CN119102004A - A modified polyester filament and preparation method thereof - Google Patents
A modified polyester filament and preparation method thereof Download PDFInfo
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- CN119102004A CN119102004A CN202411462716.3A CN202411462716A CN119102004A CN 119102004 A CN119102004 A CN 119102004A CN 202411462716 A CN202411462716 A CN 202411462716A CN 119102004 A CN119102004 A CN 119102004A
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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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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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
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Polyesters Or Polycarbonates (AREA)
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Abstract
本发明公开了一种改性聚酯长丝，包括改性聚酯和消光剂，所述改性聚酯包括对苯二甲酸链段、间苯二甲酸链段、乙二醇链段、二甘醇链段和5‑氨基间苯二酸双‑3‑羟基乙酯链段，所述消光剂为无机介孔粉体，所述无机介孔粉体表面含有氨基官能团。本发明的改性聚酯长丝将含氨基的无机介孔粉体代替传统的消光剂引入到熔融纺丝体系中，同时起到乙醛清除作用和消光作用，易实现工业生产，纺丝过程中可减少乙醛蒸汽的释放，改善生产环境本发明另一个目的是公开了一种改性聚酯长丝的制备方法。本发明的制备方法减少了纺丝过程中乙醛蒸汽的释放对环境的恶化，降低改性聚酯长丝中的乙醛的含量，有益于其应用的安全性。The present invention discloses a modified polyester filament, including a modified polyester and a matting agent, wherein the modified polyester includes a terephthalic acid segment, an isophthalic acid segment, an ethylene glycol segment, a diethylene glycol segment and a 5-aminoisophthalic acid bis-3-hydroxyethyl ester segment, and the matting agent is an inorganic mesoporous powder, and the inorganic mesoporous powder surface contains an amino functional group. The modified polyester filament of the present invention introduces an amino-containing inorganic mesoporous powder into a melt spinning system instead of a traditional matting agent, and simultaneously plays an acetaldehyde removal effect and a matting effect, and is easy to realize industrial production, and the release of acetaldehyde vapor can be reduced during spinning, and the production environment is improved. Another object of the present invention is to disclose a method for preparing a modified polyester filament. The preparation method of the present invention reduces the deterioration of the release of acetaldehyde vapor during spinning to the environment, reduces the content of acetaldehyde in the modified polyester filament, and is beneficial to the safety of its application.
Description
Technical Field
The invention relates to the technical field of spinning production, in particular to a modified polyester filament and a preparation method thereof.
Background
The hot melt adhesive is a novel adhesive which is developed at home and abroad in recent years, and compared with other types of adhesives, the hot melt adhesive has the excellent characteristics of short bonding time, high strength, no toxicity, no pollution and the like, and is known as a green adhesive. For more than ten years, hot melt adhesives have found wide application in the textile industry (e.g., adhesive liners), and the key to the manufacture of high quality adhesive liners is the need for high performance hot melt adhesives. Because the copolyester hot melt adhesive has excellent hand feeling, price, washing resistance, sand washing resistance, steam pressure ironing resistance and other aspects, the copolyester hot melt adhesive has wider development prospect. The polyester hot melt adhesive is a new type of hot melt adhesive developed in recent decades, is a modified low-melting-point saturated copolyester, and is mostly prepared by adopting a copolymerization method of two or more than two kinds of dibasic acid and dihydric alcohol, so that the crystallinity, the glass transition temperature and the melting point of the polyester hot melt adhesive are greatly reduced to meet the special requirements of the hot melt adhesive.
Thermally bonding low-melting fibers is one of the important raw materials for nonwoven fabrics. It is counted to be about 28% of the total nonwoven fabric fiber. In the current rapidly developed nonwoven industry, the thermal bonding method is preferentially developed because of the processing method of using the fiber type adhesive, which has the advantages of simple processing, high production speed, low energy consumption, flexible application, no chemical reagent in the product, no environmental pollution and no harm to human body. The thermal bonding method is a reinforcing method in which a polymer fiber material is partially softened and melted by applying a certain amount of heat to the polymer fiber material by using the thermoplastic properties of the polymer material, and the fibers are bonded to each other after cooling and solidifying. For the polyester-based nonwoven industry, there is a need for a polymer that has a lower melting point than conventional polyester fibers and good compatibility with conventional polyesters as a thermally bonded low melting point fiber. According to the principle of similar compatibility, the non-woven fabric using terylene as main body fiber is bonded by the same family of polyester fibers, and practice shows that the bonding fiber is spun by low-melting-point copolyester, so that the terylene flocculus is softer and bulkier, thereby providing a wide space for the application of the polyester low-melting-point thermal bonding fiber.
However, a series of side reactions occur during the esterification reaction of the low melting point copolyester, and many byproducts are generated, wherein the most affected byproduct is acetaldehyde, which can cause discomfort symptoms such as flushing, palpitation, and blood pressure drop. Meanwhile, acetaldehyde can cause eye, nose and upper respiratory tract irritation symptoms and bronchitis, and high-concentration acetaldehyde is inhaled to have anesthesia effect, so that the acetaldehyde has great harm to human health.
In the preparation process of the low-melting-point copolyester filament, the involved cooling and stretching temperatures are low, the time is short, and the acetaldehyde content of the fiber cannot be reduced below a safe value. Therefore, a new solution is needed to solve at least one of the above technical problems.
Disclosure of Invention
In view of the above-mentioned shortcomings, an object of the present invention is to provide a modified polyester filament, wherein an amino-containing inorganic mesoporous powder is introduced into a melt spinning system instead of a conventional matting agent, and has an acetaldehyde scavenging effect and a matting effect, so that industrial production is easy to realize, release of acetaldehyde vapor can be reduced during spinning, and production environment is improved. The invention also aims to provide a preparation method of the modified polyester filament, which is characterized in that the modified polyester with the amino-containing side groups is synthesized in a simple copolymerization mode by inorganic, so that the thermal oxidative degradation is inhibited in the polymerization and processing processes, the generation of acetaldehyde is inhibited, the deterioration of the environment caused by the release of acetaldehyde steam in the spinning process is reduced, the content of acetaldehyde in the modified polyester filament is reduced, and the application safety is benefited.
In order to achieve the technical purpose and meet the technical requirements, the invention adopts the technical scheme that:
the modified polyester filament comprises a modified polyester and a matting agent, wherein the modified polyester comprises a terephthalic acid chain segment, an isophthalic acid chain segment, an ethylene glycol chain segment, a diethylene glycol chain segment and a 5-amino isophthalic acid bis-3-hydroxyethyl ester chain segment, the matting agent is inorganic mesoporous powder, and the surface of the inorganic mesoporous powder contains amino functional groups.
As a preferable technical scheme, the inorganic mesoporous powder is mesoporous titanium dioxide powder, the pore diameter of the mesoporous titanium dioxide powder is 2nm-4nm, the specific surface area is 100m 2/g-300m2/g, the particle size is 200nm-300nm, and the content of the amino functional group is 1wt% -3wt%.
As a preferable technical scheme, the melting point of the modified polyester is 110-150 ℃, and the molecular weight of the modified polyester is 18000-22000.
The invention also provides a preparation method of the modified polyester filament, which comprises the following steps:
Preparing a delustering agent and modified polyester, mixing the delustering agent and the modified polyester to obtain modified polyester chips, and metering, melting, extruding, cooling, oiling, stretching, heat setting and winding the modified polyester chips to obtain modified polyester filaments.
As a preferred technical scheme, the specific steps for preparing the matting agent are as follows:
The preparation method comprises the steps of taking alkylamine as a template agent, taking isopropyl titanate or n-butyl titanate as a titanium source, adding the template agent and the titanium source into ethanol, mixing and dissolving, adding deionized water to generate precipitate, aging, filtering, extracting to remove part of the template agent, and then washing and drying to obtain the matting agent, wherein the matting agent is mesoporous titanium dioxide powder;
the specific steps for preparing the modified polyester are as follows:
Dissolving 5-amino isophthalic acid in methanol, adding thionyl chloride under the condition of ice water bath, reacting for 3-4 hours, evaporating to remove methanol, separating an esterification product by adding water, extracting the esterification product by using ethyl acetate, and volatilizing to remove ethyl acetate to obtain 5-amino isophthalic acid dimethyl ester;
performing transesterification reaction on the 5-amino isophthalic acid dimethyl ester and ethylene glycol under the action of a first catalyst, wherein the esterification temperature is 180-210 ℃ and the esterification time is 2-3 hours until the transesterification reaction is complete, so as to obtain the 5-amino isophthalic acid bis-3-hydroxyethyl ester;
Preparing terephthalic acid, isophthalic acid, ethylene glycol, diglycol and mesoporous titanium dioxide powder into slurry, and performing esterification reaction to obtain an esterification product, wherein the pressure is 0.1-0.3Mpa, and the temperature is 230-250 ℃;
After the esterification reaction is finished, adding 5-amino isophthalic acid bis-3-hydroxyethyl ester into an esterification product, adding a second catalyst and a stabilizer, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, wherein the pressure in the low vacuum stage is steadily reduced to below 500Pa absolute pressure from normal pressure, the temperature is controlled to be 260-270 ℃ and the reaction time is 30-50 min, then continuously vacuumizing, performing the polycondensation reaction in a high vacuum stage, the pressure in the high vacuum stage is reduced to be less than 70Pa absolute pressure, the reaction temperature is controlled to be 275-280 ℃ and the reaction time is 50-90 min, and obtaining the modified polyester.
According to the preferable technical scheme, the alkylamine is twelve, fourteen, sixteen or octadecylamine, the molar ratio of the alkylamine to the titanium source is 1 (2-3), the volume ratio of the ethanol to the deionized water is 1 (4-5), the concentration of the alkylamine is 2-2.2 wt%, the aging condition is that the room temperature is firstly carried out, the room temperature time is 20-24 hours, the temperature is then increased to 90-100 ℃, the heating time is 40-48 hours, the extraction condition is that the treatment is carried out for 12-15 hours in an ethanol nitrate solution with pH=2 at the room temperature, the washing condition is that the washing is carried out for 3-5 times by ethanol suction filtration, the drying condition is that the drying temperature is 50-60 ℃, and the drying time is 24-30 hours.
As the preferable technical scheme, the mole ratio of 5-amino isophthalic acid, methanol and thionyl chloride is 1 (35.0-37.5) (3-3.5), the added water volume is 2-3 times that of methanol, the added ethyl acetate volume is 1-1.2 times that of methanol, the mole ratio of 5-amino isophthalic acid dimethyl ester to ethylene glycol is 1 (1.8-2.2), the first catalyst is added in an amount of 0.02-0.03% of the weight of 5-amino isophthalic acid dimethyl ester, and the mole ratio of terephthalic acid, isophthalic acid, ethylene glycol and diethylene glycol is 1 (0.4-0.6) (0.08-0.12) (1.8-2.5).
As a preferable technical scheme, the weight of the delustrant is 0.20-0.25% of the weight of the modified polyester, and the molar ratio of the 5-amino isophthalic acid bis-3-hydroxyethyl ester to the terephthalic acid is 1 (0.02-0.03).
As a preferable technical scheme, the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite, the addition of the stabilizer is 0.03-0.05% of the total weight of the terephthalic acid, the second catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, and the addition of the second catalyst is 0.03-0.05% of the total weight of the terephthalic acid.
As a preferable technical scheme, the modified polyester filament is prepared by the parameters of 270-280 ℃ of extrusion temperature, 20-25 ℃ of cooling temperature, 2200-2400 m/min of roller speed, 65-70 ℃ of roller speed, 3000-3200 m/min of roller speed, 150-180 ℃ of roller speed, 2960-3230 m/min of winding speed, 1.5dtex-3.0dtex of titer, more than or equal to 3.5cN/dtex of breaking elongation of 50.0+/-5.0% of breaking elongation of the modified polyester filament, and the content of acetaldehyde in the modified polyester filament is less than 0.5ppm.
Compared with the traditional technical scheme, the invention has the beneficial effects that:
1) According to the invention, the amino-containing inorganic mesoporous powder is introduced into a melt spinning system instead of the traditional matting agent, and has the effects of removing acetaldehyde and matting, so that industrial production is easy to realize, the release of acetaldehyde steam can be reduced in the spinning process, the production environment is improved, the modified polyester with amino-containing side groups is synthesized in a simple copolymerization mode, the thermal oxidative degradation is inhibited in the polymerization and processing processes, the generation of acetaldehyde is inhibited, the deterioration of the environment caused by the release of acetaldehyde steam in the spinning process is reduced, the content of acetaldehyde in the modified polyester filament is reduced, and the application safety is benefited;
2) Adding mesoporous titanium dioxide powder with high refractive index into the modified polyester filament, and preparing the mesoporous titanium dioxide powder into a mesoporous form containing amino functional groups, thereby having extinction function and acetaldehyde removal function;
3) The preparation method of the modified polyester filament synthesizes the modified polyester with the amino group on the side group through an inorganic simple copolymerization mode, so that the thermal oxidative degradation is inhibited in the polymerization and processing processes, the generation of acetaldehyde is inhibited, the deterioration of the environment caused by the release of acetaldehyde steam in the spinning process is reduced, the content of the acetaldehyde in the modified polyester filament is reduced, and the application safety of the modified polyester filament is benefited.
Detailed Description
The invention is further described below.
In the description of the present invention, it should be understood that, if the terms "top", "bottom", "left", "right", "front", "rear", "inner", "outer", etc. indicate orientations or positional relationships, they are merely used to facilitate describing the present invention, and they do not indicate or imply that the devices or elements being referred to must have a specific orientation, be configured and operated in a specific orientation, and thus the terms describing the positional relationships are merely used for exemplary illustration and should not be construed as limiting the present patent, and that the specific meaning of the terms described above should be understood by those of ordinary skill in the art according to the specific circumstances.
The modified polyester filament provided by one embodiment of the invention comprises modified polyester and a matting agent, wherein the modified polyester comprises a terephthalic acid chain segment, an isophthalic acid chain segment, an ethylene glycol chain segment, a diethylene glycol chain segment and a 5-amino isophthalic acid bis-3-hydroxyethyl ester chain segment, the matting agent is inorganic mesoporous powder, the surface of the inorganic mesoporous powder contains amino functional groups, the invention introduces the amino-containing inorganic mesoporous powder into a melt spinning system instead of the traditional matting agent, meanwhile, the method plays roles of eliminating acetaldehyde and extinction, is easy to realize industrial production, can reduce the release of acetaldehyde steam in the spinning process, improves the production environment, synthesizes the modified polyester with amino groups on side groups through a simple copolymerization mode, inhibits thermal oxidative degradation in the polymerization and processing processes, inhibits the generation of acetaldehyde, reduces the deterioration of the environment caused by the release of the acetaldehyde steam in the spinning process, reduces the content of acetaldehyde in the modified polyester filament, and is beneficial to the application safety of the modified polyester filament.
In some embodiments, the inorganic mesoporous powder is mesoporous titanium dioxide powder, the pore diameter of the mesoporous titanium dioxide powder is 2nm-4nm, the specific surface area is 100m 2/g-300m2/g, the particle diameter is 200nm-300nm, the content of amino functional groups is 1wt% -3wt%, and the mesoporous titanium dioxide powder with high refractive index is required to be added into the modified polyester filament, so that the mesoporous titanium dioxide powder is prepared into a mesoporous form containing amino functional groups, and the mesoporous titanium dioxide powder has the functions of extinction and acetaldehyde removal. On the one hand, the porous structure can increase the refraction times of light to generate better extinction effect, and on the other hand, the mesopores are favorable for absorbing acetaldehyde vapor molecules, because the modified polyester is changed into a modified polyester melt after being heated and extruded, the acetaldehyde vapor molecules can be released, the mesopores can well absorb the acetaldehyde vapor molecules, and the specific surface area of mesoporous titanium dioxide powder and the absorption sites of the acetaldehyde molecules are greatly improved by the mesoporous structure.
The invention adopts an inorganic mesoporous material to absorb acetaldehyde generated in the polymerization and spinning processes, and the inorganic mesoporous material is mesoporous titanium dioxide powder, which has the function of absorbing acetaldehyde molecules and high-efficiency extinction capability, and the mesoporous titanium dioxide powder is added into a melt spinning system instead of the traditional extinction agent on the basis of not changing the existing low-melting-point polyester filament production process.
In some of these embodiments, the modified polyester has a melting point of 110 ℃ to 150 ℃ and a molecular weight of 18000 to 22000, and the low melting point of the modified polyester does not affect the absorption of acetaldehyde.
The invention also provides a preparation method of the modified polyester filament, which comprises the following steps:
Preparing a delustering agent and modified polyester, mixing the delustering agent and the modified polyester to obtain a modified polyester chip, and metering, melting, extruding, cooling, oiling, stretching, heat setting and winding the modified polyester chip to obtain the modified polyester filament.
In some of these embodiments, the specific steps for preparing the matting agent are:
The invention takes alkylamine as template agent, isopropyl titanate or n-butyl titanate as titanium source, adds the template agent and titanium source into ethanol to mix and dissolve, thus forming amino functional group, adds deionized water to generate precipitate, aging, filtering, extracting to remove part of template agent, then washing and drying to obtain flatting agent, the flatting agent is mesoporous titanium dioxide powder, when preparing amino-containing mesoporous titanium dioxide powder, the method directly adopts alkylamine as a template agent, and is different from the conventional method for preparing mesoporous titanium dioxide powder, the template agent is completely removed, and part of the template agent is reserved, so that the step of reintroducing amino functional groups is reduced, the production cost is reduced, and the amino functional groups are positioned on the inner wall of mesopores, so that the whiteness of the mesoporous titanium dioxide powder and the color of a final product are not influenced.
The specific steps for preparing the modified polyester are as follows:
Dissolving 5-amino isophthalic acid in methanol, adding thionyl chloride under the condition of ice water bath, reacting for 3-4 hours, evaporating to remove methanol, separating an esterification product by adding water, extracting the esterification product by using ethyl acetate, and volatilizing to remove ethyl acetate to obtain 5-amino isophthalic acid dimethyl ester;
The invention also adds 5-amino isophthalic acid di-3-hydroxyethyl into comonomer based on mesoporous titanium dioxide powder with amino functional group, on the 5-amino isophthalic acid di-3-hydroxyethyl, on one hand, aniline group in the structure is used as aromatic amine antioxidant to inhibit thermal oxidative degradation of macromolecule, on the other hand, 5-amino isophthalic acid breaks down the macromolecular structure of polyester, which is beneficial to reducing melting point of modified polyester, on the other hand, amino in the structure reacts with acetaldehyde to generate Schiff base, the acetaldehyde generated by high temperature pyrolysis is chemically bonded on macromolecular chain in situ, reducing acetaldehyde content in polyester melt, reducing acetaldehyde content in modified polyester filament, and reducing influence of modified polyester filament on environment in application.
Esterification reaction of 5-amino isophthalic acid, methanol and thionyl chloride in ice water bath to form dimethyl 5-amino isophthalate. In the reaction process, methyl alcohol and thionyl chloride generate intermediate methyl sulfite chloride, wherein a-OSOCl group in the methyl sulfite is easy to be separated from methyl, and H + which is free from carboxylic acid generates sulfurous acid chloride, the sulfurous acid chloride is easy to decompose, so that the reaction has higher yield and reaction rate, and the separated methyl is combined with carboxylate to form ester. In addition, because of steric hindrance effect, amino on benzene ring does not participate in amidation reaction of carboxylic acid group, amino group is kept unchanged, and synthesized 5-amino isophthalic acid dimethyl ester and ethylene glycol are subjected to transesterification reaction at 180-210 ℃ to obtain a third monomer 5-amino isophthalic acid bis-3-hydroxyethyl ester, wherein by-product is methanol, the boiling point of which is far lower than the reaction temperature, and the methanol is easy to evaporate and remove.
Preparing terephthalic acid, isophthalic acid, ethylene glycol, diglycol and mesoporous titanium dioxide powder into slurry, and performing esterification reaction to obtain an esterification product, wherein the pressure is 0.1-0.3Mpa, and the temperature is 230-250 ℃;
After the esterification reaction is finished, adding 5-amino isophthalic acid bis-3-hydroxyethyl ester into an esterification product, adding a second catalyst and a stabilizer, starting the polycondensation reaction at a low vacuum stage under the condition of negative pressure, smoothly reducing the pressure at the low vacuum stage from normal pressure to below 500Pa absolute pressure, controlling the temperature at 260-270 ℃ for 30-50 min, continuously vacuumizing, performing the polycondensation reaction at a high vacuum stage, reducing the pressure at the high vacuum stage to less than 70Pa absolute pressure, controlling the reaction temperature at 275-280 ℃ and controlling the reaction time at 50-90 min, and thus obtaining the modified polyester.
In some embodiments, the alkylamine is twelve, fourteen, sixteen or octadecylamine, the molar ratio of the alkylamine to the titanium source is 1 (2-3), the volume ratio of the ethanol to the deionized water is 1 (4-5), the concentration of the alkylamine is 2-2.2 wt%, the aging condition is that the room temperature is 20-26 ℃ firstly, the room temperature time is 20-24 h, the temperature is then increased to 90-100 ℃, the heating time is 40-48 h, the extraction condition is that the treatment is performed in an ethanol nitrate solution with pH=2 at room temperature for 12-15 h, the washing condition is that the washing is performed by ethanol suction filtration for 3-5 times, the drying condition is that the drying temperature is 50-60 ℃ and the drying time is 24-30 h.
In some embodiments, the molar ratio of 5-amino isophthalic acid, methanol and thionyl chloride is 1 (35.0-37.5): (3-3.5), the added water volume is 2-3 times that of methanol, the added ethyl acetate volume is 1-1.2 times that of methanol, the molar ratio of 5-amino isophthalic acid dimethyl ester to ethylene glycol is 1 (1.8-2.2), the first catalyst is added in an amount of 0.02% -0.03% of the weight of 5-amino isophthalic acid dimethyl ester, the molar ratio of terephthalic acid, isophthalic acid, ethylene glycol and diethylene glycol is 1 (0.4-0.6): (0.08-0.12): (1.8-2.5), the controllability of the reaction process is good, and the finally obtained modified polyester filament has better performance and better stability.
In some embodiments, the weight of the matting agent is 0.20% -0.25% of the weight of the modified polyester, the molar ratio of the 5-amino isophthalic acid bis-3-hydroxyethyl ester to the terephthalic acid is1 (0.02-0.03), if the weight of the matting agent is less than 0.20% of the weight of the modified polyester, the matting effect is poor, the acetaldehyde absorption effect is poor, and if the weight of the matting agent is more than 0.25% of the weight of the modified polyester, the performance and stability of the modified polyester are affected, and the acetaldehyde absorption effect is not improved obviously.
In some embodiments, the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite, the stabilizer is added in an amount of 0.03-0.05% of the total weight of the terephthalic acid, the second catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, the second catalyst is added in an amount of 0.03-0.05% of the total weight of the terephthalic acid, and the stability and the reaction rate of the reaction process are improved. If the components of the invention are not mentioned in terms of mass percent, mole ratio or volume, the technical effect of the invention is less affected, and the invention is not particularly limited.
In some embodiments, the spinning process of the modified polyester filament comprises the steps of metering and melting modified polyester chips to obtain modified polyester melt, extruding the modified polyester melt through a spinneret orifice, cooling, oiling, stretching, heat setting and winding to obtain the modified polyester filament, wherein the modified polyester filament is stretched by a roller and a roller, the speed difference of the roller and the roller forms a stretching, the roller heats the fiber, the roller heat setting is carried out, the parameters of the modified polyester filament are as follows, the extrusion temperature is 270-280 ℃, the cooling temperature is 20-25 ℃, the roller speed is 2200-2400 m/min, the roller temperature is 65-70 ℃, the roller speed is 3000-3200 m/min, the roller temperature is 150-180 ℃, the winding speed is 2960-3230 m/min, the fineness of the modified polyester filament is 1.5dtex-3.0dtex, the breaking strength is more than or equal to 3.5cN/dtex, the breaking elongation is 50.0+/-5.0% and the acetaldehyde content in the modified polyester filament is less than 0.5ppm.
Example 1
A modified polyester filament comprises a modified polyester and a matting agent, wherein the modified polyester comprises a terephthalic acid chain segment, an isophthalic acid chain segment, an ethylene glycol chain segment, a diethylene glycol chain segment and a 5-amino isophthalic acid bis-3-hydroxyethyl ester chain segment, the matting agent is inorganic mesoporous powder, the surface of the inorganic mesoporous powder contains amino functional groups, the inorganic mesoporous powder is mesoporous titanium dioxide powder, the pore diameter of the mesoporous titanium dioxide powder is 2nm, the specific surface area is 100m 2/g, the particle diameter is 200nm, the content of the amino functional groups is 1wt%, the melting point of the modified polyester is 110 ℃, and the molecular weight of the modified polyester is 18000.
The invention also provides a preparation method of the modified polyester filament, which comprises the following steps:
Preparing a delustering agent and modified polyester, mixing the delustering agent and the modified polyester to obtain a modified polyester chip, and metering, melting, extruding, cooling, oiling, stretching, heat setting and winding the modified polyester chip to obtain the modified polyester filament.
The preparation method of the matting agent comprises the following specific steps:
Adding alkylamine as a template agent and isopropyl titanate as a titanium source into ethanol, mixing and dissolving the template agent and the titanium source, adding deionized water to generate precipitate, aging, filtering, extracting to remove part of the template agent, and then washing and drying to obtain a matting agent, wherein the matting agent is mesoporous titanium dioxide powder;
The aging condition is that the room temperature is 20 ℃ at first, the room temperature time is 20 hours, the temperature is raised to 90 ℃, the temperature rise time is 40 hours, the extraction condition is that the extraction is carried out for 12 hours in an ethanol nitrate solution with the pH value of 2 at room temperature, the washing condition is that the extraction is carried out for 3 times by ethanol suction filtration, the drying condition is that the drying temperature is 50 ℃, and the drying time is 24 hours.
The specific steps for preparing the modified polyester are as follows:
Dissolving 5-amino isophthalic acid in methanol, adding thionyl chloride under the condition of ice water bath, reacting for 3 hours, evaporating to remove methanol, adding water to separate out an esterification product, extracting the esterification product with ethyl acetate, and volatilizing to remove ethyl acetate to obtain 5-amino dimethyl isophthalate;
Performing transesterification reaction on the 5-amino isophthalic acid dimethyl ester and ethylene glycol under the action of a first catalyst, wherein the esterification temperature is 180 ℃ and the esterification time is 2 hours until the transesterification reaction is complete, so as to obtain the 5-amino isophthalic acid bis-3-hydroxyethyl ester;
Preparing terephthalic acid, isophthalic acid, ethylene glycol, diglycol and mesoporous titanium dioxide powder into slurry, and performing esterification reaction to obtain an esterification product, wherein the pressure is 0.1Mpa, the temperature is 230 ℃, and when the distillation amount of water in the esterification reaction reaches more than 95% of theoretical value, the end point of the esterification reaction is the end point of the esterification reaction, so that the esterification product is obtained;
After the esterification reaction is finished, adding 5-amino isophthalic acid bis-3-hydroxyethyl ester into an esterification product, adding a second catalyst and a stabilizer, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, smoothly reducing the pressure in the low vacuum stage from normal pressure to absolute pressure 450Pa, controlling the temperature to 260 ℃, controlling the reaction time to 30min, continuously vacuumizing, performing the polycondensation reaction in a high vacuum stage, reducing the pressure in the high vacuum stage to absolute pressure 60Pa, controlling the reaction temperature to 275 ℃, and controlling the reaction time to 50min, thereby preparing the modified polyester.
The alkylamine is dodecylamine, the mol ratio of the alkylamine to the titanium source is 1:2, the volume ratio of the ethanol to the deionized water is 1:4, and the concentration of the alkylamine is 2wt%.
The molar ratio of 5-amino isophthalic acid, methanol and thionyl chloride is 1:35.0:3, the added water volume is 2 times that of methanol, the added ethyl acetate volume is 1 time that of methanol, the molar ratio of 5-amino isophthalic acid dimethyl ester to ethylene glycol is 1:1.8, the added amount of the first catalyst is 0.02 percent of the weight of 5-amino isophthalic acid dimethyl ester, the molar ratio of terephthalic acid, isophthalic acid, ethylene glycol and diethylene glycol is 1:0.4:0.08:1.8, the weight of the matting agent is 0.20 percent of the weight of the modified polyester, and the molar ratio of 5-amino isophthalic acid bis-3-hydroxyethyl ester to terephthalic acid is 1:0.02.
The stabilizer is triphenyl phosphate, the addition amount of the stabilizer is 0.03 percent of the total weight of terephthalic acid, the second catalyst is antimonous oxide, and the addition amount of the second catalyst is 0.03 percent of the total weight of terephthalic acid.
The spinning process of the modified polyester filament comprises the steps of metering and melting modified polyester chips to obtain modified polyester melt, extruding the modified polyester melt through a spinneret orifice, cooling, oiling, stretching, heat setting and winding to obtain the modified polyester filament, wherein the modified polyester filament is stretched through a first roller and a second roller, the speed difference of the first roller and the second roller is equal to that of the first roller, the first roller heats the modified polyester filament, the second roller is heat set, and parameters of preparing the modified polyester filament are that the extruding temperature is 270 ℃, the cooling temperature is 20 ℃, the first roller speed is 2200m/min, the first roller temperature is 65 ℃, the second roller speed is 3000m/min, the second roller temperature is 150 ℃, and the winding speed is 2960m/min.
The test shows that the fineness of the modified polyester filament is 1.5dtex, the breaking strength is 3.76cN/dtex, the elongation at break is 50.0%, and the acetaldehyde content of the modified polyester filament is 0.43ppm.
Example 2
The modified polyester filament comprises a modified polyester and a matting agent, wherein the modified polyester comprises a terephthalic acid chain segment, an isophthalic acid chain segment, an ethylene glycol chain segment, a diethylene glycol chain segment and a 5-amino isophthalic acid bis-3-hydroxyethyl ester chain segment, the matting agent is inorganic mesoporous powder, the surface of the inorganic mesoporous powder contains amino functional groups, the inorganic mesoporous powder is mesoporous titanium dioxide powder, the pore diameter of the mesoporous titanium dioxide powder is 4nm, the specific surface area is 300m 2/g, the particle diameter is 300nm, the content of the amino functional groups is 3wt%, the melting point of the modified polyester is 150 ℃, and the molecular weight of the modified polyester is 20000.
The invention also provides a preparation method of the modified polyester filament, which comprises the following steps:
Preparing a delustering agent and modified polyester, mixing the delustering agent and the modified polyester to obtain a modified polyester chip, and metering, melting, extruding, cooling, oiling, stretching, heat setting and winding the modified polyester chip to obtain the modified polyester filament.
The preparation method of the matting agent comprises the following specific steps:
Adding alkylamine as a template agent and n-butyl titanate as a titanium source into ethanol, mixing and dissolving the template agent and the titanium source, adding deionized water to generate precipitate, aging, filtering, extracting to remove part of the template agent, and then washing and drying to obtain a matting agent, wherein the matting agent is mesoporous titanium dioxide powder;
The aging condition is that the room temperature is 23 ℃ at first, the room temperature time is 24 hours, the temperature is raised to 100 ℃, the temperature raising time is 48 hours, the extraction condition is that the extraction is carried out in an ethanol nitrate solution with the pH value of 2 at room temperature for 15 hours, the washing condition is that the extraction is carried out by filtering with ethanol for 5 times, the drying condition is that the drying temperature is 60 ℃, and the drying time is 30 hours.
The specific steps for preparing the modified polyester are as follows:
Dissolving 5-amino isophthalic acid in methanol, adding thionyl chloride under the condition of ice water bath, reacting for 4 hours, evaporating to remove methanol, adding water to separate out an esterification product, extracting the esterification product with ethyl acetate, and volatilizing to remove ethyl acetate to obtain 5-amino isophthalic acid dimethyl ester;
Performing transesterification reaction on the 5-amino isophthalic acid dimethyl ester and ethylene glycol under the action of a first catalyst, wherein the esterification temperature is 210 ℃ and the esterification time is 3 hours until the transesterification reaction is complete, so as to obtain the 5-amino isophthalic acid bis-3-hydroxyethyl ester;
Preparing terephthalic acid, isophthalic acid, ethylene glycol, diglycol and mesoporous titanium dioxide powder into slurry, and performing esterification reaction to obtain an esterification product, wherein the pressure is 0.3Mpa, the temperature is 250 ℃, and when the distillation amount of water in the esterification reaction reaches more than 95% of theoretical value, the end point of the esterification reaction is the end point of the esterification reaction, so that the esterification product is obtained;
After the esterification reaction is finished, adding 5-amino isophthalic acid bis-3-hydroxyethyl ester into an esterification product, adding a second catalyst and a stabilizer, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, smoothly reducing the pressure in the low vacuum stage from normal pressure to absolute pressure 450Pa, controlling the temperature to 270 ℃, controlling the reaction time to 50min, continuously vacuumizing, performing the polycondensation reaction in a high vacuum stage, reducing the pressure in the high vacuum stage to absolute pressure 65Pa, controlling the reaction temperature to 280 ℃, and controlling the reaction time to 90min to obtain the modified polyester.
The alkylamine is tetradecylamine, the mole ratio of the alkylamine to the titanium source is 1:3, the volume ratio of ethanol to deionized water is 1:5, the concentration of the alkylamine is 2.2wt%, and the mole ratio of the 5-amino isophthalic acid bis-3-hydroxyethyl ester to terephthalic acid is 1:0.025.
The molar ratio of 5-amino isophthalic acid, methanol and thionyl chloride is 1:37.5:3.5, the added water volume is 3 times that of methanol, the added ethyl acetate volume is 1.2 times that of methanol, the molar ratio of 5-amino isophthalic acid dimethyl ester to ethylene glycol is 1:2.2, the added amount of the first catalyst is 0.03 percent of the weight of 5-amino isophthalic acid dimethyl ester, the molar ratio of terephthalic acid, isophthalic acid, ethylene glycol and diethylene glycol is 1:0.6:0.12:2.5, the weight of the matting agent is 0.25 percent of the weight of modified polyester, and the molar ratio of 5-amino isophthalic acid bis-3-hydroxyethyl ester to terephthalic acid is 1:0.03.
The stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite, the addition of the stabilizer is 0.05% of the total weight of terephthalic acid, the second catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, and the addition of the second catalyst is 0.05% of the total weight of terephthalic acid.
The spinning process of the modified polyester filament comprises the steps of metering and melting modified polyester chips to obtain modified polyester melt, extruding the modified polyester melt through a spinneret orifice, cooling, oiling, stretching, heat setting and winding to obtain the modified polyester filament, wherein the modified polyester filament is stretched by a first roller and a second roller, the first roller and the second roller are subjected to speed difference to heat the modified polyester filament, the second roller is subjected to heat setting, and parameters of the modified polyester filament preparation are that the extruding temperature is 280 ℃, the cooling temperature is 25 ℃, the first roller speed is 2400m/min, the first roller temperature is 70 ℃, the second roller speed is 3200m/min, the second roller temperature is 180 ℃, and the winding speed is 3230m/min.
The test shows that the fineness of the modified polyester filament is 3.0dtex, the breaking strength is 3.82cN/dtex, the elongation at break is 55.0%, and the acetaldehyde content in the modified polyester filament is 0.38ppm.
Example 3
A modified polyester filament comprises a modified polyester and a matting agent, wherein the modified polyester comprises a terephthalic acid chain segment, an isophthalic acid chain segment, an ethylene glycol chain segment, a diethylene glycol chain segment and a 5-amino isophthalic acid bis-3-hydroxyethyl ester chain segment, the matting agent is inorganic mesoporous powder, the surface of the inorganic mesoporous powder contains amino functional groups, the inorganic mesoporous powder is mesoporous titanium dioxide powder, the pore diameter of the mesoporous titanium dioxide powder is 3nm, the specific surface area is 200m 2/g, the particle diameter is 260nm, the content of the amino functional groups is 2wt%, the melting point of the modified polyester is 130 ℃, and the molecular weight of the modified polyester is 22000.
The invention also provides a preparation method of the modified polyester filament, which comprises the following steps:
Preparing a delustering agent and modified polyester, mixing the delustering agent and the modified polyester to obtain a modified polyester chip, and metering, melting, extruding, cooling, oiling, stretching, heat setting and winding the modified polyester chip to obtain the modified polyester filament.
The preparation method of the matting agent comprises the following specific steps:
the preparation method comprises the steps of taking alkylamine as a template agent, taking isopropyl titanate or n-butyl titanate as a titanium source, adding the template agent and the titanium source into ethanol, mixing and dissolving, adding deionized water to generate precipitate, aging, filtering, extracting to remove part of the template agent, and then washing and drying to obtain a matting agent, wherein the matting agent is mesoporous titanium dioxide powder;
The aging condition is room temperature 25 ℃, the room temperature time is 24 hours, the temperature is raised to 95 ℃, the temperature raising time is 45 hours, the extraction condition is that the mixture is treated in an ethanol nitrate solution with pH=2 for 13 hours at room temperature, the washing condition is that the mixture is washed by ethanol suction filtration for 4 times, the drying condition is that the drying temperature is 55 ℃, and the drying time is 25 hours.
The specific steps for preparing the modified polyester are as follows:
Dissolving 5-amino isophthalic acid in methanol, adding thionyl chloride under the condition of ice water bath, reacting for 4 hours, evaporating to remove methanol, adding water to separate out an esterification product, extracting the esterification product with ethyl acetate, and volatilizing to remove ethyl acetate to obtain 5-amino isophthalic acid dimethyl ester;
Performing transesterification reaction on the 5-amino isophthalic acid dimethyl ester and ethylene glycol under the action of a first catalyst, wherein the esterification temperature is 200 ℃ and the esterification time is 3 hours until the transesterification reaction is complete, so as to obtain the 5-amino isophthalic acid bis-3-hydroxyethyl ester;
Preparing terephthalic acid, isophthalic acid, ethylene glycol, diglycol and mesoporous titanium dioxide powder into slurry, and performing esterification reaction to obtain an esterification product, wherein the pressure is 0.2Mpa, the temperature is 240 ℃, and when the distillation amount of water in the esterification reaction reaches more than 95% of theoretical value, the end point of the esterification reaction is the end point of the esterification reaction, so that the esterification product is obtained;
After the esterification reaction is finished, adding 5-amino isophthalic acid bis-3-hydroxyethyl ester into an esterification product, adding a second catalyst and a stabilizer, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, smoothly reducing the pressure in the low vacuum stage from normal pressure to absolute pressure 450Pa, controlling the temperature at 265 ℃, controlling the reaction time at 40min, continuously vacuumizing, performing the polycondensation reaction in a high vacuum stage, reducing the pressure in the high vacuum stage to absolute pressure 65Pa, controlling the reaction temperature at 280 ℃ and controlling the reaction time at 80min, and thus obtaining the modified polyester.
The alkylamine is octadecylamine, the mol ratio of the alkylamine to the titanium source is 1:3, the volume ratio of the ethanol to the deionized water is 1:5, and the concentration of the alkylamine is 2.1wt%.
The molar ratio of 5-amino isophthalic acid, methanol and thionyl chloride is 1:36:3.5, the added water volume is 3 times that of methanol, the added ethyl acetate volume is 1.2 times that of methanol, the molar ratio of 5-amino isophthalic acid dimethyl ester to ethylene glycol is 1:2, the added amount of the first catalyst is 0.03 percent of the weight of 5-amino isophthalic acid dimethyl ester, the molar ratio of terephthalic acid, isophthalic acid, ethylene glycol and diethylene glycol is 1:0.5:0.1:2, the weight of the flatting agent is 0.22 percent of the weight of the modified polyester, and the molar ratio of 5-amino isophthalic acid bis-3-hydroxyethyl ester to terephthalic acid is 1:0.03.
The stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite, the addition of the stabilizer is 0.04% of the total weight of terephthalic acid, the second catalyst is ethylene glycol antimony, and the addition of the second catalyst is 0.04% of the total weight of terephthalic acid.
The modified polyester filaments were prepared at an extrusion temperature of 275℃and a cooling temperature of 24℃and a roll speed of 2300m/min, a roll temperature of 70℃and a roll speed of 3100m/min, a roll temperature of 160℃and a winding speed of 3200m/min.
The test shows that the titer of the modified polyester filament is 2.0dtex, the breaking strength is 3.78cN/dtex, the elongation at break is 52.0%, and the acetaldehyde content in the modified polyester filament is 0.46ppm.
It is seen from examples 1, 2 and 3 that the content of acetaldehyde is small, the effect of eliminating acetaldehyde is good, and the mechanical properties are good.
Any numerical value recited herein includes all values of the lower and upper values that are incremented by one unit from the lower value to the upper value, as long as there is a separation of at least two units between any lower value and any higher value. For example, if it is stated that the number of components or the value of a process variable (e.g., temperature, pressure, time, etc.) is from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, then the purpose is to explicitly list such values as 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc. in this specification as well. For values less than 1, one unit is suitably considered to be 0.0001, 0.001, 0.01, 0.1. These are merely examples that are intended to be explicitly recited in this description, and all possible combinations of values recited between the lowest value and the highest value are believed to be explicitly stated in the description in a similar manner.
Unless otherwise indicated, all ranges include endpoints and all numbers between endpoints. "about" or "approximately" as used with a range is applicable to both endpoints of the range. Thus, "about 20 to 30" is intended to cover "about 20 to about 30," including at least the indicated endpoints.
All articles and references, including patent applications and publications, disclosed herein are incorporated by reference for all purposes. The term "consisting essentially of" describing a combination shall include the identified element, ingredient, component or step as well as other elements, ingredients, components or steps that do not substantially affect the essential novel features of the combination. The use of the terms "comprises" or "comprising" to describe combinations of elements, components, or steps herein also contemplates embodiments consisting essentially of such elements, components, or steps. By using the term "may" herein, it is intended that any attribute described as "may" be included is optional.
Multiple elements, components, parts or steps can be provided by a single integrated element, component, part or step. Alternatively, a single integrated element, component, part or step may be divided into separate plural elements, components, parts or steps. The disclosure of "a" or "an" to describe an element, component, section or step is not intended to exclude other elements, components, sections or steps.
It is to be understood that the above description is not intended to be limiting. Many embodiments and many applications other than the examples provided will be apparent to those of skill in the art upon reading the above description. The scope of the present teachings should, therefore, be determined not with reference to the above description, but instead should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated herein by reference for the purpose of completeness. The omission of any aspect of the subject matter disclosed herein in the preceding claims is not intended to forego such subject matter, nor should the inventors regard such subject matter as not be considered to be part of the disclosed subject matter.
Claims (10)
1. The modified polyester filament is characterized by comprising a modified polyester and a matting agent, wherein the modified polyester comprises a terephthalic acid chain segment, an isophthalic acid chain segment, an ethylene glycol chain segment, a diethylene glycol chain segment and a 5-amino isophthalic acid bis-3-hydroxyethyl segment, and the matting agent is inorganic mesoporous powder, and the surface of the inorganic mesoporous powder contains amino functional groups.
2. The modified polyester filament according to claim 1, wherein the inorganic mesoporous powder is mesoporous titanium dioxide powder, the pore diameter of the mesoporous titanium dioxide powder is 2nm-4nm, the specific surface area is 100m 2/g-300m2/g, the particle size is 200nm-300nm, and the content of the amino functional group is 1wt% to 3wt%.
3. The modified polyester filament according to claim 2, wherein the modified polyester has a melting point of 110 ℃ to 150 ℃ and a molecular weight of 18000 to 22000.
4. A process for the preparation of modified polyester filaments according to any one of claims 2 to 3, characterized by comprising the steps of:
Preparing a delustering agent and modified polyester, mixing the delustering agent and the modified polyester to obtain modified polyester chips, and metering, melting, extruding, cooling, oiling, stretching, heat setting and winding the modified polyester chips to obtain modified polyester filaments.
5. The preparation method according to claim 4, wherein the specific steps for preparing the matting agent are as follows:
The preparation method comprises the steps of taking alkylamine as a template agent, taking isopropyl titanate or n-butyl titanate as a titanium source, adding the template agent and the titanium source into ethanol, mixing and dissolving, adding deionized water to generate precipitate, aging, filtering, extracting to remove part of the template agent, and then washing and drying to obtain the matting agent, wherein the matting agent is mesoporous titanium dioxide powder;
the specific steps for preparing the modified polyester are as follows:
Dissolving 5-amino isophthalic acid in methanol, adding thionyl chloride under the condition of ice water bath, reacting for 3-4 hours, evaporating to remove methanol, separating an esterification product by adding water, extracting the esterification product by using ethyl acetate, and volatilizing to remove ethyl acetate to obtain 5-amino isophthalic acid dimethyl ester;
performing transesterification reaction on the 5-amino isophthalic acid dimethyl ester and ethylene glycol under the action of a first catalyst, wherein the esterification temperature is 180-210 ℃ and the esterification time is 2-3 hours until the transesterification reaction is complete, so as to obtain the 5-amino isophthalic acid bis-3-hydroxyethyl ester;
Preparing terephthalic acid, isophthalic acid, ethylene glycol, diglycol and mesoporous titanium dioxide powder into slurry, and performing esterification reaction to obtain an esterification product, wherein the pressure is 0.1-0.3Mpa, and the temperature is 230-250 ℃;
After the esterification reaction is finished, adding 5-amino isophthalic acid bis-3-hydroxyethyl ester into an esterification product, adding a second catalyst and a stabilizer, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, wherein the pressure in the low vacuum stage is steadily reduced to below 500Pa absolute pressure from normal pressure, the temperature is controlled to be 260-270 ℃ and the reaction time is 30-50 min, then continuously vacuumizing, performing the polycondensation reaction in a high vacuum stage, the pressure in the high vacuum stage is reduced to be less than 70Pa absolute pressure, the reaction temperature is controlled to be 275-280 ℃ and the reaction time is 50-90 min, and obtaining the modified polyester.
6. The method according to claim 5, wherein the alkylamine is twelve, fourteen, sixteen or octadecylamine, the molar ratio of the alkylamine to the titanium source is 1 (2-3), the volume ratio of the ethanol to the deionized water is 1 (4-5), the concentration of the alkylamine is 2-2.2 wt%, the aging condition is room temperature first, the room temperature time is 20-24 hours, the temperature is raised to 90-100 ℃, the temperature is raised to 40-48 hours, the extraction condition is 12-15 hours in an ethanol nitrate solution with pH=2 at room temperature, the washing condition is 3-5 times of washing with ethanol by suction, the drying condition is 50-60 ℃ and the drying time is 24-30 hours.
7. The process according to claim 5, wherein the molar ratio of 5-aminoisophthalic acid, methanol and thionyl chloride is 1 (35.0-37.5) (3-3.5), the water content is 2-3 times that of methanol, the ethyl acetate is 1-1.2 times that of methanol, the molar ratio of 5-aminoisophthalic acid dimethyl ester to ethylene glycol is 1 (1.8-2.2), the first catalyst is added in an amount of 0.02-0.03% by weight of 5-aminoisophthalic acid dimethyl ester, and the molar ratio of terephthalic acid, isophthalic acid, ethylene glycol and diethylene glycol is 1 (0.4-0.6) (0.08-0.12) (1.8-2.5).
8. The process according to claim 5, wherein the matting agent comprises 0.20 to 0.25% by weight of the modified polyester and the molar ratio of 5-aminoisophthalic acid bis-3-hydroxyethyl ester to terephthalic acid is 1 (0.02 to 0.03).
9. The preparation method according to claim 5, wherein the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite, the stabilizer is added in an amount of 0.03-0.05% of the total weight of terephthalic acid, the first catalyst is zinc acetate, the second catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, and the second catalyst is added in an amount of 0.03-0.05% of the total weight of terephthalic acid.
10. The process according to claim 4, wherein the modified polyester filaments having a fineness of 1.5dtex to 3.0dtex, a breaking strength of not less than 3.5cN/dtex, an elongation at break of 50.0.+ -. 5.0% and an acetaldehyde content of <0.5ppm are produced by extruding at 270 ℃ to 280 ℃ and cooling at 20 ℃ to 25 ℃, a roll speed of 2200m/min to 2400m/min, a roll temperature of 65 ℃ to 70 ℃, a roll speed of 3000m/min to 3200m/min, a roll temperature of 150 ℃ to 180 ℃ and a winding speed of 2960m/min to 3230 m/min.
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| US20020128427A1 (en) * | 2000-09-15 | 2002-09-12 | Eckehart Schaaf | Method for producing polyesters with a reduced content of free acetaldehyde |
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| WO2021035122A1 (en) * | 2019-08-22 | 2021-02-25 | Penn Color, Inc. | Delustered fiber |
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| US20020128427A1 (en) * | 2000-09-15 | 2002-09-12 | Eckehart Schaaf | Method for producing polyesters with a reduced content of free acetaldehyde |
| JP2004307597A (en) * | 2003-04-04 | 2004-11-04 | Mitsui Chemicals Inc | Method for producing polyethylene terephthalate |
| CN107641196A (en) * | 2017-09-25 | 2018-01-30 | 张家港美景荣化学工业有限公司 | A kind of dull polyester and low-gloss elastic composite fiber |
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