CN112724390A - Antimony-free polyester melt preparation system and method for preparing antimony-free polyester fine denier FDY fiber - Google Patents
Antimony-free polyester melt preparation system and method for preparing antimony-free polyester fine denier FDY fiber Download PDFInfo
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- 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
- C08G63/785—Preparation processes characterised by the apparatus used
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- 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
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G63/82—Preparation processes characterised by the catalyst used
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
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- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/04—Melting filament-forming substances
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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Abstract
The invention discloses a system for preparing antimony-free polyester melt and a method for preparing antimony-free polyester fine denier FDY fiber, wherein the method comprises the following steps: (1) adding terephthalic acid, ethylene glycol and dihydric alcohol containing branched chains into a first esterification kettle to carry out primary esterification reaction; (2) conveying the primary esterification reaction product to a second esterification kettle, adding a coloring agent and a titanium catalyst, and carrying out secondary esterification reaction; (3) refluxing part of the secondary esterification reaction product to the first esterification kettle, and conveying the rest of the secondary esterification reaction product to the prepolymerization kettle for reaction to obtain a prepolycondensation product; (4) conveying the pre-polycondensation product to a final polymerization kettle for reaction to obtain a polyester melt; (5) and (3) directly spinning the polyester melt obtained from the final polymerization kettle through a melt to obtain the antimony-free polyester fine denier FDY fiber. The invention promotes the esterification rate and the esterification rate in the direct spinning process of the melt of the antimony-free polyester filament by improving the spinning process equipment and the molecular structure of the polyester, improves the fluidity of the melt and improves the quality of the prepared antimony-free polyester filament.
Description
Technical Field
The invention relates to the technical field of chemical fiber preparation, in particular to a preparation system of antimony-free polyester melt and a method for preparing antimony-free polyester fine denier FDY fiber.
Background
In 2019, the total yield of Chinese chemical fibers exceeds 7000 million tons, which accounts for over 70% of the whole world, wherein the yield of polyester accounts for about 80% of the total yield of the chemical fibers. The polyester is mainly polyethylene terephthalate (PET), also called terylene, and the clothes made of the polyester have good stiffness, difficult deformation, quick washing and easy drying, and are applied to many fields. The catalyst used for preparing PET by polycondensation reaction is mainly antimony-containing catalyst. The antimony catalyst is reduced into metallic antimony in the reaction, so that the polyester is grey; and antimony is a heavy metal, and is easily leached out in the dyeing process, so that a water source is polluted, and therefore PET is possibly harmful to the ecological environment in the using and recycling processes, and has chronic toxicity and carcinogenicity to a human body. The titanium catalyst is the most likely to replace antimony catalyst due to its high catalytic activity, relatively moderate cost, environmental friendliness and no harm to human body.
In the prior patent publications, there are many related patents for preparing titanium catalysts for polyester polycondensation and technologies for preparing polyester chips and polyester staple fibers by using titanium catalysts, for example, the patent publication of China discloses "an antimony-free environment-friendly flame-retardant polyester chip and a preparation method thereof", and the publication number is CN 106700042A. the polyester chip in the invention is prepared by polymerization reaction of ethylene glycol, purified terephthalic acid, a flame retardant, a dye and a titanium catalyst, and the intrinsic viscosity is 0.55-0.75 dL/g, so that the fiber-grade polyester chip with flame retardant property and without releasing heavy metal antimony harmful to the environment in the use process is obtained.
However, due to the excessively high activity of the titanium catalyst, more side reactions are easily caused in the melt conveying process, so that molecular chains are broken, the viscosity of the obtained spinning melt is not ideal, and the phenomena of slow spinning speed, broken ends, filament floating and the like are easily caused; and the titanium catalyst is used for catalyzing polyester esterification, so that the melt uniformity is poor, meanwhile, the melt is poor in heat resistance and easy to degrade, the viscosity is reduced greatly, and the spinning speed is low, so that the natural yarn breakage quantity is high during production of FDY (fully drawn yarn) yarns, and therefore, the antimony-free polyester filament yarn melt direct spinning is difficult to perform by adopting the titanium catalyst at present.
Disclosure of Invention
The invention aims to overcome the defects that in the prior art, due to the overhigh activity of a titanium catalyst, more side reactions are easily caused in the melt conveying process, molecular chains are broken, the viscosity of the obtained spinning melt is not ideal, and the phenomena of slow spinning speed, broken ends, filament floating and the like are easily caused; the titanium catalyst is used for catalyzing the polyester esterification speed to be slow, so that the melt is poor in uniformity, the melt is poor in heat resistance and easy to degrade, the viscosity is reduced greatly, the natural yarn breakage quantity is high during production of FDY (fully drawn yarn) yarns due to low spinning speed, and therefore the problem that antimony-free polyester filament yarn melt direct spinning is difficult to carry out by adopting the titanium catalyst is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation system of antimony-free polyester melt comprises a first esterification kettle, a second esterification kettle, a prepolymerization kettle and a final polymerization kettle which are sequentially connected, and a catalyst feeding unit and a coloring agent feeding unit which are respectively connected with the second esterification kettle; the second esterification kettle comprises an esterification I chamber, an esterification II chamber and an esterification III chamber which are sequentially communicated, the esterification I chamber is communicated with the first esterification kettle, the esterification II chamber is communicated with a colorant feeding unit, and the esterification III chamber is respectively communicated with the first esterification kettle, a prepolymerization kettle and a catalyst feeding unit.
Preferably, the colorant feed unit comprises a colorant preparation tank and a colorant supply tank connected, the colorant supply tank being in communication with the esterification II compartment of the second esterification vessel; the catalyst feeding unit comprises a catalyst preparation tank and a catalyst feeding tank which are connected, and the catalyst feeding tank is communicated with the esterification III chamber of the second esterification kettle.
The invention also provides a method for preparing the antimony-free polyester fine-denier FDY fiber by using the system to carry out melt direct spinning, which comprises the following steps:
(1) adding terephthalic acid, ethylene glycol and dihydric alcohol containing branched chains into a first esterification kettle to carry out primary esterification reaction;
(2) conveying the primary esterification reaction product to an esterification I chamber in a second esterification kettle, sequentially flowing through an esterification II chamber and an esterification III chamber, adding a colorant into the esterification II chamber, and adding a titanium catalyst into the esterification III chamber to perform secondary esterification reaction;
(3) partially refluxing a secondary esterification reaction product in the esterification III chamber to the first esterification kettle to participate in a primary esterification reaction; conveying the rest to a prepolymerization kettle for prepolymerization reaction to obtain a prepolycondensation product;
(4) conveying the pre-polycondensation product to a final polymerization kettle for final polycondensation reaction to obtain a titanium-based polyester melt;
(5) and (3) directly spinning the polyester melt obtained from the final polymerization kettle through a melt to obtain the antimony-free polyester fine denier FDY fiber.
The invention firstly improves the process, introduces partial catalyst into the first esterification kettle from the esterification III chamber of the second esterification kettle, plays the role of esterification catalysis, promotes the esterification rate and improves the esterification rate. In addition, the titanium catalyst is added into the esterification III chamber of the second esterification kettle, so that the hydrolysis of the catalyst can be effectively avoided, and the catalyst entering the polycondensation kettle can be ensured to keep higher activity.
In addition, the invention starts from the molecular structure design, and introduces dihydric alcohol containing branched chain into the polyester, so that the melt fluidity is improved, the melting point is reduced, the crystallization speed and the processing temperature are reduced, the degradation rate is reduced, the viscosity drop is reduced, the spinning speed can be improved, the degree of tiny particles such as coloring agent entering the interior is facilitated, and the dyeing rate is improved; and the introduction of the dihydric alcohol chain segment containing the branched chain does not greatly damage the structural regularity of the antimony-free polyester fiber, maintains the excellent performance of the polyester fiber, and the prepared antimony-free polyester fine denier FDY fiber has excellent dyeing performance and mechanical performance.
Preferably, the mass ratio of the terephthalic acid to the ethylene glycol in the step (1) is 1: 0.43-0.52; the dihydric alcohol containing the branched chain is one or more selected from 2-amyl-1, 3-propylene glycol, 2-amyl-1, 4-butanediol and 2-amyl-1, 5-pentanediol, and the adding amount of the dihydric alcohol containing the branched chain accounts for 40-80 ppm of the weight of the polyester.
Preferably, the pressure of the primary esterification reaction in the step (1) is 100 to 400KPa, the temperature is 245 to 250 ℃, and the time is 60 to 90 min.
Preferably, the temperature of the secondary esterification reaction in the step (2) is 250-260 ℃, and the time is 30-60 min; the addition amount of the titanium catalyst is 4-15 ppm.
Preferably, the secondary esterification reaction product refluxed into the first esterification kettle in the step (3) accounts for 1-3% of the mass of the secondary esterification reaction product in the esterification III chamber.
Preferably, the pressure of the pre-polycondensation reaction in the step (3) is 150-500 Pa, the temperature is 260-270 ℃, and the time is 50-70 min.
Preferably, the pressure of the final polycondensation reaction in the step (4) is 150-200 Pa, the temperature is 270-275 ℃, and the time is 30-120 min.
Preferably, the melt direct spinning process parameters in the step (5) are as follows:
temperature of spinning beam: 280-290 ℃;
cooling air temperature: 20-25 ℃;
oiling rate of oiling: 0.42 to 1.5 wt%;
speed of winding: 4000-4600 m/min.
Therefore, the invention has the following beneficial effects:
(1) introducing part of catalyst into the first esterification kettle from an esterification III chamber of the second esterification kettle to play a role of esterification catalysis, promote the esterification rate and improve the esterification rate;
(2) the titanium catalyst is added into the esterification III chamber of the second esterification kettle, so that the catalyst can be effectively prevented from being hydrolyzed, and the catalyst entering the polycondensation kettle can be ensured to keep higher activity;
(3) the dihydric alcohol containing the branched chain is added in the polymerization process to improve the fluidity and the strength of the melt, so that the spinning speed can be improved, the degree of tiny particles such as a coloring agent entering the inside is facilitated, and the coloring rate is improved;
(4) the introduction of the dihydric alcohol chain segment containing the branched chain does not greatly damage the structural regularity of the antimony-free polyester fiber, maintains the excellent performance of the polyester fiber, and the prepared antimony-free polyester fine denier FDY fiber has excellent dyeing property and mechanical property;
(5) no heavy metal is added, and the prepared polyester has the advantages of high efficiency, environmental protection, cost saving and the like.
Drawings
FIG. 1 is a schematic view of the connection structure of the antimony-free polyester melt production system of the present invention.
In the figure: 1 first esterification kettle, 2 second esterification kettle, 201 esterification I room, 202 esterification II room, 203 esterification III room, 3 prepolymerization kettle, 4 final polymerization kettle, 501 colorant preparation tank, 502 colorant supply tank, 601 catalyst preparation tank, 602 catalyst supply tank.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
As shown in FIG. 1, an antimony-free polyester melt production system used in the present invention comprises a first esterification tank 1, a second esterification tank 2, a prepolymerization tank 3 and a finisher tank 4, which are connected in this order, and a catalyst feeding unit and a colorant feeding unit, which are connected to the second esterification tank, respectively. The colorant dosing unit includes a colorant formulation tank 501 and a colorant supply tank 502 connected together, and the catalyst dosing unit includes a catalyst formulation tank 601 and a catalyst supply tank 602 connected together.
The second esterify including the I room 201, the II room 202 and the III room 203 of esterifying that communicate in proper order in the cauldron, esterify I room and first esterify the cauldron and pass through the pipeline intercommunication, esterify II room and colorant feed tank and pass through the pipeline intercommunication, esterify III room and first esterify cauldron, prepolymerization cauldron and catalyst feed tank respectively and pass through the pipeline intercommunication.
When the system operates, monomers for producing polyester are mixed in a first esterification kettle to carry out primary esterification reaction; then conveying the primary esterification reaction product to an esterification I chamber in a second esterification kettle, sequentially flowing through an esterification II chamber and an esterification III chamber, and respectively adding the colorant and the catalyst which are prepared in advance in a colorant preparing tank and a catalyst preparing tank into the esterification II chamber and the esterification III chamber through a colorant feeding tank and a catalyst feeding tank to perform secondary esterification reaction; then partially refluxing the secondary esterification reaction product in the esterification III chamber to the first esterification kettle to participate in the primary esterification reaction; conveying the rest to a prepolymerization kettle for prepolymerization reaction to obtain a prepolycondensation product; and finally, conveying the pre-polycondensation product to a final polymerization kettle for final polycondensation reaction to obtain a polyester melt, and performing subsequent melt direct spinning.
Example 1:
a method for preparing antimony-free polyester fine-denier FDY fibers by melt direct spinning comprises the following steps:
(1) adding terephthalic acid, ethylene glycol and 2-amyl-1, 3-propanediol into a first esterification kettle to carry out primary esterification reaction, wherein the mass ratio of the terephthalic acid to the ethylene glycol is 1:0.43, and the addition amount of the 2-amyl-1, 3-propanediol accounts for 80ppm of the mass of the polyester; the reaction temperature is 245 ℃, the pressure is 300Kpa, and the retention time is 80 min;
(2) conveying the primary esterification reaction product to an esterification I chamber in a second esterification kettle, sequentially flowing through an esterification II chamber and an esterification III chamber, adding 2ppm of a redness agent and 5ppm of a blueness agent into the esterification II chamber through a colorant feeding tank, and adding 10ppm of nano titanium dioxide into the esterification III chamber through a catalyst feeding tank to perform secondary esterification reaction; the reaction temperature is 255 ℃ and the reaction time is 40 min;
(3) refluxing 2 wt% of a secondary esterification reaction product in the esterification III chamber into the first esterification kettle to participate in a primary esterification reaction; conveying the rest to a prepolymerization kettle for prepolymerization reaction to obtain a prepolycondensation product, wherein the reaction temperature is 270 ℃, the pressure is 380pa, and the retention time is 60 min;
(4) conveying the pre-polycondensation product to a final polymerization kettle for final polycondensation reaction to obtain a titanium-based polyester melt, wherein the reaction temperature is 275 ℃, the pressure is 160pa, and the retention time is 90 min;
(5) and (3) directly spinning the polyester melt obtained from the final polymerization kettle through a melt to prepare the antimony-free polyester fine denier FDY fiber, wherein the melt direct spinning process parameters are as follows: number of holes of spinneret plate: 48; temperature of spinning beam: 285 ℃; cooling air temperature: 22 ℃; oiling rate of oiling: 0.5 wt%; speed of winding: 4000 m/min.
Example 2:
a method for preparing antimony-free polyester fine-denier FDY fibers by melt direct spinning comprises the following steps:
(1) adding terephthalic acid, ethylene glycol and 2-amyl-1, 3-propanediol into a first esterification kettle to carry out primary esterification reaction, wherein the mass ratio of the terephthalic acid to the ethylene glycol is 1:0.43, and the addition amount of the 2-amyl-1, 3-propanediol accounts for 80ppm of the mass of the polyester; the reaction temperature is 245 ℃, the pressure is 300Kpa, and the retention time is 80 min;
(2) conveying the primary esterification reaction product to an esterification I chamber in a second esterification kettle, sequentially flowing through an esterification II chamber and an esterification III chamber, adding 2ppm of a red agent and 5ppm of a blue agent into the esterification II chamber through a colorant feeding tank, and adding 10ppm of a heterogeneous titanium catalyst into the esterification III chamber through a catalyst feeding tank to perform secondary esterification reaction; the reaction temperature is 255 ℃ and the reaction time is 40 min;
(3) refluxing 2 wt% of a secondary esterification reaction product in the esterification III chamber into the first esterification kettle to participate in a primary esterification reaction; conveying the rest to a prepolymerization kettle for prepolymerization reaction to obtain a prepolycondensation product, wherein the reaction temperature is 270 ℃, the pressure is 380Pa, and the retention time is 60 min;
(4) conveying the pre-polycondensation product to a final polymerization kettle for final polycondensation reaction to obtain a titanium-based polyester melt, wherein the reaction temperature is 275 ℃, the pressure is 160Pa, and the retention time is 90 min;
(5) and (3) directly spinning the polyester melt obtained from the final polymerization kettle through a melt to prepare the antimony-free polyester fine denier FDY fiber, wherein the melt direct spinning process parameters are as follows: number of holes of spinneret plate: 48; temperature of spinning beam: 285 ℃; cooling air temperature: 22 ℃; oiling rate of oiling: 0.5 wt%; speed of winding: 4000 m/min.
Wherein, the preparation method of the heterogeneous titanium catalyst used in the step (2) comprises the following steps:
A) fully dispersing 30g of porous alumina nanospheres with the aperture of 1-50 nm and the particle size of 100-700 nm in 70mL of water, pumping to-60 kPa at the speed of 100Pa/s, standing for 2h to enable the water to be fully immersed in a pore channel, centrifuging to recover a porous carrier, and drying at 80 ℃ for 2h to obtain a water-carrying porous carrier;
B) adding 14.22g of tetrabutyl titanate into 696g of ethylene glycol, adding 60g of citric acid and 44g of triethyl phosphate, and continuously stirring at the speed of 300rpm for 60min to obtain a titanate solution;
C) adding a water-carrying porous carrier into a titanate solution under the condition of continuously stirring at the speed of 1000rpm, condensing and refluxing for 2 hours at the temperature of 80 ℃, then carrying out centrifugal separation, and drying the precipitate at the temperature of 110 ℃ for 4 hours to obtain a titanium dioxide/porous carrier composite material;
D) and (3) dispersing 20g of titanium dioxide/porous carrier composite material into 30g of ethylene glycol, and grinding for 3 hours to obtain the heterogeneous titanium catalyst.
Example 3:
a method for preparing antimony-free polyester fine-denier FDY fibers by melt direct spinning comprises the following steps:
(1) adding terephthalic acid, ethylene glycol and 2-amyl-1, 4-butanediol into a first esterification kettle to carry out primary esterification reaction, wherein the mass ratio of the terephthalic acid to the ethylene glycol is 1:0.48, and the addition amount of the 2-amyl-1, 4-butanediol accounts for 50ppm of the mass of the polyester; the reaction temperature is 248 ℃, the pressure is 100Kpa, and the retention time is 90 min;
(2) conveying the primary esterification reaction product to an esterification I chamber in a second esterification kettle, sequentially flowing through an esterification II chamber and an esterification III chamber, adding 2ppm of a red agent and 5ppm of a blue agent into the esterification II chamber through a colorant feeding tank, and adding 4ppm of a heterogeneous titanium catalyst into the esterification III chamber through a catalyst feeding tank to perform secondary esterification reaction; the reaction temperature is 250 ℃ and the reaction time is 60 min;
(3) 3 wt% of secondary esterification reaction products in the esterification III chamber are refluxed into the first esterification kettle to participate in primary esterification reaction; conveying the rest to a prepolymerization kettle for prepolymerization reaction to obtain a prepolycondensation product, wherein the reaction temperature is 260 ℃, the pressure is 180Pa, and the retention time is 70 min;
(4) conveying the pre-polycondensation product to a final polymerization kettle for final polycondensation reaction to obtain a titanium-based polyester melt, wherein the reaction temperature is 272 ℃, the pressure is 150Pa, and the retention time is 120 min;
(5) and (3) directly spinning the polyester melt obtained from the final polymerization kettle through a melt to prepare the antimony-free polyester fine denier FDY fiber, wherein the melt direct spinning process parameters are as follows: number of holes of spinneret plate: 48; temperature of spinning beam: 280 ℃; cooling air temperature: 20 ℃; oiling rate of oiling: 0.42 wt%; speed of winding: 4200 m/min.
Wherein, the preparation method of the heterogeneous titanium catalyst used in the step (2) comprises the following steps:
A) fully dispersing 30g of porous alumina nanospheres with the aperture of 1-50 nm and the particle size of 100-700 nm in 70mL of water, pumping to-60 kPa at the speed of 100Pa/s, standing for 1h to enable the water to be fully immersed in a pore channel, centrifuging to recover a porous carrier, and drying at 80 ℃ for 4h to obtain a water-carrying porous carrier;
B) adding 1.07g of tetrabutyl titanate into 212g of ethylene glycol, adding 6g of citric acid and 4.4g of triethyl phosphate into the mixture, and continuously stirring the mixture at the speed of 300rpm for 60min to obtain a titanate solution;
C) adding a water-carrying porous carrier into a titanate solution under the condition of continuously stirring at the speed of 1000rpm, condensing and refluxing for 2 hours at the temperature of 80 ℃, then carrying out centrifugal separation, and drying the precipitate at the temperature of 110 ℃ for 4 hours to obtain a titanium dioxide/porous carrier composite material;
D) and (3) dispersing 20g of titanium dioxide/porous carrier composite material into 380g of ethylene glycol, and grinding for 3 hours to obtain the heterogeneous titanium catalyst.
Example 4:
a method for preparing antimony-free polyester fine-denier FDY fibers by melt direct spinning comprises the following steps:
(1) adding terephthalic acid, ethylene glycol and 2-amyl-1, 4-butanediol into a first esterification kettle to carry out primary esterification reaction, wherein the mass ratio of the terephthalic acid to the ethylene glycol is 1:0.52, and the addition amount of the 2-amyl-1, 4-butanediol accounts for 40ppm of the mass of the polyester; the reaction temperature is 250 ℃, the pressure is 400Kpa, and the retention time is 60 min;
(2) conveying the primary esterification reaction product to an esterification I chamber in a second esterification kettle, sequentially flowing through an esterification II chamber and an esterification III chamber, adding 2ppm of a red agent and 5ppm of a blue agent into the esterification II chamber through a colorant feeding tank, and adding 15ppm of a heterogeneous titanium catalyst into the esterification III chamber through a catalyst feeding tank to perform secondary esterification reaction; the reaction temperature is 260 ℃ and the reaction time is 30 min;
(3) 1 wt% of secondary esterification reaction products in the esterification III chamber are refluxed into the first esterification kettle to participate in primary esterification reaction; conveying the rest to a prepolymerization kettle for prepolymerization reaction to obtain a prepolycondensation product, wherein the reaction temperature is 270 ℃, the pressure is 500Pa, and the retention time is 50 min;
(4) conveying the pre-polycondensation product to a final polymerization kettle for final polycondensation reaction to obtain a titanium-based polyester melt, wherein the reaction temperature is 270 ℃, the pressure is 200Pa, and the retention time is 30 min;
(5) and (3) directly spinning the polyester melt obtained from the final polymerization kettle through a melt to prepare the antimony-free polyester fine denier FDY fiber, wherein the melt direct spinning process parameters are as follows: number of holes of spinneret plate: 48; temperature of spinning beam: 290 ℃; cooling air temperature: 25 ℃; oiling rate of oiling: 1.5 wt%; speed of winding: 4600 m/min.
Wherein, the preparation method of the heterogeneous titanium catalyst used in the step (2) comprises the following steps:
A) fully dispersing 30g of porous alumina nanospheres with the aperture of 1-50 nm and the particle size of 100-700 nm in 70mL of water, pumping to-60 kPa at the speed of 100Pa/s, standing for 1h to enable the water to be fully immersed in a pore channel, centrifuging to recover a porous carrier, and drying at 80 ℃ for 4h to obtain a water-carrying porous carrier;
B) adding 4.26g of tetrabutyl titanate into 209g of ethylene glycol, adding 1.2g of citric acid and 8.8g of triethyl phosphate, and continuously stirring at the speed of 300rpm for 60min to obtain a titanate solution;
C) adding a water-carrying porous carrier into a titanate solution under the condition of continuously stirring at the speed of 1000rpm, condensing and refluxing for 1h at 70 ℃, then carrying out centrifugal separation, and drying the precipitate for 4h at 110 ℃ to obtain a titanium dioxide/porous carrier composite material;
D) and (3) dispersing 20g of titanium dioxide/porous carrier composite material into 380g of ethylene glycol, and grinding for 1 hour to obtain the heterogeneous titanium catalyst.
Comparative example 1:
a method for preparing antimony-free polyester fine-denier FDY fibers by melt direct spinning comprises the following steps:
(1) adding terephthalic acid and ethylene glycol into a first esterification kettle to carry out primary esterification reaction, wherein the mass ratio of the terephthalic acid to the ethylene glycol is 1: 0.43; the reaction temperature is 245 ℃, the pressure is 300Kpa, and the retention time is 80 min;
(2) conveying the primary esterification reaction product to an esterification I chamber in a second esterification kettle, sequentially flowing through an esterification II chamber and an esterification III chamber, adding 2ppm of a redness agent and 5ppm of a blueness agent into the esterification II chamber through a colorant feeding tank, and adding 10ppm of nano titanium dioxide into the esterification III chamber through a catalyst feeding tank to perform secondary esterification reaction; the reaction temperature is 255 ℃ and the reaction time is 40 min;
(3) refluxing 2 wt% of a secondary esterification reaction product in the esterification III chamber into the first esterification kettle to participate in a primary esterification reaction; conveying the rest to a prepolymerization kettle for prepolymerization reaction to obtain a prepolycondensation product, wherein the reaction temperature is 270 ℃, the pressure is 380pa, and the retention time is 60 min;
(4) conveying the pre-polycondensation product to a final polymerization kettle for final polycondensation reaction to obtain a titanium-based polyester melt, wherein the reaction temperature is 275 ℃, the pressure is 160pa, and the retention time is 90 min;
(5) and (3) directly spinning the polyester melt obtained from the final polymerization kettle through a melt to prepare the antimony-free polyester fine denier FDY fiber, wherein the melt direct spinning process parameters are as follows: number of holes of spinneret plate: 48; temperature of spinning beam: 285 ℃; cooling air temperature: 22 ℃; oiling rate of oiling: 0.5 wt%; speed of winding: 4000 m/min.
Comparative example 2:
a method for preparing antimony-free polyester fine-denier FDY fibers by melt direct spinning comprises the following steps:
(1) adding terephthalic acid, ethylene glycol and 2-amyl-1, 3-propanediol into a first esterification kettle to carry out primary esterification reaction, wherein the mass ratio of the terephthalic acid to the ethylene glycol is 1:0.43, and the addition amount of the 2-amyl-1, 3-propanediol accounts for 80ppm of the mass of the polyester; the reaction temperature is 245 ℃, the pressure is 300Kpa, and the retention time is 80 min;
(2) conveying the primary esterification reaction product to an esterification I chamber in a second esterification kettle, sequentially flowing through an esterification II chamber and an esterification III chamber, adding 2ppm of a redness agent and 5ppm of a blueness agent into the esterification II chamber through a colorant feeding tank, and adding 10ppm of nano titanium dioxide into the esterification III chamber through a catalyst feeding tank to perform secondary esterification reaction; the reaction temperature is 255 ℃ and the reaction time is 40 min;
(3) conveying the secondary esterification reaction product in the esterification III chamber to a prepolymerization reactor for prepolymerization reaction to obtain a prepolycondensation product, wherein the reaction temperature is 270 ℃, the pressure is 380pa, and the retention time is 60 min;
(4) conveying the pre-polycondensation product to a final polymerization kettle for final polycondensation reaction to obtain a titanium-based polyester melt, wherein the reaction temperature is 275 ℃, the pressure is 160pa, and the retention time is 90 min;
(5) and (3) directly spinning the polyester melt obtained from the final polymerization kettle through a melt to prepare the antimony-free polyester fine denier FDY fiber, wherein the melt direct spinning process parameters are as follows: number of holes of spinneret plate: 48; temperature of spinning beam: 285 ℃; cooling air temperature: 22 ℃; oiling rate of oiling: 0.5 wt%; speed of winding: 4000 m/min.
The viscosity drop during melt-conveying and the properties of the obtained antimony-free polyester fine FDY fibers in the above examples and comparative examples were measured, and the results are shown in Table 1.
Table 1: and (3) testing the performance of the melt conveying viscosity reduction and the antimony-free polyester fine denier FDY fiber.
As can be seen from Table 1, the antimony-free polyester melt prepared by the method in the invention in the embodiments 1-4 has good performance and low viscosity reduction in the conveying process; the finally prepared antimony-free polyester fine-denier FDY fiber has good mechanical property.
In contrast, in comparative example 1, dihydric alcohol containing a branched chain is not introduced into the polyester, in comparative example 2, a product containing a catalyst in the second esterification kettle is not refluxed into the first esterification kettle in the preparation process, and the viscosity of the prepared melt is higher, so that the mechanical property of the finally prepared antimony-free polyester fine-denier FDY fiber is reduced.
In addition, in the embodiments 2-4, titanium dioxide is attached to the pore channels of the porous alumina to prepare the heterogeneous titanium catalyst, when the catalyst is used for catalyzing polyester synthesis, the viscosity reduction of the melt in the conveying process is further reduced compared with the case of using nano titanium dioxide as the catalyst in the embodiment 1, and the mechanical property of the obtained antimony-free polyester fine-denier FDY fiber is obviously improved compared with the case of using nano titanium dioxide as the catalyst in the embodiment 1.
This is because the degree of polymerization cannot be controlled when nano titanium dioxide is directly used as a catalyst, and the obtained polyester has a wide molecular weight distribution range, resulting in poor spinning performance. When the heterogeneous titanium catalyst is prepared by attaching titanium dioxide in the pore channel of the porous alumina, the surface of the water-carrying porous alumina prepared in the step A) is dry, and the pore channel contains water; in step C), the contact speed between the two phases can be retarded due to the relatively slow mass transfer in the channels, the reaction between the two phases will be determined by both the diffusion time and the reaction time, whereas for the hydrolysis reaction of titanate in the aqueous phase, the diffusion time becomes the dominant factor of the reaction due to the short hydrolysis time. Based on the reasons, after the water-carrying porous alumina is added into the titanate solution, the organic phase and the water phase are mutually diffused in the pore channel, so that the titanate is promoted to contact with water on the surface of the pore channel and be hydrolyzed, and in the obtained composite catalyst, the titanium dioxide is attached in the pore channel of the porous carrier, and almost no titanium dioxide exists outside the pore channel. And D), intensifying the molecular collision between the glycol and the product (namely the titanium dioxide/porous carrier composite material) by utilizing the grinding effect, so that the glycol is adsorbed on the surface of the titanium dioxide/porous carrier composite material through hydrogen bonds. The heterogeneous titanium polyester catalyst treated by the ethylene glycol can improve the dispersion stability of the catalyst in a polyester monomer, thereby improving the catalytic efficiency, improving the dispersion stability of the catalyst in a polyester melt and preventing the catalyst from precipitating to influence the spinning performance of the polyester.
When the heterogeneous titanium catalyst prepared by the invention is used for catalyzing the synthesis of polyester, a polymerization monomer needs to enter a porous carrier pore channel to contact with titanium dioxide for catalysis, although the polycondensation time is prolonged to a certain extent, long-chain polyester cannot continuously enter the pore channel for reaction due to the function of pore channel screening, so that the molecular weight of a polymerization product is more concentrated, namely the polymerization reaction is more uniform, the spinning performance of the polyester is obviously improved, and the yarn breaking and the yarn floating are not easy to occur during spinning. And when the polymerization reaction is finished, the polyester with large molecular weight exists in the pore channel of the heterogeneous catalyst, so that titanium dioxide is not easy to contact with other polyester molecular chains, and therefore, the polyester is not easy to degrade and the viscosity is reduced less in the melt conveying process.
According to the invention, the alumina is used as the porous carrier, the nano porous alumina has good affinity with water, can adsorb water in a pore channel more easily, and the surface of the nano porous alumina has electropositivity and is easy to adsorb a titanate hydrolysis electronegativity intermediate; in addition, the nano porous alumina has good catalytic activity, the electropositive surface is easy to adsorb polyester monomers, the contact between the polyester monomers and a catalyst in a pore channel is promoted, and after the titanium dioxide is coupled with the alumina, the electron transfer can be promoted, the activation energy is reduced, and the reaction rate is improved.
In addition, the pore diameter of the porous alumina is controlled to be 1-50 nm, and the water content is controlled to be 0.1-1.5 wt%. The reason is that: porous alumina with an excessively small pore diameter is difficult to prepare, and even if the porous alumina is prepared, when water is absorbed in the step A) due to the excessively small pore diameter, gas in a pore channel is difficult to discharge, water is difficult to wet into the pore channel, so that the water content in the obtained water-carrying porous carrier is too low, and further the titanium dioxide content in the heterogeneous titanium polyester catalyst is too low, and the catalytic activity of the catalyst is influenced; if the pore diameter is too large, a large amount of moisture in the pore channel is lost when the surface of the porous alumina is dried in the step A) before the surface of the porous alumina is sufficiently dried, the water content in the water-carrying porous carrier is too low, and the excessive pore diameter also causes rapid mass transfer of moisture in the air after the water-carrying porous carrier is added into a titanate solution, the titanate is hydrolyzed outside the pore to form titanium dioxide, and in the prepared catalyst, the molecular weight of polyester is difficult to control due to the titanium dioxide existing outside the pore channel. When the water content in the water-carrying porous alumina is lower, the diffusion mass transfer is slow, the titanate hydrolysis is more uniform and sufficient, the titanium dioxide is more easily synthesized in the pore channel, and the uncontrolled polycondensation reaction caused by the hydrolysis of excessive titanate outside the pore channel can be avoided; however, when the water content is too low, the titanium dioxide loading in the catalyst becomes too low, resulting in low catalytic activity. The water content is controlled within a certain range, and the dosage of the titanate is adjusted based on the water content, so that the polycondensation reaction rate can be improved, and the molecular weight of the product can be well controlled.
Claims (10)
1. A system for preparing antimony-free polyester melt is characterized by comprising a first esterification kettle (1), a second esterification kettle (2), a prepolymerization kettle (3) and a final polymerization kettle (4) which are sequentially connected, and a catalyst feeding unit and a coloring agent feeding unit which are respectively connected with the second esterification kettle; the second esterification kettle comprises an esterification I chamber (201), an esterification II chamber (202) and an esterification III chamber (203) which are sequentially communicated, the esterification I chamber is communicated with the first esterification kettle, the esterification II chamber is communicated with a colorant feeding unit, and the esterification III chamber is respectively communicated with the first esterification kettle, a prepolymerization kettle and a catalyst feeding unit.
2. The system of claim 1, wherein said colorant supply unit comprises a colorant preparation tank (501) and a colorant supply tank (502) connected to each other, said colorant supply tank being in communication with the esterification II compartment of the second esterification vessel; the catalyst addition unit comprises a catalyst preparation tank (601) and a catalyst feed tank (602) connected in communication with the esterification III chamber of the second esterification tank.
3. A method for preparing antimony-free polyester fine FDY fiber by melt direct spinning using the system of claim 1 or 2, comprising the steps of:
(1) adding terephthalic acid, ethylene glycol and dihydric alcohol containing branched chains into a first esterification kettle to carry out primary esterification reaction;
(2) conveying the primary esterification reaction product to an esterification I chamber in a second esterification kettle, sequentially flowing through an esterification II chamber and an esterification III chamber, adding a colorant into the esterification II chamber, and adding a titanium catalyst into the esterification III chamber to perform secondary esterification reaction;
(3) partially refluxing a secondary esterification reaction product in the esterification III chamber to the first esterification kettle to participate in a primary esterification reaction; conveying the rest to a prepolymerization kettle for prepolymerization reaction to obtain a prepolycondensation product;
(4) conveying the pre-polycondensation product to a final polymerization kettle for final polycondensation reaction to obtain a titanium-based polyester melt;
(5) and (3) directly spinning the polyester melt obtained from the final polymerization kettle through a melt to obtain the antimony-free polyester fine denier FDY fiber.
4. The method for preparing the antimony-free polyester fine-denier FDY fiber through melt direct spinning according to claim 3, wherein the mass ratio of terephthalic acid to ethylene glycol in the step (1) is 1: 0.43-0.52; the dihydric alcohol containing the branched chain is one or more selected from 2-amyl-1, 3-propylene glycol, 2-amyl-1, 4-butanediol and 2-amyl-1, 5-pentanediol, and the adding amount of the dihydric alcohol containing the branched chain accounts for 40-80 ppm of the weight of the polyester.
5. The method for preparing the antimony-free polyester fine-denier FDY fiber through melt direct spinning according to claim 3 or 4, wherein the pressure of the primary esterification reaction in the step (1) is 100 to 400KPa, the temperature is 245 to 250 ℃, and the time is 60 to 90 min.
6. The method for preparing the antimony-free polyester fine-denier FDY fiber through melt direct spinning according to claim 3, wherein the temperature of the secondary esterification reaction in the step (2) is 250-260 ℃ and the time is 30-60 min; the addition amount of the titanium catalyst is 4-15 ppm.
7. The method for preparing the antimony-free polyester fine-denier FDY fiber through melt direct spinning according to claim 3 or the claim, wherein the mass of the secondary esterification reaction product refluxed into the first esterification kettle in the step (3) accounts for 1-3% of the mass of the secondary esterification reaction product in the esterification III chamber.
8. The method for preparing antimony-free polyester fine-denier FDY fiber through melt direct spinning according to claim 3 or 7 or the above, wherein the pressure of the pre-polycondensation reaction in the step (3) is 150-500 Pa, the temperature is 260-270 ℃, and the time is 50-70 min.
9. The method for preparing the antimony-free polyester fine-denier FDY fiber through melt direct spinning according to claim 3 or the claim, wherein the final polycondensation reaction in the step (4) is carried out at a pressure of 150-200 Pa, a temperature of 270-275 ℃ and a time of 30-120 min.
10. The method for preparing the antimony-free polyester fine FDY fiber by melt direct spinning according to claim 3 or the claim, wherein the melt direct spinning process parameters in the step (5) are as follows:
temperature of spinning beam: 280-290 ℃;
cooling air temperature: 20-25 ℃;
oiling rate of oiling: 0.42 to 1.5 wt%;
speed of winding: 4000-4600 m/min.
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| CN115572382A (en) * | 2022-10-25 | 2023-01-06 | 四川汇维仕化纤有限公司 | Antimony-free polyester melt and preparation method thereof |
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Address after: 310000 Yaqian town Chenghu Road, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee after: ZHEJIANG HENGYI PETROCHEMICAL Co.,Ltd. Patentee after: Zhejiang Hengyi Petrochemical Research Institute Co.,Ltd. Address before: 310000 Yaqian town Chenghu Road, Xiaoshan District, Hangzhou City, Zhejiang Province Patentee before: ZHEJIANG HENGYI PETROCHEMICAL Co.,Ltd. Patentee before: Zhejiang Henglan Technology Co., Ltd |