Yellow polyester color master batch as well as preparation method and application thereof

Abstract

The invention discloses a yellow polyester color master batch as well as a preparation method and application thereof, and belongs to the technical field of polymer dye synthesis. The preparation method of the yellow polyester color master batch comprises the following steps: in the presence of a catalyst, carrying out prepolymerization reaction on a yellow monomer containing diester groups, dibasic acid and dihydric alcohol to obtain a prepolymer; and carrying out vacuum polycondensation on the prepolymer. The method is simple to operate and suitable for industrial production. The obtained yellow polyester color master batch has excellent migration resistance and color fastness, also has good thermal stability and polyester compatibility, can effectively reduce color migration of fiber products, and significantly improves color fastness and coloring uniformity.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer dye synthesis, and more particularly, to a yellow polyester color masterbatch, a preparation method thereof, and an application thereof. Background Art

[0002] Traditional colorants are mostly based on small molecule compounds and pigments. Among them, the structures of small molecule dyes are relatively simple, and they may degrade and fade under extreme conditions. Due to their poor solubility, pigments may cause uneven dyeing and quality problems such as color difference. In addition, the coloring of small molecule dyes and pigments is based on intermolecular van der Waals forces, hydrogen bonds, π-π stacking, electrostatic interactions, etc., and often relies on chemical bonding or physical adsorption to adhere to the surface of the substrate. Therefore, the stability and uniformity of the dyeing effect are poor.

[0003] In the textile industry, the coloring mechanism of traditional color masterbatches mainly relies on non-covalent interactions between pigments or small molecule dyes and substrates. This non-covalent force is relatively weak, resulting in easy migration of dye molecules during storage, washing, and mechanical friction, etc., which in turn causes significant decolorization phenomena. This not only affects the product performance but also may cause environmental pollution.

[0004] In view of this, the present invention is specifically proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide a yellow polyester color masterbatch, a preparation method thereof, and an application thereof to solve or improve the above technical problems.

[0006] The present invention can be implemented as follows:

[0007] In a first aspect, the present invention provides a preparation method of a yellow polyester color masterbatch, including the following steps: under the condition of the presence of a catalyst, subject a yellow monomer containing a double ester group, a dicarboxylic acid, and a diol to a prepolymerization reaction to obtain a prepolymer; subject the prepolymer to vacuum polycondensation.

[0008] In an optional embodiment, the prepolymerization reaction is carried out at 230°C to 250°C and normal pressure for 2 h to 5 h.

[0009] In an optional embodiment, the molar ratio of the yellow monomer containing a double ester group, the diol, and the dicarboxylic acid is (0.5 - 0.7):(1 - 1.1):(0.3 - 0.5).

[0010] In an optional embodiment, the diol includes at least one of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, neopentyl glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, and decylene glycol.

[0011] In an alternative embodiment, the dibasic acid includes at least one of terephthalic acid, isophthalic acid, phthalic acid, adipic acid, succinic acid, and glutaric acid.

[0012] In an alternative embodiment, the catalyst includes at least one of dibutyltin oxide, tetrabutyl titanate, and antimony glycolate.

[0013] In an alternative embodiment, the addition amount of the catalyst is 200 ppm to 300 ppm of the reaction raw materials by mass, and the reaction raw materials are composed of a yellow monomer containing a double ester group, a diol, and a dibasic acid.

[0014] In an alternative embodiment, the polycondensation reaction is carried out at 260 °C to 280 °C and a vacuum degree < 200 Pa for 4 h to 8 h.

[0015] In an alternative embodiment, the chemical structural formula of the yellow monomer containing a double ester group includes

[0016]

[0017] at least one of;

[0018] wherein, R is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl.

[0019] In an alternative embodiment, the synthesis method of the yellow monomer containing a double ester group includes: reacting diaminoanthraquinone with an acyl chloride substance in the presence of a base and a solvent.

[0020] In an alternative embodiment, the reaction of diaminoanthraquinone with an acyl chloride substance is carried out at 0 °C to 20 °C for 10 h to 18 h.

[0021] In an alternative embodiment, the diaminoanthraquinone includes at least one of 1,8-diaminoanthraquinone and 1,5-diaminoanthraquinone.

[0022] In an alternative embodiment, the acyl chloride substance includes at least one of 4-alkoxycarbonylbenzoyl chloride and 3-alkoxycarbonylbenzoyl chloride.

[0023] In an alternative embodiment, the molar amount of the acyl chloride substance is 2.0 times to 2.2 times that of diaminoanthraquinone.

[0024] In an alternative embodiment, the base includes at least one of triethylamine, tri-n-butylamine, pyridine, dicyclohexylamine, di-tert-butylamine, potassium carbonate, potassium phosphate, and sodium phosphate.

[0025] In an alternative embodiment, the molar addition amount of the base is 2 times to 4 times that of diaminoanthraquinone.

[0026] In an alternative embodiment, the solvent comprises at least one of dichloromethane, dichloroethane, and chloroform.

[0027] In an alternative embodiment, the weight of the solvent is 4 to 5 times that of diaminoanthraquinone.

[0028] In an alternative embodiment, the addition amount of the solvent is 50% to 60% of the reactor volume.

[0029] In a second aspect, the present invention provides a yellow polyester color masterbatch prepared by the preparation method of any one of the foregoing embodiments.

[0030] In an alternative embodiment, the molecular weight of the yellow polyester color masterbatch is 10,000 g / mol to 30,000 g / mol;

[0031] and / or, the glass transition temperature of the yellow polyester color masterbatch is 40°C to 85°C.

[0032] In a third aspect, the present invention provides a fiber product, and the raw materials for preparing the fiber product include polyester and the yellow polyester color masterbatch of the foregoing embodiments.

[0033] In an alternative embodiment, the polyester comprises at least one of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polylactic acid.

[0034] In a fourth aspect, the present invention provides a method for preparing a fiber product as in the foregoing embodiments, comprising the following steps: melt-blending and spinning the polyester and the yellow polyester color masterbatch together.

[0035] In an alternative embodiment, the mass of the yellow polyester color masterbatch is 1% to 10% of the total mass of the polyester and the yellow polyester color masterbatch.

[0036] The beneficial effects of the present invention include:

[0037] The present invention provides a novel covalently bonded macromolecular yellow polyester color masterbatch. Specifically, a yellow monomer is introduced into the polymer main chain by a chemical bonding method, realizing the covalent embedding of the chromophore into the polymer chain. This molecular design strategy endows the color masterbatch with significant advantages: First, due to the strong covalent bonding of the chromophore, its migration resistance is significantly improved; second, this type of polyester color masterbatch has excellent compatibility with the matrix polyester, enabling uniform dispersion without granulation. This characteristic enables the polyester colored thereby to be processed into high-performance fibers such as filaments and long filaments, while the traditional pigment coloring system is limited by the pigment particle size and it is difficult to prepare filaments.

[0038] More importantly, while maintaining the excellent coloring uniformity of small molecule dyes, this new type of masterbatch system also inherits the stability characteristics of pigments and polymers. Its excellent color fastness and migration resistance can significantly reduce the potential environmental pollution of products during processing and use, embodying the concept of green chemistry. This molecular design strategy provides a new idea for the development of high-performance and environmentally friendly textile masterbatches. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as limiting the scope. For those of ordinary skill in the art, other related drawings can be obtained based on these drawings without creative efforts.

[0040] Figure 1 A physical picture of the fiber obtained in Example 1;

[0041] Figure 2 A physical picture of the polyester fiber cloth sample made from the fiber provided in Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0042] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. For those conditions not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0043] The following specifically describes the yellow polyester masterbatch provided by the present invention, its preparation method, and its application.

[0044] The present invention provides a method for preparing a yellow polyester masterbatch, which includes the following steps: under the presence of a catalyst, subject a yellow monomer containing a diester group, a dibasic acid, and a diol to a prepolymerization reaction to obtain a prepolymer; subject the prepolymer to vacuum polycondensation.

[0045] Among them, the prepolymerization reaction is carried out at 230°C to 250°C and normal pressure for 2h to 5h. Among them, the temperature of the prepolymerization reaction can be 230°C, 235°C, 240°C, 245°C, or 250°C, etc., or other values within the range of 230°C to 250°C. The time of the prepolymerization reaction can be 2h to 5h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, or 5h, etc., or other values within the range of 2h to 5h.

[0046] The molar ratio of the yellow monomer containing a diester group, diol, and dibasic acid can be (0.5 - 0.7):(1 - 1.1):(0.3 - 0.5), such as 0.5:1:0.3, 0.5:1:0.4, 0.5:1:0.5, 0.6:1.05:0.4, or 0.7:1.1:0.5, etc., and can also be other values within the range of (0.5 - 0.7):(1 - 1.1):(0.3 - 0.5).

[0047] The colorless diol can include at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol.

[0048] The dibasic acid can include at least one of terephthalic acid, isophthalic acid, phthalic acid, adipic acid, succinic acid, and glutaric acid.

[0049] The catalyst can include at least one of dibutyltin oxide, tetrabutyl titanate, and ethylene glycol antimonide. By mass, the addition amount of the catalyst can be 200 ppm - 300 ppm of the reaction raw materials, such as 200 ppm, 250 ppm, or 300 ppm, etc., and can also be other values within the range of 200 ppm - 300 ppm. Among them, the reaction raw materials are composed of the yellow monomer containing a diester group, diol, and dibasic acid.

[0050] In the present invention, the polycondensation reaction is carried out for 4 h - 8 h under the conditions of 260°C - 280°C and a vacuum degree < 200 Pa. Among them, the temperature of the polycondensation reaction can be 260°C - 280°C, such as 260°C, 265°C, 270°C, 275°C, or 280°C, etc., and can also be other values within the range of 260°C - 280°C. The vacuum degree of the polycondensation reaction can be 250 Pa, 200 Pa, 150 Pa, 100 Pa, or 50 Pa, etc., and can also be other values within the range of < 300 Pa.

[0051] In the present invention, the chemical structural formula of the yellow monomer containing a diester group includes:

[0052]

[0053] at least one of them; among them, R is selected from hydrogen, methyl, ethyl, n - propyl, isopropyl, n - butyl, or tert - butyl.

[0054] In the present invention, the synthesis method of the yellow monomer containing a diester group includes: reacting diaminoanthraquinone with acyl chloride substances in the presence of a base and a solvent.

[0055] Among them, the reaction of diaminoanthraquinone with acyl chloride substances is carried out under the conditions of 0°C to 20°C for 10h to 18h. The reaction temperature of diaminoanthraquinone with acyl chloride substances can be 0°C, 5°C, 10°C, 15°C or 20°C, etc., or other values within the range of 0°C to 20°C. The reaction time of diaminoanthraquinone with acyl chloride substances can be 10h, 12h, 14h, 16h or 18h, etc., or other values within the range of 10h to 18h.

[0056] The above-mentioned diaminoanthraquinone can include at least one of 1,8-diaminoanthraquinone and 1,5-diaminoanthraquinone. The acyl chloride substances can include at least one of 4-alkoxycarbonylbenzoyl chloride and 3-alkoxycarbonylbenzoyl chloride. The molar amount of the acyl chloride substance can be 2.0 times to 2.2 times that of diaminoanthraquinone, such as 2 times, 2.05 times, 2.1 times, 2.15 times or 2.2 times, etc., or other values within the range of 2.0 times to 2.2 times.

[0057] The above-mentioned base can include at least one of triethylamine, tri-n-butylamine, pyridine, dicyclohexylamine, di-tert-butylamine, potassium carbonate, potassium phosphate and sodium phosphate. The molar addition amount of the base can be 2 times to 4 times that of diaminoanthraquinone, such as 2 times, 2.5 times, 3 times, 3.5 times or 4 times, etc., or other values within the range of 2 times to 4 times.

[0058] The above-mentioned solvent can include at least one of dichloromethane, dichloroethane and chloroform. The weight of the solvent can be 4 times to 5 times that of diaminoanthraquinone, such as 4 times, 4.5 times or 5 times, etc., or other values within the range of 4 times to 5 times. In the actual synthesis or preparation process, the addition amount of the solvent can be controlled to be 50% to 60% of the reactor volume (such as 50%, 55% or 60%, etc.).

[0059] The heat-resistant yellow monomer used in the present invention is based on anthraquinone solvent yellow dye, in which the amide bond is a strong chemical bond, ensuring its sufficient thermal stability and no color change during the polymerization or melt spinning process; at the same time, the double ester groups in the molecule ensure that it can be introduced into the polyester macromolecule through copolymerization. In addition, the overall molecular structure of this type of monomer is linear, making the corresponding polymer have sufficient flexibility to ensure its processability. This type of yellow monomer is based on industrialized diaminoanthraquinone and other cheap and easily available industrial products, and the overall cost is controllable, which is conducive to large-scale production and promotion. Copolymerizing the yellow monomer with diol and dicarboxylic acid can prepare the corresponding color masterbatch. During the polymerization process, by adjusting conditions such as reaction temperature, pressure, time, catalyst, etc., the molecular weight range of the color masterbatch can be controlled, and at the same time, it is ensured that the yellow monomer is evenly distributed in the polymer chain to achieve uniform coloring.

[0060] Continuing from the above, the present invention provides a novel covalently bonded macromolecular yellow polyester color masterbatch. Specifically, the yellow monomer is introduced into the polymer main chain through chemical bonding, realizing the covalent embedding of the chromophore into the polymer chain. This molecular design strategy endows the color masterbatch with significant advantages: First, due to the firm covalent bonding of the chromophore, its migration resistance performance is significantly improved; Second, this type of polyester color masterbatch has excellent compatibility with the matrix polyester, enabling uniform dispersion without granulation. This property allows the polyester colored thereby to be processed into high-performance fibers such as filaments and long filaments, while the traditional pigment coloring system is limited by the pigment particle size and it is difficult to prepare filaments.

[0061] More importantly, while maintaining the excellent coloring uniformity of small molecule dyes, this novel color masterbatch system also inherits the stability characteristics of pigments and polymers. Its excellent color fastness and migration resistance performance can significantly reduce the potential environmental pollution during the processing and use of products, embodying the concept of green chemistry. This molecular design strategy provides a new idea for the development of high-performance and environmentally friendly textile color masterbatches.

[0062] Correspondingly, the present invention also provides a yellow polyester color masterbatch prepared by the above preparation method.

[0063] The yellow polyester color masterbatch provided by the present invention not only has the coloring uniformity of small molecule dyes, but also has the stability of pigments and polymers, and can reduce color migration, improve the color fastness and coloring uniformity of products during the melt spinning process.

[0064] The molecular weight of the above yellow polyester color masterbatch can be 10,000 g / mol to 30,000 g / mol (the test method is the viscosity method, specifically referring to GB / T 14189-2015), and the glass transition temperature can be 40 °C to 85 °C.

[0065] In addition, the present invention also provides a fiber product, and the raw materials for preparing this fiber product include polyester and the above yellow polyester color masterbatch.

[0066] The above polyester can include at least one of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polylactic acid.

[0067] Correspondingly, the present invention also provides a preparation method for the above fiber product, including the following steps: melt-blending and spinning the polyester and the yellow polyester color masterbatch together.

[0068] The mass of the above yellow polyester color masterbatch accounts for about 1% to 10% of the total mass of the polyester and the yellow polyester color masterbatch, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc., and can also be other values within the range of 1% to 10%.

[0069] Exemplarily, melt blending and spinning can be carried out in the UDY mode (untreated draw yarn mode), POY mode (pre-oriented yarn mode) or FDY mode (fully drawn yarn mode).

[0070] Among them, the process parameters corresponding to the UDY mode may include: the spinning temperature is 220°C to 260°C (such as 220°C, 240°C or 260°C, etc.), the spinning speed is 500 m / min to 1500 m / min (such as 500 m / min, 1000 m / min or 1500 m / min, etc.), the cooling air temperature is 20°C to 30°C (such as 20°C, 25°C or 30°C, etc.), the cooling air speed is 0.4 m / s to 1 m / s (such as 0.4 m / s, 0.8 m / s or 1 m / s, etc.), and the relative humidity of the cooling air is 60% to 70% (such as 60%, 65% or 70%, etc.).

[0071] The process parameters corresponding to the POY mode may include: the spinning temperature is 220°C to 260°C (such as 220°C, 240°C or 260°C, etc.), the spinning speed is 1000 m / min to 2500 m / min (such as 1000 m / min, 1500 m / min, 2000 m / min or 2500 m / min, etc.), the cooling air temperature is 15°C to 25°C (such as 15°C, 20°C or 25°C, etc.), the cooling air speed is 0.4 m / s to 0.7 m / s (such as 0.4 m / s, 0.6 m / s or 0.7 m / s, etc.), and the relative humidity of the cooling air is 60% to 75% (such as 60%, 65%, 70% or 75%, etc.).

[0072] The process parameters corresponding to the FDY mode may include: the spinning temperature is 220°C to 260°C (such as 220°C, 240°C or 260°C, etc.), the spinning speed is 1500 m / min to 3500 m / min (such as 1500 m / min, 2000 m / min, 2500 m / min, 3000 m / min or 3500 m / min, etc.), the cooling air temperature is 15°C to 20°C (such as 15°C, 18°C or 20°C, etc.), the cooling air speed is 0.3 m / s to 0.6 m / s (such as 0.3 m / s, 0.5 m / s or 0.6 m / s, etc.), and the relative humidity of the cooling air is 70% to 85% (such as 70%, 75%, 80% or 85%, etc.).

[0073] The features and properties of the present invention will be further described in detail below in conjunction with the embodiments.

[0074] Example 1

[0075] This example provides a fiber product, and its preparation method is as follows:

[0076] (1) Synthesize the yellow monomer according to the following route:

[0077]

[0078] Under an ice - water bath, dichloromethane (the weight of dichloromethane is 4 times that of 1,8 - diaminoanthraquinone) was added to the reaction kettle, and the volume was 50% of the total volume of the container; subsequently, 1,8 - diaminoanthraquinone and triethylamine were added thereto, and the molar ratio of 1,8 - diaminoanthraquinone to triethylamine was 1:2.2. After the temperature dropped below 5°C, 4 - ethoxycarbonylbenzoyl chloride (4 - ethoxycarbonylbenzoyl chloride was 2.05 times the molar amount of 1,8 - diaminoanthraquinone) was added dropwise. After stirring and reacting at this temperature for 18 h, the solvent was removed by distillation, saturated sodium bicarbonate solution was added until no bubbles were generated, and after filtration, washing with water and drying, yellow monomer 1 was obtained.

[0079] (2) Synthesis of yellow polyester color masterbatch:

[0080] Neopentyl glycol, terephthalic acid, yellow monomer 1 and tetrabutyl titanate were put into a reactor for prepolymerization reaction. The molar ratio of neopentyl glycol, terephthalic acid to yellow monomer 1 was 0.6:1.1:0.4. The addition amount of tetrabutyl titanate was 250 ppm of the reaction raw materials. After prepolymerization at 240°C for 4 h, vacuum polycondensation was carried out at 260°C and 150 Pa for 8 h. The obtained melt was filtered (60 μm) and then water - cooled and pelletized to obtain a yellow masterbatch. The molecular weight of this yellow polyester color masterbatch was 25000 g / mol, and the glass transition temperature was 75°C.

[0081] (3) Preparation of polyester fibers:

[0082] The polyester and the yellow polyester color masterbatch were melt - blended and spun together. The yellow polyester color masterbatch accounted for 3% of the total mass of the polyester and the yellow polyester color masterbatch. The spinning process was UDY, and the process parameters included: the spinning temperature was 260°C, the spinning speed was 1500 m / min, the cooling air temperature was 30°C, the cooling air speed was 0.6 m / s, and the relative humidity of the cooling air was 65%.

[0083] Example 2

[0084] This example provides a fiber product, and its preparation method is as follows:

[0085] (1) Synthesize yellow monomer according to the following route:

[0086]

[0087] Under an ice-water bath, dichloroethane (the weight of dichloroethane is 4 times that of 1,5-diaminoanthraquinone) was added to the reaction kettle, and the volume was 50% of the total volume of the container; subsequently, 1,5-diaminoanthraquinone and pyridine were added thereto, and the molar ratio of 1,5-diaminoanthraquinone to pyridine was 1:2.2. After the temperature dropped below 5 °C, 3-ethoxycarbonylbenzoyl chloride (3-ethoxycarbonylbenzoyl chloride was 2.05 times the molar amount of 1,5-diaminoanthraquinone) was added dropwise. After stirring and reacting at this temperature for 15 h, the solvent was removed by distillation, saturated sodium bicarbonate solution was added until no bubbles were generated, and after filtration, washing with water and drying, yellow monomer 2 was obtained.

[0088] (2) Synthesis of yellow polyester color masterbatch:

[0089] Neopentyl glycol, yellow monomer 2, adipic acid and dibutyltin oxide were put into a reactor for prepolymerization reaction. The molar ratio of neopentyl glycol, yellow monomer 2 to adipic acid was 1.1:0.7:0.3. The addition amount of dibutyltin oxide was 300 ppm of the reaction raw materials. After prepolymerization at 240 °C for 4 h, vacuum polycondensation was carried out at 260 °C and 100 Pa for 7 h. The obtained melt was filtered (30 μm) and then water-cooled and pelletized to obtain a yellow masterbatch. The molecular weight of this yellow polyester color masterbatch was 20000 g / mol, and the glass transition temperature was 42 °C.

[0090] (3) Preparation of polyester fibers:

[0091] The polyester and the yellow polyester color masterbatch were melt-blended and spun together. The yellow polyester color masterbatch accounted for 4% of the total mass of the polyester and the yellow polyester color masterbatch. The spinning process was POY, and the process parameters included: the spinning temperature was 220 °C, the spinning speed was 1600 m / min, the cooling air temperature was 20 °C, the cooling air speed was 0.5 m / s, and the relative humidity of the cooling air was 75%.

[0092] Example 3

[0093] This example provides a fiber product, and its preparation method is as follows:

[0094] (1) Synthesize yellow monomer according to the following route:

[0095]

[0096] Under an ice-water bath, pyridine (the weight of pyridine is 4 times that of 1,8-diaminoanthraquinone) was added to the reaction kettle, and the volume was 50% of the total volume of the container; subsequently, 1,8-diaminoanthraquinone was added thereto. After the temperature dropped below 5 °C, 3-ethoxycarbonylbenzoyl chloride (3-ethoxycarbonylbenzoyl chloride was 2.05 times the molar amount of 1,8-diaminoanthraquinone) was added dropwise. After stirring and reacting at this temperature for 15 h, saturated sodium bicarbonate solution was added until no bubbles were generated, and after filtration, washing with water and drying, yellow monomer 3 was obtained.

[0097] (2) Synthesize yellow polyester masterbatch:

[0098] Put hexanediol, yellow monomer 3, adipic acid, and dibutyltin oxide into the reactor for prepolymerization. The molar ratio of hexanediol, yellow monomer 3 to adipic acid is 1.1:0.7:0.3. The addition amount of dibutyltin oxide is 300 ppm of the reaction raw materials. After prepolymerization at 240 °C for 4 h, vacuum polycondensation is carried out at 260 °C and 100 Pa for 7 h. The obtained melt is filtered (30 μm) and then water-cooled granulated to obtain the yellow masterbatch. The molecular weight of this yellow polyester masterbatch is 22000 g / mol, and the glass transition temperature is 40 °C.

[0099] (3) Prepare polyester fibers:

[0100] Melt-blend and spin the polyester and the yellow polyester masterbatch together. The yellow polyester masterbatch accounts for 5% of the total mass of the polyester and the yellow polyester masterbatch. The spinning process is FDY, and the process parameters include: the spinning temperature is 240 °C, the spinning speed is 1500 m / min, the cooling air temperature is 20 °C, the cooling air speed is 0.5 m / s, and the relative humidity of the cooling air is 70%.

[0101] Example 4

[0102] This example provides a fiber product, and its preparation method is as follows:

[0103] (1) Synthesize yellow monomer according to the following route:

[0104]

[0105] Under an ice-water bath, add pyridine (the weight of pyridine is 4 times that of 1,5-diaminoanthraquinone) to the reaction kettle, and the volume is 50% of the total volume of the container; then add 1,5-diaminoanthraquinone to it. After the temperature drops below 5 °C, add 4-ethoxycarbonylbenzoyl chloride dropwise (4-ethoxycarbonylbenzoyl chloride is 2.02 times the molar amount of 1,5-diaminoanthraquinone). Stir and react at this temperature for 15 h, add saturated sodium bicarbonate solution until no bubbles are generated, filter, wash with water, and dry to obtain yellow monomer 4.

[0106] (2) Synthesize yellow polyester masterbatch:

[0107] Put pentanediol, yellow monomer 4, succinic acid, and ethylene glycol antimonate into the reactor for prepolymerization. The molar ratio of pentanediol, yellow monomer 4 to succinic acid is 1.1:0.7:0.3. The addition amount of ethylene glycol antimonate is 300 ppm of the reaction raw materials. After prepolymerization at 240 °C for 4 h, vacuum polycondensation is carried out at 260 °C and 100 Pa for 7 h. The obtained melt is filtered (30 μm) and then water-cooled granulated to obtain the yellow masterbatch. The molecular weight of this yellow polyester masterbatch is 21500 g / mol, and the glass transition temperature is 42 °C.

[0108] (3) Preparation of polyester fiber:

[0109] The polyester and the yellow polyester masterbatch are melt-blended and spun together. The yellow polyester masterbatch accounts for 6% of the total mass of the polyester and the yellow polyester. The spinning process is POY, and the process parameters include: the spinning temperature is 250 °C, the spinning speed is 1000 m / min, the cooling air temperature is 25 °C, the cooling air speed is 0.6 m / s, and the relative humidity of the cooling air is 75%.

[0110] Test Example 1

[0111] This Test Example 1 studied the condensation reaction results of differently substituted diaminoanthraquinones and isomers of ethoxycarbonylbenzoyl chloride, as shown in Table 1.

[0112] Table 1 Reaction Results of Substituted Diaminoanthraquinones and Ethoxycarbonylbenzoyl Chloride

[0113]

[0114] It can be seen from Table 1 that when ortho-substituted 2-ethoxycarbonylbenzoyl chloride is selected as the acylating agent, there are more by-products in the reaction system and the product purity is insufficient, so its feasibility as a monomer for combination is excluded. When meta-(3-position) and para-(4-position) substituted ethoxycarbonylbenzoyl chlorides are used, six dicarboxyanthraquinone derivatives are successfully prepared. Specifically: the two compounds condensed with 1,4-diaminoanthraquinone show dark purple-red; while the four groups of products obtained by reacting with 1,5- and 1,8-diaminoanthraquinone are all yellow and can be used as monomers for preparing yellow polyester:

[0115] Test Example 2

[0116] The physical picture of the fiber prepared in Example 1 is as Figure 1 shown. Taking the polyester fiber cloth sample further prepared from the fiber prepared in Example 1 (the physical picture is as Figure 2 shown) as an example, its rubbing color fastness, soaping color fastness and heat pressing color fastness are tested, and the results are shown in Table 2. Among them, the test standards include: 《GB / T 3920-2008》, 《GB / T 3921-2008》 and 《GB / T6152-1997》.

[0117] Table 2 Detection Results of Example 1

[0118]

[0119]

[0120] Further, the light fastness of the above-mentioned polyester fiber cloth sample was tested. The test method was "Method 3 of GB / T 8427-2019, referring to the 8th grade blue wool standard sample", and the result showed that the color change level in the first stage was 8th grade.

[0121] In addition, the polyester fiber cloth samples further prepared from the fibers obtained in Examples 2 to 4 were tested for rubbing fastness, soaping fastness, heat pressing fastness, and light fastness in the same manner as in Example 1. The results all showed that the polyester fiber cloth samples corresponding to the preparations in Examples 2 to 4 could also simultaneously have good rubbing fastness (4-5 grades), soaping fastness (4th grade), heat pressing fastness (4th grade), and light fastness (8th grade).

[0122] In summary, the solution of the present invention has at least the following advantages:

[0123] (1) The yellow monomer is copolymerized and embedded in the polymer chain, and the stability to light, heat, and chemicals is significantly improved. The fibers and fabrics colored by it can maintain good color fastness without other color fixation means.

[0124] (2) The yellow polyester color masterbatch has good compatibility with polyester. During the preparation process of the masterbatch, it is not necessary to disperse it, eliminating the problems of pigment dispersion and color migration of traditional small molecule dyes.

[0125] (3) The preparation route provided by the present invention is simple, the process controllability is strong, it can be compatible with traditional polyester processes and equipment, and it is easy to be industrialized and promoted.

[0126] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a yellow polyester masterbatch, characterized in that: The following steps are involved: In the presence of a catalyst, a yellow monomer containing a diester group, a dibasic acid and a diol are prepolymerized to obtain a prepolymer; and the prepolymer is vacuum polycondensed.

2. The preparation method according to claim 1, characterized in that: The prepolymerization reaction is carried out at 230°C to 250°C and normal pressure for 2h to 5h; Wherein, the molar ratio of the diester-containing yellow monomer, the diol and the dibasic acid is (0.5-0.7):(1-1.1):(0.3-0.5); The diol comprises at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, heptanediol, octanediol, nonanediol and decanediol; The dibasic acid comprises at least one of terephthalic acid, isophthalic acid, phthalic acid, adipic acid, succinic acid and glutaric acid; The catalyst comprises at least one of dibutyltin oxide, tetrabutyl titanate and antimony glycol; The catalyst is added in an amount of 200 ppm to 300 ppm of the reaction raw materials by mass, and the reaction raw materials consist of the diester-containing yellow monomer, the diol and the dibasic acid.

3. The preparation method according to claim 1, characterized in that: The polycondensation reaction is carried out at 260°C to 280°C and a vacuum degree of less than 200 Pa for 4h to 8h.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The chemical structural formula of the yellow monomer containing a diester group includes At least one of; Wherein, R is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl.

5. The preparation method according to claim 4, characterized in that: The method for synthesizing the diester-containing yellow monomer comprises: reacting diaminoanthraquinone with acyl chloride substances in the presence of a base and a solvent.

6. The preparation method according to claim 5, characterized in that: The reaction of diaminoanthraquinone and acyl chloride is carried out at 0°C to 20°C for 10h to 18h; Wherein, the diaminoanthraquinone includes at least one of 1,8-diaminoanthraquinone and 1,5-diaminoanthraquinone; The acyl chloride substance includes at least one of 4-alkoxycarbonylbenzoyl chloride and 3-alkoxycarbonylbenzoyl chloride; The molar amount of the acyl chloride substance is 2.0 to 2.2 times that of the diaminoanthraquinone; The base includes at least one of triethylamine, tri-n-butylamine, pyridine, dicyclohexylamine, di-tert-butylamine, potassium carbonate, potassium phosphate and sodium phosphate; The molar amount of the base added is 2 to 4 times that of the diaminoanthraquinone; The solvent comprises at least one of dichloromethane, dichloroethane and chloroform; The weight of the solvent is 4 to 5 times that of the diaminoanthraquinone, and the added amount of the solvent is 50% to 60% of the volume of the reactor.

7. A yellow polyester masterbatch, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 6.

8. The yellow polyester masterbatch according to claim 7, characterized in that: The molecular weight of the yellow polyester masterbatch is 10000 g / mol to 30000 g / mol; and / or the glass transition temperature of the yellow polyester masterbatch is 40° C. to 85° C.

9. A fiber product, characterized in that: The raw materials for preparing the fiber product include polyester and the yellow polyester masterbatch according to claim 7 or 8; Wherein, the polyester includes at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and polylactic acid.

10. A method for preparing a fiber product according to claim 9, characterized in that: The method comprises the following steps: melt-blending and spinning polyester and the yellow polyester masterbatch; Wherein, the mass of the yellow polyester masterbatch is 1% to 10% of the total mass of the polyester and the yellow polyester masterbatch.

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