Blue macromolecular polyester color master batch, spinning product and preparation method of spinning product

Abstract

The invention discloses a blue macromolecular polyester color master batch, a spinning product and a preparation method of the spinning product, and belongs to the technical field of macromolecular dye synthesis. The preparation method of the blue macromolecular polyester color master batch comprises the following steps: carrying out esterification reaction on a blue monomer containing diester groups, colorless binary acid and colorless dihydric alcohol in the presence of a catalyst to obtain a prepolymer; and carrying out condensation polymerization on the prepolymer under a vacuum condition. The preparation method is simple and easy to operate, a blue monomer is introduced into a macromolecular chain through a chemical reaction, and a color development part is embedded into the macromolecular chain through a covalent bond, so that the dye has higher migration resistance and color fastness compared with a small molecular dye, and the pollution to the environment during processing and use is reduced; the obtained blue polymer polyester color master batch has good thermal stability and good compatibility with polyester, can be directly used for polyester melt spinning, and can be subjected to transesterification with a polyester matrix during melt spinning, so that color migration is reduced, and the color fastness and coloring uniformity of a product are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer dye synthesis, and more specifically, to a blue polymer polyester color masterbatch, a spinning product and a preparation method thereof. Background Art

[0002] Traditional dyes are mostly based on small molecule compounds with relatively simple molecular structures, which may degrade under extreme conditions, leading to color loss or pollution. Secondly, due to their poor solubility, traditional small molecule dyes may cause uneven dyeing, resulting in quality problems such as color difference. Thirdly, with the increasing global attention to environmental protection, the demand for environmentally friendly dyes is also rising continuously. Traditional small molecule dyes are usually difficult to degrade, and the wastewater generated during the dyeing process often contains a large amount of toxic chemicals, and the discharge of these substances has caused serious pollution to water bodies, soil and ecosystems.

[0003] In the textile field, the color-forming components of color masterbatches are pigments or small molecule dyes, and both mainly achieve coloring by acting on the dyed materials through non-covalent bonds such as ionic bonds, hydrogen bonds, and hydrophobic interactions. Their coloring power is relatively weak, and they will migrate to the material surface during storage, washing, and friction, resulting in decolorization.

[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 blue polymer polyester color masterbatch, a spinning product and a preparation method 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 blue polymer polyester color masterbatch, which includes the following steps: subjecting a blue monomer containing a double ester group, a colorless dibasic acid, and a colorless diol to an esterification reaction in the presence of a catalyst to obtain a prepolymer; subjecting the prepolymer to a polycondensation reaction under vacuum conditions.

[0008] In an alternative embodiment, the esterification reaction includes at least one of the following characteristics:

[0009] Characteristic 1: The temperature of the esterification reaction is 230°C to 250°C;

[0010] Characteristic 2: The pressure of the esterification reaction is normal pressure;

[0011] Characteristic 3: The time of the esterification reaction is 2h to 5h;

[0012] Characteristic 4: The molar ratio of the colorless diol, the blue monomer containing a double ester group, and the colorless dibasic acid is (1.0 to 1.1):(0.5 to 0.7):(0.3 to 0.5);

[0013] Feature 5: The colorless 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;

[0014] Feature 6: The colorless dibasic acid includes at least one of terephthalic acid, isophthalic acid, phthalic acid, adipic acid, succinic acid, and glutaric acid;

[0015] Feature 7: The catalyst includes at least one of organotin catalysts, tetrabutyl titanate, and antimony glycolate;

[0016] Feature 8: By mass, the addition amount of the catalyst is 200 ppm to 300 ppm of the reaction materials, and the reaction materials are composed of a blue monomer containing a double ester group, a colorless dibasic acid, and a colorless diol.

[0017] In an alternative embodiment, the polycondensation reaction includes at least one of the following features:

[0018] Feature 9: The temperature of the polycondensation reaction is 260 °C to 280 °C;

[0019] Feature 10: The vacuum degree of the polycondensation reaction < 300 Pa;

[0020] In an alternative embodiment, the chemical structural formula of the blue monomer containing a double ester group is as follows:

[0021]

[0022] Wherein, R 1 、R 2 、R 3 、R 4 are each independently selected from methyl or ethyl, and R 5 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl, and the ester group is located at the para or meta position of the oxygen atom of the ether bond.

[0023] In an alternative embodiment, the preparation method of the blue monomer containing a double ester group includes: subjecting anthraquinone solvent blue dye and a halogenating reagent to a halogenation reaction in a halogenated solvent to obtain a dihalogenated intermediate; subjecting the dihalogenated intermediate to a coupling reaction with a hydroxybenzoate in the presence of a copper catalyst, a base, and a coupling solvent.

[0024] In an alternative embodiment, the halogenation reaction includes at least one of the following features:

[0025] Feature 12: The temperature of the halogenation reaction is 20 °C to 25 °C;

[0026] Feature 13: The time of the halogenation reaction is 15 h to 24 h;

[0027] Feature 14: The anthraquinone solvent blue dye includes at least one of solvent blue 104 and solvent blue 97;

[0028] Feature 15: The halogenated solvent includes at least one of dichloromethane, dichloroethane, chloroform and carbon tetrachloride;

[0029] Feature 16: The weight of the halogenated solvent is 4 to 5 times that of the anthraquinone solvent blue dye; preferably, the addition amount of the halogenated solvent is 50% to 60% of the reactor volume;

[0030] Feature 17: The halogenating agent includes at least one of dibromohydantoin, N-bromosuccinimide, liquid bromine, dibromo isocyanuric acid, tribromo isocyanuric acid, tetrabutylammonium tribromide, N-iodosuccinimide and iodine;

[0031] Feature 18: The molar amount of the halogenating agent is 1.0 to 2.2 times that of the anthraquinone solvent blue dye.

[0032] In an alternative embodiment, the coupling reaction includes at least one of the following features:

[0033] Feature 19: The temperature of the coupling reaction is 110°C to 150°C;

[0034] Feature 20: The time of the coupling reaction is 18 h to 24 h;

[0035] Feature 21: The hydroxybenzoate includes at least one of m-hydroxybenzoate and p-hydroxybenzoate;

[0036] Feature 22: The molar amount of the hydroxybenzoate is 2.0 to 2.2 times that of the above-mentioned halogenated intermediate;

[0037] Feature 23: The copper catalyst includes at least one of copper powder, cuprous iodide, cuprous bromide and cuprous chloride;

[0038] Feature 24: The addition amount of the copper catalyst is 5 mol% to 10 mol% of the dihalogenated intermediate;

[0039] Feature 25: The base includes at least one of potassium carbonate, potassium hydroxide, potassium fluoride and potassium phosphate;

[0040] Feature 26: The molar addition amount of the base is 3 to 4 times that of the halogenated intermediate;

[0041] Feature 27: The coupling solvent includes at least one of N-methylpyrrolidone, 1,4-dioxane, hexamethylphosphoramide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and dimethyl sulfoxide;

[0042] Feature 28: The weight of the coupling solvent is 5 to 6 times that of the halogenated intermediate, preferably, the addition amount of the coupling solvent is 40% to 50% of the reactor volume.

[0043] In a second aspect, the present invention provides a blue polymer polyester color masterbatch, which is prepared by the preparation method of any one of the foregoing embodiments;

[0044] In an optional embodiment, the molecular weight of the blue polymer polyester color masterbatch is 10,000 g / mol to 30,000 g / mol.

[0045] In an optional embodiment, the glass transition temperature of the blue polymer polyester color masterbatch is 40°C to 90°C.

[0046] In a third aspect, the present invention provides a spun product, and the raw materials for preparing the spun product include polyester and the blue polymer polyester color masterbatch of the foregoing embodiments.

[0047] In an optional embodiment, the polyester includes at least one of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polylactic acid.

[0048] In a fourth aspect, the present invention provides a preparation method of a spun product as in the foregoing embodiments, including the following steps: melt-blending and spinning the polyester and the blue polymer polyester color masterbatch together.

[0049] In an optional embodiment, the mass of the blue polymer polyester color masterbatch accounts for 1% to 10% of the total mass of the polyester and the blue polymer polyester color masterbatch.

[0050] In an optional embodiment, the melt-blending and spinning method includes UDY, POY, or FDY.

[0051] In an optional embodiment, when the melt-blending and spinning method is UDY, the process parameters include: the spinning temperature is 220°C to 260°C, the spinning speed is 500 m / min to 1500 m / min, the cooling air temperature is 20°C to 30°C, the cooling air speed is 0.4 m / s to 1 m / s, and the relative humidity of the cooling air is 60% to 70%;

[0052] When the melt-blending and spinning method is POY, the process parameters include: the spinning temperature is 220°C to 260°C, the spinning speed is 1000 m / min to 2500 m / min, the cooling air temperature is 15°C to 30°C, the cooling air speed is 0.4 m / s to 0.7 m / s, and the relative humidity of the cooling air is 60% to 70%;

[0053] When the melt-blending and spinning method is FDY, the process parameters include: the spinning temperature is 220°C to 260°C, the spinning speed is 2500 m / min to 3500 m / min, the cooling air temperature is 15°C to 20°C, the cooling air speed is 0.3 m / s to 0.6 m / s, and the relative humidity of the cooling air is 70% to 85%.

[0054] The beneficial effects of the present invention include:

[0055] In the present invention, a blue monomer is introduced into the macromolecular chain through a chemical reaction, and the coloring part is embedded in the polymer chain through a covalent bond, making it have higher migration resistance than small molecule dyes. This blue polymer polyester color masterbatch can be directly used for polyester melt spinning, perfectly compatible with polyester, without particle feeling. The polyester after coloring can be processed into filaments and long filaments, while chemical fibers colored with pigments are difficult to manufacture filaments due to the particle size of the pigments. In addition, the high color fastness and migration resistance of the blue polymer polyester color masterbatch provided by the present invention can reduce environmental pollution during processing and use.

[0056] The blue polymer polyester color masterbatch prepared by the preparation method provided by the present invention not only has good thermal stability, but also can undergo transesterification reaction with the polyester matrix during melt spinning, thereby reducing color migration, improving the color fastness and coloring uniformity of the product. That is, the blue polymer 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. Description of the Drawings

[0057] 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 therefore 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.

[0058] Figure 1 It is a physical diagram of the spun product (polyester fiber) prepared in Example 1;

[0059] Figure 2 It is a physical diagram of the cloth sample further prepared from the polyester fiber in Example 1. Detailed Embodiments

[0060] 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. Those not specified in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. Those reagents or instruments not specified by the manufacturer can be obtained as conventional products through commercial purchase.

[0061] The blue polymer polyester color masterbatch, spun product, and their preparation methods provided by the present invention will be specifically described below.

[0062] The present invention provides a method for preparing a blue polymer polyester color masterbatch, which comprises the following steps: carrying out an esterification reaction on a blue monomer containing a double ester group, a colorless dibasic acid, and a colorless diol in the presence of a catalyst to obtain a prepolymer; carrying out a polycondensation reaction on the prepolymer under vacuum conditions.

[0063] In some alternative embodiments, the temperature of the esterification reaction can be 230°C to 250°C, such as 230°C, 235°C, 240°C, 245°C, or 250°C, etc., or other values within the range of 230°C to 250°C.

[0064] The pressure of the esterification reaction is normal pressure.

[0065] The time of the esterification 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.

[0066] The molar ratio of the colorless diol, the blue monomer containing a double ester group, and the colorless dibasic acid can be (1.0 to 1.1):(0.5 to 0.7):(0.3 to 0.5), such as 1:0.5:0.3, 1:0.5:0.4, 1:0.5:0.5, 1.05:0.6:0.3, 1.05:0.6:0.4, 1.05:0.6:0.5, 1.1:0.7:0.3, 1.1:0.7:0.4, or 1.1:0.7:0.5, etc., or other values within the range of (1.0 to 1.1):(0.5 - 0.7):(0.3 to 0.5).

[0067] In some alternative embodiments, the colorless diol can exemplarily but non - restrictively include 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.

[0068] The colorless dibasic acid can exemplarily but non - restrictively include at least one of terephthalic acid, isophthalic acid, phthalic acid, adipic acid, succinic acid, and glutaric acid.

[0069] The catalyst can exemplarily but non - restrictively include at least one of organotin catalysts, tetrabutyl titanate, and antimony glycolate.

[0070] By mass, the addition amount of the catalyst can be 200 ppm to 300 ppm, such as 200 ppm, 250 ppm, or 300 ppm, etc., or other values within the range of 200 ppm to 300 ppm. Among them, the reaction materials are composed of a blue monomer containing a double ester group, a colorless dibasic acid, and a colorless diol.

[0071] In some alternative embodiments, the temperature of the polycondensation reaction can be 260°C to 280°C, such as 260°C, 265°C, 270°C, 275°C or 280°C, etc., or other values within the range of 260°C to 280°C.

[0072] The vacuum degree of the polycondensation reaction < 300 Pa, such as it can be 250 Pa, 200 Pa, 150 Pa, 100 Pa or 50 Pa, etc., or other values within the range of < 300 Pa.

[0073] In some alternative embodiments, the chemical structural formula of the blue monomer containing a diester group is as follows: Among them, R 1 、R 2 、R 3 、R 4 are each independently selected from methyl or ethyl, and R 5 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, and the ester group is located at the para or meta position of the oxygen atom of the ether bond.

[0074] In some alternative embodiments, the preparation method of the above blue monomer containing a diester group includes: carrying out a halogenation reaction on anthraquinone solvent blue dye and a halogenating agent in a halogenated solvent to obtain a dihalogenated intermediate; carrying out a coupling reaction on the dihalogenated intermediate with a hydroxybenzoate in the presence of a copper catalyst, a base and a coupling solvent.

[0075] In some alternative embodiments, the temperature of the halogenation reaction can be 20°C to 25°C, such as 20°C, 21°C, 22°C, 23°C, 24°C or 25°C, etc., or other values within the range of 20°C to 25°C.

[0076] The time of the halogenation reaction can be 15 h to 24 h, such as 15 h, 18 h, 20 h, 22 h or 24 h, etc., or other values within the range of 15 h to 24 h.

[0077] In some alternative embodiments, the anthraquinone solvent blue dye can include at least one of solvent blue 104 and solvent blue 97.

[0078] The halogenated solvent can exemplarily but not restrictively include at least one of dichloromethane, dichloroethane, chloroform and carbon tetrachloride.

[0079] The weight of the halogenated solvent can be 4 to 5 times that of the anthraquinone solvent blue dye, such as 4 times, 4.5 times or 5 times, etc., or other values within the range of 4 to 5 times. In the actual synthesis or preparation process, the addition amount of the halogenated solvent can be controlled to be 50% to 60% of the reactor volume, such as 50%, 55% or 60%, etc., or other values within the range of 50% to 60%.

[0080] The halogenating agent may include, by way of example but not limitation, at least one of dibromohydantoin, N-bromosuccinimide, liquid bromine, dibromo isocyanuric acid, tribromo isocyanuric acid, tetrabutylammonium tribromide, N-iodosuccinimide, and elemental iodine.

[0081] The molar amount of the halogenating agent may be 1.0 to 2.2 times that of the anthraquinone solvent blue dye, such as 1.0 times, 1.5 times, 2.0 times, 2.1 times, or 2.2 times, etc., or other values within the range of 1.0 to 2.2 times.

[0082] In some alternative embodiments, the temperature of the coupling reaction may be 110°C to 150°C, such as 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, or 150°C, etc., or other values within the range of 110°C to 150°C.

[0083] The time of the coupling reaction may be 18 h to 24 h, such as 18 h, 19 h, 20 h, 21 h, 22 h, 23 h, or 24 h, etc., or other values within the range of 18 h to 24 h.

[0084] In some alternative embodiments, the hydroxybenzoate may include at least one of m-hydroxybenzoate and p-hydroxybenzoate.

[0085] The molar amount of the hydroxybenzoate may be 2.0 to 2.2 times that of the above-mentioned halogenated intermediate, such as 2.0 times, 2.1 times, or 2.2 times, etc., or other values within the range of 2.0 to 2.2 times.

[0086] In some alternative embodiments, the copper catalyst may include, by way of example but not limitation, at least one of copper powder, cuprous iodide, cuprous bromide, and cuprous chloride.

[0087] The addition amount of the copper catalyst may be 5 mol% to 10 mol% of the dihalogenated intermediate, such as 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, or 10 mol%, etc., or other values within the range of 5 mol% to 10 mol%.

[0088] In some alternative embodiments, the base may include, by way of example but not limitation, at least one of potassium carbonate, potassium hydroxide, potassium fluoride, and potassium phosphate.

[0089] The molar addition amount of the base may be 3 to 4 times that of the halogenated intermediate, such as 3 times, 3.5 times, or 4 times, etc., or other values within the range of 3 to 4 times.

[0090] In some alternative embodiments, the coupling solvent may illustratively but non - limitatively include at least one of N - methylpyrrolidone, 1,4 - dioxane, hexamethylphosphoramide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and dimethyl sulfoxide.

[0091] The weight of the coupling solvent can be 5 to 6 times that of the halogenated intermediate, such as 5 times, 5.5 times, or 6 times, etc., or other values within the range of 5 to 6 times. In the actual synthesis or preparation process, the addition amount of the coupling solvent can be controlled to be 40% - 50% of the reactor volume, such as 40%, 45%, or 50%, etc., or other values within the range of 40% - 50%.

[0092] The blue monomer used in the present invention is a heat - resistant blue monomer. This type of monomer is based on anthraquinone solvent blue dye, where strong chemical bonds such as C - N bonds and C - O bonds ensure its sufficient thermal stability without color change during the polymerization or melt - spinning process; at the same time, the diester 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 blue monomer is synthesized from industrialized solvent blue dye and other cheap and easily available industrial products, with the overall cost controllable, which is conducive to large - scale production and promotion. After obtaining the required blue monomer, it is copolymerized with diol and colorless diacid to form the corresponding color masterbatch. During the polymerization process, by adjusting conditions such as reaction temperature, pressure, time, and catalyst, the molecular weight range of the color masterbatch can be controlled, and at the same time, it is ensured that the blue monomer is evenly distributed in the polymer chain to achieve uniform coloring.

[0093] As mentioned above, the present invention introduces the blue monomer into the macromolecular chain through a chemical reaction, and the chromogenic part is embedded in the polymer chain through a covalent bond, making it have higher migration resistance than small - molecule dyes. This blue polymer polyester color masterbatch can be directly used for polyester melt - spinning, perfectly compatible with polyester, without particle feeling. The polyester after coloring can be processed into fine filaments and filaments, while chemical fibers colored with pigments are difficult to manufacture fine filaments due to the particle size of the pigments. In addition, the high color fastness and migration resistance of the blue polymer polyester color masterbatch provided by the present invention can reduce environmental pollution during processing and use.

[0094] Correspondingly, the present invention also provides a blue polymer polyester color masterbatch prepared by the above - mentioned preparation method.

[0095] The blue polymer polyester color masterbatch prepared by the preparation method provided by the present invention not only has good thermal stability, but also can undergo transesterification reaction with the polyester matrix during melt - spinning, thereby reducing color migration, improving the color fastness and coloring uniformity of the product. That is, the blue polymer 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.

[0096] In some alternative embodiments, the molecular weight of the blue high molecular polyester color masterbatch can be 10,000 g / mol to 30,000 g / mol. The test method for the molecular weight of the blue high molecular polyester color masterbatch adopts the viscosity method (GB / T 14189-2015).

[0097] In some alternative embodiments, the glass transition temperature of the blue high molecular polyester color masterbatch is 40°C to 90°C.

[0098] In addition, the present invention also provides a spun product, and the raw materials for preparing the spun product include polyester and the above-mentioned blue high molecular polyester color masterbatch.

[0099] In some alternative embodiments, the polyester can exemplarily but non-limitingly include at least one of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polylactic acid.

[0100] Correspondingly, the present invention also provides a method for preparing the above-mentioned spun product, including the following steps: melt-blending and spinning the polyester and the blue high molecular polyester color masterbatch together.

[0101] In some alternative embodiments, the mass of the blue high molecular polyester color masterbatch can account for 1% to 10% of the total mass of the polyester and the blue high molecular polyester color masterbatch, such as 1%, 2%, 5%, 8%, or 10%, etc., or other values within the range of 1% to 10%.

[0102] In some alternative embodiments, the melt-blending and spinning method can include UDY, POY, or FDY. Among them, UDY is an undrawn yarn, POY is a pre-oriented yarn, and FDY is a fully drawn yarn.

[0103] When the melt-blending and spinning method is UDY, the process parameters can include: the spinning temperature is 220°C to 260°C (such as 220°C, 230°C, 240°C, 250°C, or 260°C, etc.), the spinning speed is 500 m / min to 1500 m / min (such as 500 m / min, 800 m / min, 1000 m / min, 1200 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, 0.6 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.).

[0104] When the melt blending spinning method is POY, the process parameters may include: the spinning temperature is 220°C to 260°C (such as 220°C, 230°C, 240°C, 250°C or 260°C, etc.), the spinning speed is 1500 m / min to 2500 m / min (such as 1500 m / min, 1800 m / min, 2000 m / min, 2200 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, 0.5 m / s, 0.6 m / s or 0.7 m / s, etc.), and the relative humidity of the cooling air is 60% to 70% (such as 60%, 65% or 70%, etc.).

[0105] When the melt blending spinning method is FDY, the process parameters may include: the spinning temperature is 220°C to 260°C (such as 220°C, 230°C, 240°C, 250°C or 260°C, etc.), the spinning speed is 1000 m / min to 3500 m / min (such as 1000 m / min, 1500 m / min, 2000 m / min, 2500 m / min, 2800 m / min, 3000 m / min, 3200 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, 0.4 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.).

[0106] The features and performance of the present invention will be further described in detail below in conjunction with embodiments.

[0107] Example 1

[0108] This example provides a spinning product, and its preparation method is as follows:

[0109] (1) Synthesize a blue monomer containing a diester group:

[0110] The synthesis route of this blue monomer is as follows:

[0111]

[0112] ①. Under an ice-water bath, dichloromethane was added to the reaction kettle, with a volume of 50% of the total volume of the container. Subsequently, Solvent Blue 97 (the weight of dichloromethane was 4 times that of Solvent Blue 97) was dissolved therein, and N-bromosuccinimide (2 times the molar amount of Solvent Blue 97) was added in small portions and multiple batches. The reaction was stirred at this temperature (25 °C) for 18 h. After the reaction ended, the product was precipitated by distillation and concentration, filtered, and washed successively with saturated sodium sulfite solution and water. Recrystallization with acetone gave the corresponding dihalo intermediate (denoted as Intermediate 1).

[0113] ②. Intermediate 1, ethyl 4-hydroxybenzoate, potassium carbonate, and copper iodide were added to the reaction kettle, and their molar ratio was 1:2.2:4.0:0.05. Subsequently, N-methylpyrrolidone was added, with a weight of 5 times that of Intermediate 1 (the addition amount of N-methylpyrrolidone was 50% of the volume of the reaction kettle). Under nitrogen protection, the reaction was carried out at 140 °C for 24 h. The insoluble substances were filtered off, water was added to precipitate the product, and recrystallization with acetone gave the blue monomer (denoted as Monomer 1).

[0114] (2) Synthesis of blue polymer polyester color masterbatch:

[0115] Ethylene glycol, Monomer 1, terephthalic acid, and tetrabutyl titanate were put into the reactor for esterification reaction. The molar ratio of ethylene glycol, terephthalic acid to the blue monomer was 1.1:0.4:0.6, and the addition amount of tetrabutyl titanate was 200 ppm. After esterification at 240 °C and atmospheric pressure for 4 h, polycondensation was carried out at 260 °C and 150 Pa vacuum for 8 h. The obtained melt was filtered (60 μm) and then water-cooled and pelletized to obtain the blue polymer polyester color masterbatch. The molecular weight of this polyester color masterbatch was 30000 g / mol, and the glass transition temperature was 85 °C.

[0116] (3) Preparation of polyester fibers:

[0117] The polyester and the blue polymer polyester color masterbatch were melt-blended and spun together. The blue polymer polyester color masterbatch accounted for 5% of the total mass of the polyester and the blue polymer polyester. The spinning process was UDY, and the process parameters included: the spinning temperature was 260 °C, the spinning speed was 1200 m / min, the cooling air temperature was 25 °C, the cooling air speed was 0.6 m / s, and the relative humidity of the cooling air was 70%.

[0118] Example 2

[0119] This example provides a spun product, and its preparation method is as follows:

[0120] (1) Synthesis of a blue monomer containing a double ester group:

[0121] The synthesis route of this blue monomer is as follows:

[0122]

[0123] ① Under an ice-water bath, add dichloroethane to the reaction kettle, with a volume of 50% of the total volume of the container; then dissolve Solvent Blue 104 (the weight of dichloroethane is 4.5 times that of Solvent Blue 104) in it, and add N-bromosuccinimide (2 times the molar amount of Solvent Blue 104) in small portions and in batches. Stir and react at this temperature (25 °C) for 18 h. After the reaction is completed, distill and concentrate to precipitate the product, filter and wash successively with saturated sodium sulfite solution and water, and recrystallize with acetone to obtain the corresponding dihalogenated intermediate (denoted as Intermediate 2).

[0124] ② Add Intermediate 2, ethyl 4-hydroxybenzoate, potassium phosphate, and copper(I) iodide to the reaction kettle, and the molar ratio of the four is 1:2.2:4.0:0.05. Then add dimethyl sulfoxide, with a weight of 5 times that of Intermediate 2 (the addition amount of dimethyl sulfoxide is 50% of the volume of the reaction kettle). Under nitrogen protection, react at 150 °C for 24 h, filter to remove insoluble substances, add water to precipitate the product, and recrystallize with acetone to obtain the blue monomer (denoted as Monomer 2).

[0125] (2) Synthesis of blue polymer polyester color masterbatch:

[0126] Put neopentyl glycol, Monomer 2, isophthalic acid, and tetrabutyl titanate into the reactor for esterification reaction. The molar ratio of neopentyl glycol, isophthalic acid to the blue monomer is 1.1:0.3:0.7, and the addition amount of tetrabutyl titanate is 300 ppm. After esterification at 240 °C and normal pressure for 4 h, polycondensation is carried out at 260 °C and 100 Pa vacuum for 7 h. The obtained melt is filtered (60 μm) and then water-cooled and pelletized to obtain the blue polymer polyester color masterbatch. The molecular weight of this polyester color masterbatch is 26,000 g / mol, and the glass transition temperature is 72 °C.

[0127] (3) Preparation of polyester fiber:

[0128] Carry out melt blending and spinning of the polyester and the blue polymer polyester color masterbatch together. The blue polymer polyester color masterbatch accounts for 5% of the total mass of the polyester and the blue polymer polyester. The spinning process is POY, and the process parameters include: the spinning temperature is 220 °C, the spinning speed is 2000 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%.

[0129] Example 3

[0130] This example provides a spinning product, and its preparation method is as follows:

[0131] (1) Synthesis of blue monomer containing double ester groups:

[0132] The synthesis route of this blue monomer is as follows:

[0133]

[0134] ① Under an ice-water bath, add dichloroethane into the reaction kettle, with a volume of 50% of the total volume of the container. Subsequently, dissolve Solvent Blue 104 (the weight of dichloroethane is 4 times that of Solvent Blue 104) in it, and add N-iodosuccinimide (2 times the molar amount of Solvent Blue 104) in small portions and multiple batches. Stir and react at this temperature (25 °C) for 18 h. After the reaction is completed, distill and concentrate to precipitate the product, filter and wash successively with saturated sodium sulfite solution and water, and recrystallize with acetone to obtain the corresponding dihalo intermediate (denoted as Intermediate 3).

[0135] ② Add Intermediate 3, ethyl 4-hydroxybenzoate, potassium phosphate, and copper(I) iodide into the reaction kettle, and the molar ratio of the four is 1:2.1:3.0:0.1. Subsequently, add dimethyl sulfoxide, with a weight of 5 times that of Intermediate 2 (the addition amount of dimethyl sulfoxide is 50% of the volume of the reaction kettle). Under nitrogen protection, react at 150 °C for 24 h, filter to remove insoluble substances, add water to precipitate the product, and recrystallize with acetone to obtain the blue monomer (denoted as Monomer 3).

[0136] (2) Synthesis of blue polymer polyester color masterbatch:

[0137] Put neopentyl glycol, Monomer 3, isophthalic acid, and antimony glycol into the reactor for esterification reaction. The molar ratio of neopentyl glycol, isophthalic acid to the blue monomer is 1.1:0.3:0.7, and the addition amount of antimony glycol is 300 ppm. Esterify at 240 °C and atmospheric pressure for 4 h, and then polycondense at 260 °C and 100 Pa vacuum for 7 h. The obtained melt is filtered (60 μm) and then water-cooled and pelletized to obtain the blue polymer polyester color masterbatch. The molecular weight of this polyester color masterbatch is 20000 g / mol, and the glass transition temperature is 68 °C.

[0138] (3) Preparation of polyester fiber:

[0139] Melt-blend and spin the polyester and the blue polymer polyester color masterbatch together. The blue polymer polyester color masterbatch accounts for 3% of the total mass of the polyester and the blue polymer polyester. The spinning process is FDY, and the process parameters include: the spinning temperature is 230 °C, the spinning speed is 1000 m / min, the cooling air temperature is 25 °C, the cooling air speed is 0.5 m / s, and the relative humidity of the cooling air is 75%.

[0140] Example 4

[0141] This example provides a spun product, and its preparation method is as follows:

[0142] (1) Synthesis of a blue monomer containing a diester group:

[0143] The synthesis route of this blue monomer is as follows:

[0144]

[0145] ① Under an ice - water bath, dichloromethane was added to the reaction kettle, with a volume of 50% of the total volume of the container. Subsequently, Solvent Blue 97 (the weight of dichloromethane was 4 times that of Solvent Blue 97) was dissolved therein, and 1,3 - dibromo - 5,5 - dimethylhydantoin (1 - fold molar amount of Solvent Blue 97) was added in small portions at multiple times. Stirring reaction was carried out at this temperature (25 °C) for 18 h. After the reaction ended, distillation and concentration were carried out to precipitate the product, which was filtered and washed successively with saturated sodium sulfite solution and water, and recrystallized with acetone to obtain the corresponding dihalo intermediate (denoted as Intermediate 1).

[0146] ② Intermediate 1, isopropyl 4 - hydroxybenzoate, potassium carbonate, and copper(I) iodide were added to the reaction kettle, and their molar ratio was 1:2.2:4.0:0.1. Subsequently, N - methylpyrrolidone was added, with a weight of 5 times that of Intermediate 1 (the addition amount of N - methylpyrrolidone was 50% of the volume of the reaction kettle). Under nitrogen protection, the reaction was carried out at 140 °C for 24 h. The insoluble substances were removed by filtration, water was added to precipitate the product, and recrystallization was carried out with acetone to obtain the blue monomer (denoted as Monomer 4).

[0147] (2) Synthesis of blue polymer polyester color masterbatch:

[0148] Ethylene glycol, Monomer 4, isophthalic acid, and tetrabutyl titanate were put into the reactor for esterification reaction. The molar ratio of ethylene glycol, isophthalic acid to the blue monomer was 1.1:0.4:0.6, and the addition amount of tetrabutyl titanate was 250 ppm. After esterification at 240 °C and normal pressure for 4 h, polycondensation was carried out at 260 °C and 150 Pa vacuum for 8 h. The obtained melt was filtered (60 μm) and then water - cooled and pelletized to obtain the blue polymer polyester color masterbatch. The molecular weight of this polyester color masterbatch was 21000 g / mol, and the glass transition temperature was 77 °C.

[0149] (3) Preparation of polyester fiber:

[0150] The polyester and the blue polymer polyester color masterbatch were melt - blended and spun together. The blue polymer polyester color masterbatch accounted for 4% of the total mass of the polyester and the blue polymer polyester. The spinning process was FDY, and the process parameters included: the spinning temperature was 250 °C, the spinning speed was 1600 m / min, the cooling air temperature was 25 °C, the cooling air speed was 0.6 m / s, and the relative humidity of the cooling air was 70%.

[0151] Example 5

[0152] This example provides a spinning product, and its preparation method is as follows:

[0153] (1) Synthesis of blue monomer containing double ester groups:

[0154] The synthetic route of the blue monomer is as follows:

[0155]

[0156] ① Under an ice-water bath, dichloromethane was added to the reaction kettle, with a volume of 50% of the total volume of the container; subsequently, Solvent Blue 97 (the weight of dichloromethane was 4 times that of Solvent Blue 97) was dissolved therein, and tetrabutylammonium tribromide (2 times the molar amount of Solvent Blue 97) was added in small portions and batches. The reaction was stirred at this temperature (20 °C) for 18 h. After the reaction was completed, the product was precipitated by distillation and concentration, filtered and washed successively with saturated sodium sulfite solution and water, and recrystallized with acetone to obtain the corresponding dihalo intermediate (denoted as Intermediate 1).

[0157] ② Intermediate 1, ethyl 3-hydroxybenzoate, potassium carbonate, and cuprous bromide were added to the reaction kettle, and the molar ratio of the four was 1:2.2:3.0:0.1. Subsequently, N-methylpyrrolidone was added, with a weight of 5 times that of Intermediate 1 (the addition amount of N-methylpyrrolidone was 50% of the volume of the reaction kettle). Under nitrogen protection, the reaction was carried out at 150 °C for 24 h. The insoluble matter was filtered off, water was added to precipitate the product, and recrystallized with acetone to obtain the blue monomer (denoted as Monomer 5).

[0158] (2) Synthesis of blue high molecular polyester color masterbatch:

[0159] Ethylene glycol, Monomer 5, isophthalic acid, and tributyltin triisooctanoate were put into the reactor for esterification reaction. The molar ratio of ethylene glycol, isophthalic acid to the blue monomer was 1.1:0.4:0.6, and the addition amount of tributyltin triisooctanoate was 300 ppm. After esterification at 240 °C and normal pressure for 4 h, polycondensation was carried out at 260 °C and 150 Pa vacuum for 8 h. The obtained melt was filtered (60 μm) and then water-cooled and pelletized to obtain the blue high molecular polyester color masterbatch. The molecular weight of this polyester color masterbatch was 23000 g / mol, and the glass transition temperature was 78 °C.

[0160] (3) Preparation of polyester fiber:

[0161] The polyester and the blue high molecular polyester color masterbatch were melt-blended and spun together. The blue high molecular polyester color masterbatch accounted for 4% of the total mass of the polyester and the blue high molecular polyester. The spinning process was FDY, and the process parameters included: the spinning temperature was 250 °C, the spinning speed was 1600 m / min, the cooling air temperature was 25 °C, the cooling air speed was 0.6 m / s, and the relative humidity of the cooling air was 70%.

[0162] Test Example 1

[0163] In this Test Example 1, the coupling reaction results of 1,4-diphenylaminoanthraquinone modified with different substituents and hydroxybenzoate were studied to investigate the influence of the steric effect of substituents on the color development characteristics of the products, and the results are shown in Table 1.

[0164] Table 1 Screening of blue dye monomer molecules

[0165]

[0166] As can be seen from Table 1: When the ortho-substituent of the aniline ring is a hydrogen atom (R 1 =R 2 =H), the resulting compound shows a dark green characteristic absorption in the visible light region; while when a methyl group (R 1 =R 2 =CH 3 ) or an ethyl group (R 1 =R 2 =C 2 H 5 ) is introduced at the ortho-position, the maximum absorption wavelength undergoes a significant blue shift, showing typical blue characteristics. It may be that the alkyl group with a large steric hindrance can effectively inhibit the torsional of the molecular plane and enhance the rigidity of the conjugated system, resulting in a blue shift of the absorption. This series of ortho-disubstituted anthraquinone derivatives with alkyl groups can be used as color-developing monomers for preparing blue polyesters.

[0167] Test Example 2

[0168] Taking the polyester fiber prepared in Example 1 (as shown in Figure 1 ) and further made into a cloth sample (the physical picture is as shown in Figure 2 ) as an example, its rubbing fastness, soaping fastness and heat pressing fastness were tested, and the results are shown in Table 2. Among them, the test standards include: "GB 18401-2010", "GB / T 3921-2008" and "GB / T 6152-1997".

[0169] Table 2 Test results

[0170]

[0171]

[0172] In addition, the rubbing fastness, soaping fastness and heat pressing fastness of the cloth samples corresponding to the polyester fibers prepared in Examples 2-5 were tested in the same method as in Example 1, and the results showed that: the cloth samples of the polyester fibers corresponding to Examples 2-5 can also simultaneously have good rubbing fastness (4-5 levels), soaping fastness (4 levels) and heat pressing fastness (4-5 levels).

[0173] In summary, the solution of the present invention has at least the following advantages:

[0174] (1) The blue monomer is copolymerized and embedded into the polymer chain, significantly improving the stability against light, heat and chemicals. Fibers and fabrics colored therewith can maintain good color fastness without other color fixation means;

[0175] (2) The blue polymer polyester color masterbatch is essentially a kind of polyester with good compatibility with polyester. During the preparation process of the masterbatch, there is no need to disperse it, eliminating the problems of pigment dispersion and color migration of traditional small molecule dyes;

[0176] (3) The polymerization route provided by the present invention is simple, with strong process controllability, and can be operated on traditional polyester equipment, being easy for industrial production.

[0177] The above are only the preferred embodiments of the present invention and are not intended 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 blue polymer polyester masterbatch, characterized in that: The following steps are involved: The blue monomer containing diester group is subjected to esterification reaction with colorless dibasic acid and colorless diol in the presence of a catalyst to obtain a prepolymer; and the prepolymer is subjected to polycondensation reaction under vacuum conditions.

2. The preparation method according to claim 1, characterized in that: The esterification reaction includes at least one of the following characteristics: Feature 1: The temperature of the esterification reaction is 230℃~250℃; Feature 2: The pressure of the esterification reaction is normal pressure; Feature 3: The esterification reaction time is 2h to 5h; Feature 4: The molar ratio of the colorless diol to the blue monomer containing a diester group and the colorless dibasic acid is (1.0-1.1):(0.5-0.7):(0.3-0.5); Feature 5: The colorless diol includes at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, heptanediol, octanediol, nonanediol and decanediol; Feature 6: The colorless dibasic acid includes at least one of terephthalic acid, isophthalic acid, phthalic acid, adipic acid, succinic acid and glutaric acid; Feature 7: The catalyst includes at least one of an organic tin catalyst, tetrabutyl titanate and antimony ethylene glycol; Feature 8: The amount of the catalyst added is 200ppm to 300ppm of the reaction material by mass, and the reaction material is composed of the blue monomer containing a diester group, the colorless dibasic acid and the colorless diol.

3. The preparation method according to claim 1, characterized in that: The polycondensation reaction includes at least one of the following characteristics: Feature 9: The temperature of the polycondensation reaction is 260°C to 280°C; Feature 10: The vacuum degree of polycondensation reaction is less than 300Pa; Feature 11: The polycondensation reaction time is 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 blue monomer containing a diester group is as follows: Among them, R 1 , R 2 , R 3 , R 4 are each independently selected from methyl or ethyl, R 5 It is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, and the ester group is located at the para position or meta position of the oxygen atom of the ether bond.

5. The preparation method according to claim 4, characterized in that: The method for preparing the blue monomer containing diester group comprises: subjecting anthraquinone solvent blue dye and a halogenating agent to a halogenating reaction in a halogenating solvent to obtain a dihalogenated intermediate; and subjecting the dihalogenated intermediate to a coupling reaction with a hydroxybenzoate in the presence of a copper catalyst, a base and a coupling solvent.

6. The preparation method according to claim 5, characterized in that: The halogenation reaction includes at least one of the following characteristics: Feature 12: The temperature of the halogenation reaction is 20°C to 25°C; Feature 13: The halogenation reaction time is 15h to 24h; Feature 14: The anthraquinone solvent blue dye comprises at least one of solvent blue 104 and solvent blue 97; Feature 15: The halogenated solvent includes at least one of dichloromethane, dichloroethane, chloroform and carbon tetrachloride; Feature 16: The weight of the halogenated solvent is 4 to 5 times that of the anthraquinone solvent blue dye; the amount of the halogenated solvent added is 50% to 60% of the reactor volume; Feature 17: The halogenating agent includes at least one of dibromohydantoin, N-bromosuccinimide, liquid bromine, dibromoisocyanuric acid, tribromoisocyanuric acid, tetrabutylammonium tribromide, N-iodosuccinimide and elemental iodine; Feature 18: The molar amount of the halogenating agent is 1.0 to 2.2 times that of the anthraquinone solvent blue dye.

7. The preparation method according to claim 5, characterized in that: The coupling reaction includes at least one of the following features: Feature 19: The coupling reaction temperature is 110°C to 150°C; Feature 20: The coupling reaction time is 18h to 24h; Feature 21: The hydroxybenzoic acid ester includes at least one of m-hydroxybenzoic acid ester and p-hydroxybenzoic acid ester; Feature 22: The molar amount of the hydroxybenzoic acid ester is 2.0 to 2.2 times that of the halogenated intermediate; Feature 23: The copper catalyst comprises at least one of copper powder, cuprous iodide, cuprous bromide and cuprous chloride; Feature 24: The amount of the copper catalyst added is 5 mol% to 10 mol% of the dihalogenated intermediate; Feature 25: The base includes at least one of potassium carbonate, potassium hydroxide, potassium fluoride and potassium phosphate; Feature 26: The molar amount of the base added is 3 to 4 times that of the halogenated intermediate; Feature 27: The coupling solvent includes at least one of N-methylpyrrolidone, 1,4-dioxane, hexamethylphosphoramide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and dimethyl sulfoxide; Feature 28: The weight of the coupling solvent is 5 to 6 times that of the halogenated intermediate. Preferably, the amount of the coupling solvent added is 40% to 50% of the reactor volume.

8. A blue polymer polyester masterbatch, characterized in that: Prepared by the preparation method according to any one of claims 1 to 7; Wherein, the molecular weight of the blue high molecular weight polyester masterbatch is 10000 g / mol to 30000 g / mol; Wherein, the glass transition temperature of the blue high molecular polyester masterbatch is 40°C to 90°C.

9. A spinning product, characterized in that: The raw materials for preparing the spinning product include polyester and the blue high molecular weight polyester masterbatch as claimed in claim 8; Wherein, the polyester includes at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and polylactic acid.

10. A method for preparing a spun product according to claim 9, characterized in that: The method comprises the following steps: melt-blending and spinning polyester and the blue high molecular weight polyester masterbatch; Wherein, the mass of the blue high molecular weight polyester masterbatch accounts for 1% to 10% of the total mass of the polyester and the blue high molecular weight polyester masterbatch; Among them, melt blending spinning methods include UDY, POY or FDY; Among them, when the melt blending spinning method is UDY, the process parameters include: spinning temperature is 220℃~260℃, spinning speed is 500m / min~1500m / min, cooling air temperature is 20℃~30℃, cooling air speed is 0.4m / s~1m / s, and cooling air relative humidity is 60%~70%; When the melt blending spinning method is POY, the process parameters include: spinning temperature of 220°C to 260°C, spinning speed of 1500m / min to 2500m / min, cooling air temperature of 15°C to 25°C, cooling air speed of 0.4m / s to 0.7m / s, and cooling air relative humidity of 60% to 70%; When the melt blending spinning method is FDY, the process parameters include: spinning temperature of 220°C to 260°C, spinning speed of 1000m / min to 3500m / min, cooling air temperature of 15°C to 30°C, cooling air speed of 0.3m / s to 0.6m / s, and cooling air relative humidity of 70% to 85%.

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