% of polyethylene glycol adipate (PEA-2000) of the low-temperature dyeable modified copolyester into an esterified substance, then reacting for 50min at 260 ℃ and 100pa pressure for pre-polycondensation, reacting for 2h at 270 ℃ and 110pa pressure for final polycondensation, discharging, and preparing the low-temperature dyeable modified copolyester; wherein the alcohol-acid ratio of the ethylene glycol to the dihydric alcohol to the terephthalic acid is 1.4;
(2) sea-island composite spinning: carrying out heat preservation on alkali-soluble polyester and low-temperature easy-dyeing modified copolyester at 130 ℃ for 30min for pre-crystallization, drying until the water content is less than or equal to 30ppm, then taking the alkali-soluble polyester as a sea part and the low-temperature easy-dyeing modified copolyester as an island part, spinning by adopting a cross-shaped section spinneret plate, wherein the box temperature of the sea part is 270 ℃, the box temperature of the island part is 280 ℃, then carrying out ring cooling heating, cross air blowing and oiling, and then winding at 4200m/min to prepare the sea-island composite fiber; wherein the mass ratio of the sea part alkali-soluble polyester to the island part low-temperature easy-dyeing modified copolyester is 30: 70;
(3) alkali dissolution treatment: the sea-island composite fiber is treated by 2 wt% NaOH solution at 120 ℃ for 40min to remove sea parts, and the disperse dye normal-pressure low-temperature easy-to-dye superfine fiber is prepared.
Comparative example 1: the preparation of the low-temperature dyeable modified copolyester is the same as that in example 1, and then the low-temperature dyeable modified copolyester melt passes through a spinning manifold to obtain a pre-oriented monofilament, and the pre-oriented monofilament is subjected to texturing to obtain the normal-pressure low-temperature dyeable stretch textured fiber.
Comparative example 2:
a preparation method of a disperse dye normal-pressure low-temperature easy-to-dye superfine fiber comprises the following preparation methods:
(1) preparing low-temperature easy-dyeing modified copolyester:
(1.1) mixing terephthalic acid, ethylene glycol and a titanium catalyst, and carrying out esterification reaction for 2 hours at 230 ℃ and under the pressure of 0.2Mpa, wherein the esterification rate is controlled to be more than 85 percent, so as to obtain an esterified substance; the addition of the titanium catalyst is 5ppm based on the theoretical polyester generation amount of Ti atom mass; (1.2) reacting the esterified product at 260 ℃ and 100pa for 50min for pre-polycondensation, reacting at 270 ℃ and 110pa for 2h for final polycondensation, discharging, and preparing the low-temperature dyeable modified copolyester; wherein the alcohol-acid ratio of ethylene glycol to terephthalic acid is 1.4;
(2) sea-island composite spinning: carrying out heat preservation on alkali-soluble polyester and low-temperature easy-dyeing modified copolyester at 130 ℃ for 30min for pre-crystallization, drying until the water content is less than or equal to 30ppm, then taking the alkali-soluble polyester as a sea part and the low-temperature easy-dyeing modified copolyester as an island part, spinning by adopting a cross-shaped section spinneret plate, wherein the box temperature of the sea part is 270 ℃, the box temperature of the island part is 280 ℃, then carrying out ring cooling heating, cross air blowing and oiling, and then winding at 4200m/min to prepare the sea-island composite fiber; wherein the mass ratio of the sea part alkali-soluble polyester to the island part low-temperature easy-dyeing modified copolyester is 30: 70;
(3) alkali dissolution treatment: the sea-island composite fiber is treated by 2 wt% NaOH solution at 120 ℃ for 40min to remove sea parts, and the disperse dye normal-pressure low-temperature easy-to-dye superfine fiber is prepared.
3g of the disperse dyes prepared in examples and comparative examples, which were easily dyeable into ultrafine fibers at normal pressure and low temperature, were dyed with disperse blue dye, and the results are shown in the following table.
As can be seen from the above table, the sea part in the superfine fiber in the embodiment of the invention has been completely dissolved, and the dye uptake is high; as can be seen from comparative example 1, the superfine fiber prepared by the sea-island composite spinning of the present invention has a higher dye uptake; as can be seen from comparative example 2, the dye uptake of the ultrafine fibers of the present invention is significantly higher than that of the conventional polyester by the modification of the diol and the polyester polyol.
Example 5: the difference from example 1 is that a self-made titanium catalyst is used, which comprises the following preparation steps:
s1: mixing the pseudo-boehmite slurry with 12 wt% nitric acid solution, and adjusting the pH to 3 to obtain pseudo-boehmite sol with the solid content of 40%;
s2: mixing pseudo-boehmite sol and 9 wt% of p-azidobenzoic acid aqueous solution according to the mass ratio of 1:7, standing for adsorption for 3h, drying, and performing concentration at 3000mW/cm2The alumina carrier is obtained by calcining for 5 hours at 800 ℃ and grinding after the ultraviolet light is irradiated for 20 minutes;
s3: soaking and absorbing water on an alumina carrier, and drying the surface of the alumina carrier to obtain a water-carrying alumina carrier with water carrying capacity of 1.2 wt%;
s4: placing tetrabutyl titanate, citric acid and triethyl phosphate into isopropanol in a mol ratio of 1:5:5 to obtain an organic mixed solution;
s5: and (3) putting the water-carrying alumina carrier into the mixed solution, reacting for 2h at the temperature of 60 ℃, and separating to prepare the titanium catalyst.
Example 6: the difference from example 1 is that a self-made titanium catalyst is used, which comprises the following preparation steps:
s1: mixing the pseudo-boehmite slurry with 10 wt% nitric acid solution, and adjusting the pH to 2 to obtain pseudo-boehmite sol with the solid content of 30%;
s2: mixing pseudo-boehmite sol and 8wt% of p-azidobenzoic acid aqueous solution according to the mass ratio of 1:10, standing for adsorption for 2h, drying, and performing concentration at 1000mW/cm2The alumina carrier is obtained by calcining for 6 hours at 700 ℃ after being irradiated for 30 minutes by ultraviolet light and grinding;
s3: soaking and absorbing water on an alumina carrier, and drying the surface of the alumina carrier to obtain a water-carrying alumina carrier with water carrying capacity of 1 wt%;
s4: placing tetrabutyl titanate, citric acid and triethyl phosphate into isopropanol in a mol ratio of 1:5:5 to obtain an organic mixed solution;
s5: and (3) putting the water-carrying alumina carrier into the mixed solution, reacting for 3 hours at 50 ℃, and separating to prepare the titanium catalyst.
Example 7: the difference from example 1 is that a self-made titanium catalyst is used, which comprises the following preparation steps:
s1: mixing the pseudo-boehmite slurry with 15 wt% nitric acid solution, and adjusting the pH to 4 to obtain pseudo-boehmite sol with the solid content of 45%;
s2: mixing pseudo-boehmite sol and 10 wt% of p-azidobenzoic acid aqueous solution according to the mass ratio of 1:5, standing for adsorption for 5 hours, drying, and performing concentration at 5000mW/cm2The alumina carrier is obtained by calcining for 4 hours at 850 ℃ and grinding after being irradiated for 15 minutes by ultraviolet light;
s3: soaking an alumina carrier to absorb water, and then drying the surface of the alumina carrier to obtain a water-carrying alumina carrier with water carrying capacity of 1.5 wt%;
s4: placing tetrabutyl titanate, citric acid and triethyl phosphate into isopropanol in a mol ratio of 1:5:5 to obtain an organic mixed solution;
s5: and (3) putting the water-carrying alumina carrier into the mixed solution, reacting for 1h at the temperature of 80 ℃, and separating to prepare the titanium catalyst.
Comparative example 3: the difference from example 1 is that a self-made titanium catalyst is used, which comprises the following preparation steps:
s1: mixing the pseudo-boehmite slurry with 12 wt% nitric acid solution, and adjusting the pH to 3 to obtain pseudo-boehmite sol with the solid content of 40%;
s2: mixing pseudo-boehmite sol and 7 wt% of p-azidobenzoic acid aqueous solution according to the mass ratio of 1:4, standing for adsorption for 3h, drying, and performing concentration at 3000mW/cm2The alumina carrier is obtained by calcining for 5 hours at 800 ℃ and grinding after the ultraviolet light is irradiated for 20 minutes;
s3: soaking and absorbing water on an alumina carrier, and drying the surface of the alumina carrier to obtain a water-carrying alumina carrier with water carrying capacity of 1.2 wt%;
s4: placing tetrabutyl titanate, citric acid and triethyl phosphate into isopropanol in a mol ratio of 1:5:5 to obtain an organic mixed solution;
s5: and (3) putting the water-carrying alumina carrier into the mixed solution, reacting for 2h at the temperature of 60 ℃, and separating to prepare the titanium catalyst.
Comparative example 4: the difference from example 1 is that a self-made titanium catalyst is used, which comprises the following preparation steps:
s1: mixing the pseudo-boehmite slurry with 12 wt% nitric acid solution, and adjusting the pH to 3 to obtain pseudo-boehmite sol with the solid content of 40%;
s2: mixing pseudo-boehmite sol and 11 wt% of p-azidobenzoic acid aqueous solution according to the mass ratio of 1:12, standing for adsorption for 3h, drying, and performing concentration at 3000mW/cm2The alumina carrier is obtained by calcining for 5 hours at 800 ℃ and grinding after the ultraviolet light is irradiated for 20 minutes;
s3: soaking and absorbing water on an alumina carrier, and drying the surface of the alumina carrier to obtain a water-carrying alumina carrier with water carrying capacity of 1.2 wt%;
s4: placing tetrabutyl titanate, citric acid and triethyl phosphate into isopropanol in a mol ratio of 1:5:5 to obtain an organic mixed solution;
s5: and (3) putting the water-carrying alumina carrier into the mixed solution, reacting for 2h at the temperature of 60 ℃, and separating to prepare the titanium catalyst.
Physical indexes of the disperse dyes obtained in the preparation of the fibers of the examples and the comparative examples 3 to 4, which are easy to be dyed at normal pressure and low temperature, were measured, and the results are shown below.
| Item | Dye uptake (%) | Elongation (%) | Percentage of full lap (%) |
| Example 1 | 3.12 | 24.86 | 92.7 |
| Example 2 | 3.23 | 25.03 | 93.1 |
| Example 3 | 3.29 | 24.91 | 92.9 |
| Example 4 | 3.15 | 24.54 | 93.0 |
| Example 5 | 3.56 | 27.61 | 95.2 |
| Example 6 | 3.74 | 28.90 | 95.8 |
| Example 7 | 3.62 | 27.31 | 96.1 |
| Comparative example 3 | 2.89 | 22.01 | 90.1 |
| Comparative example 4 | 3.13 | 24.67 | 89.7 |
From the above table, the physical indexes of the disperse dye prepared in the embodiments 1-4 of the present invention at normal pressure and low temperature can meet the application requirements, and the titanium catalyst prepared by the present invention can further improve the polyester spinning performance, and the comparative example 1 shows that the addition of azidobenzoic acid is too little, which results in too few holes and too little titanium dioxide loading in the catalyst, which results in low catalytic activity and poor polyester spinning performance; as can be seen from the comparative example 1, the addition of the azidobenzoic acid is too much, which easily causes the diameter of the pores to be too large, and causes the water in the water-carrying porous carrier to easily overflow in the organic mixed solution, so that the tetrabutyl titanate is hydrolyzed outside the pore channels, and partial titanium dioxide is loaded outside the pore channels, and the catalytic control effect cannot be achieved.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of a disperse dye normal-pressure low-temperature easy-to-dye superfine fiber is characterized by comprising the following preparation methods:
(1) preparing low-temperature easy-dyeing modified copolyester:
(1.1) mixing terephthalic acid, ethylene glycol and a catalyst for esterification reaction to obtain an esterified substance;
(1.2) adding dihydric alcohol and polyester polyol into an esterified substance, then carrying out pre-polycondensation and final polycondensation, and discharging to prepare low-temperature easy-dyeing modified copolyester;
(2) sea-island composite spinning: carrying out pre-crystallization and drying on alkali-soluble polyester and low-temperature dyeable modified copolyester, then taking the alkali-soluble polyester as a sea part and the low-temperature dyeable modified copolyester as an island part, and spinning and winding to prepare the sea-island composite fiber;
(3) alkali dissolution treatment: the sea-island composite fiber is treated by alkali solution to remove sea part, and the disperse dye normal-pressure low-temperature easy-to-dye superfine fiber is prepared.
2. The method for preparing the atmospheric pressure low temperature dyeable superfine fiber by using the disperse dye according to claim 1, wherein the alcohol-acid ratio of the glycol to the diol to the terephthalic acid in the step (1) is 1.2-1.6.
3. The method for preparing an atmospheric-pressure low-temperature dyeable superfine fiber by using a disperse dye as claimed in claim 1, wherein the esterification reaction in the step (1.1) is carried out at 225-235 ℃ and 0.1-0.3MPa for 1.5-2.5h, and the esterification rate is controlled to be more than 85%.
4. The method for preparing atmospheric pressure low temperature dyeable superfine fiber by using disperse dye according to claim 1, wherein the diol in step (1.2) comprises one or more of 1, 2-propanediol, 1, 2-butanediol, 1, 3-butanediol and 2-methyl-1, 3-propanediol, and the amount of the diol is 2-8wt% of the low temperature dyeable modified copolyester.
5. The method for preparing atmospheric pressure low temperature dyeable superfine fiber by disperse dye according to claim 1, wherein the polyester polyol in the step (1.2) comprises one or more of polyethylene glycol adipate, polypropylene glycol adipate and polybutylene adipate, and the amount of the polyester polyol is 1-5wt% of the low temperature dyeable modified copolyester.
6. The method for preparing an atmospheric-pressure low-temperature dyeable superfine fiber with disperse dye according to claim 1, wherein the pre-polycondensation in the step (1.2) is carried out at 255-265 ℃ and 50-150pa for 40-60 min; the final polycondensation is carried out at 265 ℃ and 275 ℃ and at 100Pa and 120Pa for 1.5-2.5 h.
7. The method for preparing the disperse dye atmospheric pressure low temperature dyeable superfine fiber according to claim 1, wherein the pre-crystallization in the step (2) is performed by keeping the temperature at 120-140 ℃ for 25-30min, and the water content after drying is less than or equal to 30 ppm.
8. The method for preparing the disperse dye normal-pressure low-temperature easy-dyeing superfine fiber according to claim 1, wherein a cross-shaped section spinneret plate is adopted during spinning in the step (2), the box temperature of the sea part is 265-272 ℃, and the box temperature of the island part is 275-285 ℃; the winding speed during winding is 4000-4500 m/min.
9. The method for preparing the disperse dye atmospheric pressure low temperature dyeable superfine fiber according to claim 1, wherein the mass ratio of the sea part alkali soluble polyester to the island part low temperature dyeable modified copolyester in the step (2) is 15-35: 85-65.
10. The method for preparing an atmospheric-pressure low-temperature dyeable superfine fiber by using a disperse dye as claimed in claim 1, wherein the alkali solution treatment in the step (3) is performed by using a 1-4wt% NaOH solution at 130 ℃ for 30-60 min.
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