Process for the preparation of a drip resistant colored flame retardant polyester fiber

Abstract

The application relates to a preparation method of anti-dripping colored flame-retardant polyester fibers. First, a small-molecule amine is used to pre-expand and intercalate alpha-ZrP to react with a PDI amino derivative to obtain alpha-ZrP-PDI anti-dripping colored flame-retardant molecules. Then, the alpha-ZrP-PDI anti-dripping colored flame-retardant molecules are blended with polyester chip powder matrix to obtain anti-dripping colored flame-retardant master batches. Finally, the anti-dripping colored flame-retardant master batches are blended with polyester chips to be melt spun to obtain the anti-dripping colored flame-retardant polyester fibers. The PDI amino derivative refers to a PDI derivative with a terminal group of -NH2. In the application, the small-molecule amine is used to pre-expand and intercalate the alpha-ZrP to increase the layer spacing, and then the pretreated alpha-ZrP is reacted with the PDI amino derivative to form the alpha-ZrP-PDI anti-dripping colored flame-retardant molecules, so that the flame-retardant performance and the anti-dripping performance of the polyester fibers are significantly improved.

Description

Technical Field

[0001] The invention belongs to the technical field of functional textile materials and relates to a method for preparing anti-drip colored flame-retardant polyester fiber. Background Art

[0002] Polyester fibers, with their excellent physical properties and chemical stability, have become one of the most widely used synthetic fibers in the textile industry. They are widely used in the production of clothing, home textiles, industrial textiles, etc.

[0003] Despite its many advantages, polyester fibers tend to melt and drip at high temperatures. This characteristic can cause fires to spread rapidly in the event of a fire, increasing safety risks. Furthermore, polyester fibers can release toxic fumes during combustion, posing a threat to human health. Therefore, improving the flame retardancy and anti-drip properties of polyester fibers is crucial for enhancing their application in safety-critical applications.

[0004] Currently, flame-retardant blending is an effective method for modifying polyester fibers. This method involves mixing a flame retardant with polyester chips and then producing flame-retardant fibers through a melt spinning process. While this method can improve the flame retardancy of the fibers to a certain extent, it also presents challenges, such as ensuring uniform dispersion of the flame retardant, ensuring compatibility between the flame retardant and the polyester substrate, and maintaining the mechanical properties of the fibers.

[0005] In order to solve the above problems, patent CN202211327836.3 discloses a solution-dyed regenerated colored flame-retardant polyester flat filament and its preparation method, which can obtain colored polyester filament with better flame retardant effect and higher dyeing color fastness. However, this patent is colored flame retardant and does not reflect the anti-melt dripping function.

[0006] In addition, patent CN202311844723.5 discloses a different shrinkage flame retardant anti-melt drip fiber and its preparation method, which obtains a fiber with excellent wool-like effect, flame retardant and anti-melt drip functions. However, the fiber in this patent is a flame retardant anti-melt drip fiber and does not have a color function.

[0007] Therefore, it is of great significance to study a method for preparing a colored flame-retardant polyester fiber that is resistant to dripping in order to solve the problems existing in the prior art. Summary of the Invention

[0008] The purpose of the present invention is to solve the problems existing in the prior art and provide a method for preparing anti-drip colored flame-retardant polyester fiber.

[0009] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0010] A method for preparing anti-drip colored flame-retardant polyester fiber comprises the following steps: firstly reacting α-ZrP (α-zirconium phosphate) pre-supported and intercalated with a small molecule amine with a PDI (perylene diimide) amino derivative to obtain an α-ZrP-PDI anti-drip colored flame-retardant molecule; then blending the α-ZrP-PDI anti-drip colored flame-retardant molecule with a polyester chip powder matrix to obtain an anti-drip colored flame-retardant masterbatch; and finally blending the anti-drip colored flame-retardant masterbatch with the polyester chips and melt-spinning the blended masterbatch to obtain the anti-drip colored flame-retardant polyester fiber.

[0011] PDI amino derivatives refer to PDI derivatives with a terminal group of -NH2.

[0012] Because the present invention uses a single anti-melting flame retardant molecule, it is easier to achieve uniform dispersion in the polyester matrix compared to conventional multi-component additions, thereby ensuring that the mechanical properties of the fiber are not affected while simultaneously improving the fiber's flame retardancy and anti-melting properties. In the traditional method of creating colored fibers by adding masterbatches, the addition of multiple components, including flame retardants and colored components, can affect the fiber forming process or be detrimental to improving or even maintaining flame retardancy. However, the α-ZrP-PDI designed and synthesized in the present invention combines flame retardancy and coloring functions in one, and through single-component addition, it is more conducive to blending uniformity and fiber forming stability. In addition, its colored functional component, PDI, can also synergistically enhance anti-melting properties.

[0013] As the preferred technical solution:

[0014] In the above-mentioned method for preparing a drip-resistant colored flame-retardant polyester fiber, the molecular structure of the PDI amino derivative is as follows:

[0015]

[0016] The preparation method of the above-mentioned anti-drip colored flame-retardant polyester fiber, the preparation steps of the α-ZrP-PDI anti-drip colored flame-retardant molecule are as follows:

[0017] (1) Perylene tetracarboxylic dianhydride (PTCDA) and ethylenediamine are heated in an imidazole solvent (imidazole is in a molten state at 100-110°C and can be used as a solvent) under a nitrogen atmosphere for 4-6 hours, followed by addition of ethanol to wash away the imidazole precipitated product, filtering the solid and drying it to obtain a PDI amino derivative;

[0018] (2) After α-ZrP is stirred evenly in an ethanol solvent, a small molecular amine is added and reacted for 1.5 to 2 hours to achieve pre-supported intercalation of α-ZrP;

[0019] (3) adding the PDI amino derivative obtained in step (1) to the system after the reaction in step (2), stirring the reaction for 8 to 12 hours, filtering and drying to obtain the α-ZrP-PDI anti-melting colored flame retardant molecule.

[0020] According to the method for preparing the anti-drip colored flame-retardant polyester fiber, the molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:1-3, the molar ratio of α-ZrP to small molecule amine is 4:1-4, and the molar ratio of PDI amino derivative to α-ZrP is 1:0.5-1.

[0021] In the above-mentioned method for preparing the anti-drip colored flame-retardant polyester fiber, the small molecule amine is ethylamine, propylamine or butylamine.

[0022] The method for preparing the anti-drip colored flame-retardant polyester fiber as described above is based on the total mass of the α-ZrP-PDI anti-drip colored flame-retardant molecules and the polyester chip powder matrix, and the mass percentage of the α-ZrP-PDI anti-drip colored flame-retardant molecules is 30-45%.

[0023] In the method for preparing the anti-drip colored flame-retardant polyester fiber, based on the total amount of the anti-drip colored flame-retardant masterbatch and polyester chips, the mass percentage of the anti-drip colored flame-retardant masterbatch is 5-15%.

[0024] The method for preparing the anti-drip colored flame-retardant polyester fiber as described above includes melt spinning, which includes a process flow of melt extrusion by a single-screw extruder, spinning, cooling, drawing, shaping, and winding. The specific process parameters are as follows:

[0025] The temperature of the single-screw extruder: Zone 1 temperature 275-290°C, Zone 2 temperature 285-295°C, Zone 3 temperature 285-295°C, Zone 4 temperature 285-295°C, Zone 5 temperature 285-295°C;

[0026] Spinning temperature is 285-305°C;

[0027] Cooling conditions include: temperature of 15-25°C, relative humidity of 60-75%, and air speed of 0.3-0.8 m / s;

[0028] The drawing ratio of the drawing is 3 to 6 times, the setting temperature is 80 to 110° C., and the winding speed is 2800 to 4200 m / min.

[0029] The preparation method of the anti-drip colored flame-retardant polyester fiber as described above, the anti-drip colored flame-retardant polyester fiber has a limiting oxygen index ≥31%, a vertical burning grade of V0, a ​​droplet amount ≤38 mg, a breaking strength ≥4.9 cN / dtex, and a color fastness to washing at 60°C of above level 4.

[0030] Principle of the invention:

[0031] This invention achieves an organic combination of flame retardancy, anti-melting dripping, and coloring properties through innovative chemical treatment and blending technologies. First, α-ZrP is pre-supported and intercalated with a small molecule amine to increase its interlayer spacing, providing more binding sites for subsequent reactions. Next, the pretreated α-ZrP is reacted with a PDI amino derivative, and a large amount of PDI amino derivative is grafted onto the surface and interlayers of the α-ZrP, forming an α-ZrP-PDI anti-melting dripping colored flame-retardant molecule. This molecule not only possesses the coloring properties of PDI but also forms a stable bond with polyester fibers through π-π stacking, enhancing the fiber's thermal stability and anti-melting dripping properties. At the same time, α-ZrP decomposes at high temperatures to release crystal water, which removes heat and reduces the material temperature. The protective film formed blocks heat and oxygen, effectively providing flame retardancy. Furthermore, the layered structure of α-zirconium phosphate and the synergistic effects of Lewis and Bronsted acid points promote charring and enhance the thermal stability and mechanical strength of the char layer.

[0032] Specifically, α-zirconium phosphate is a material with a layered structure that gives it unique properties. After pre-intercalation treatment, α-zirconium phosphate still has a layered structure, and the distance between layers increases. In the layered structure of α-zirconium phosphate, there are a large number of Lewis acid sites and Bronsted acid sites. These acid sites play a key role in the material's catalytic, adsorption and flame retardant applications. The Bronsted acid sites come from the H + ions, these H + Ions can diffuse freely in the space within the layer, providing protons (H + ), plays an important role in catalytic reactions. Lewis acid sites usually come from metal cations between α-zirconium phosphate layers, such as Zr 4+ These exposed metal cations can act as electron acceptors and form coordination bonds with molecules containing lone pair electrons, thereby exhibiting Lewis acidity.

[0033] The layered structure and acidic sites of α-zirconium phosphate exhibit a synergistic effect in catalyzing carbonization and enhancing the thermal stability and mechanical strength of the carbon layer. This synergistic effect not only promotes the carbonization process but also improves the quality of the carbon layer, making it more stable at high temperatures. Specifically, the Bronsted acid sites catalyze the cross-linking of polymers (polymers such as polyester fibers) into carbon, forming a dense protective layer that blocks the transfer of oxygen and heat, thereby exerting a flame retardant effect; the H provided by the Bronsted acid sites +It can act as a catalyst to promote reactions between polymer chains, such as transesterification or amidation, to form new covalent bonds. At high temperatures, polymer chains may break to form free radicals, which can recombine to form a cross-linked structure under the catalysis of Bronsted acid sites. Lewis acid sites capture macromolecular free radicals. Under the catalysis of Lewis acid sites, the captured free radicals can react with other free radicals or polymer chains, prompting them to recombine to form a new cross-linked structure, thereby enhancing the thermal stability and mechanical strength of the carbon layer.

[0034] The synergistic effect of the layered structure and acidic sites of α-zirconium phosphate is crucial for its anti-drip performance. Under high temperature conditions, the acidic sites in the layered structure of α-zirconium phosphate catalyze the cross-linking of polymers into char, forming a dense protective layer. This protective layer blocks the mass transfer of volatile products produced by polymer degradation to the gas phase. It also blocks the feedback of heat generated by gas-phase combustion to the condensed phase, providing thermal and oxygen insulation, thereby reducing melting and dripping. This synergistic effect improves the anti-drip performance of polyester fibers, making them less susceptible to melt dripping in the event of a fire, reducing the risk of fire spread. Furthermore, the large number of PDI amino derivatives grafted onto the surface and interlayers of α-zirconium phosphate interact better with the polymer matrix than α-zirconium phosphate. Therefore, the PDI amino derivatives facilitate the connection of polymers to α-zirconium phosphate, accelerate the formation of cross-linking points, and thus inhibit the flow of polyester during combustion.

[0035] In the present invention, the PDI amino derivative, as a conjugated organic component, is fixed to the surface and interlayers of α-zirconium phosphate, facilitating molecular collisions and thereby forming a dense carbon layer with a high degree of graphitization during the carbonization process, which acts as a gas barrier. Therefore, under the dual effects of the PDI amino derivative and α-zirconium phosphate, a condensed flame retardant mechanism with a 1+1>2 ratio is formed. After pre-support intercalation, a large amount of PDI amino derivative can be grafted between the α-zirconium phosphate layers. Both the PDI amino derivative and the α-zirconium phosphate have a certain effect on anti-melting dripping. The PDI amino derivative also accelerates the cross-linking reaction between the α-zirconium phosphate and the polymer, thereby achieving a better anti-melting dripping effect.

[0036] Beneficial effects:

[0037] (1) The present invention discloses a method for preparing a colored flame-retardant polyester fiber having an anti-melting droplet property. The method comprises the following steps: pre-stressing and intercalating α-ZrP with a small molecule amine to increase the interlayer spacing; then reacting the pre-treated α-ZrP with a PDI amino derivative to form an α-ZrP-PDI anti-melting droplet colored flame-retardant molecule, thereby significantly improving the flame retardant and anti-melting droplet properties of the polyester fiber; at the same time, the present invention also introduces a colored molecular unit to give the fiber a bright color, thereby meeting the market demand for color diversity.

[0038] (2) The present invention provides a method for preparing a colored flame-retardant polyester fiber that resists dripping, and achieves flame retardancy and anti-drip effects by adding a single flame-retardant molecule. The molecule is easily dispersed evenly in the polyester matrix, thereby improving the overall performance of the fiber. At the same time, the molecule has a bright color, which meets the aesthetic requirements of colored fibers.

[0039] (3) The present invention provides a method for preparing a colored flame-retardant polyester fiber that resists dripping. The colored flame-retardant polyester fiber resists dripping has better safety performance and aesthetics while maintaining its original mechanical properties, thereby broadening its application prospects in high-end textiles, interior decoration materials and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 Schematic diagram of the α-ZrP-PDI anti-drip colored flame retardant molecule prepared by grafting PDI amino derivatives on the surface and interlayer of α-zirconium phosphate;

[0041] Figure 2 X-ray diffraction patterns of α-zirconium phosphate before and after pre-intercalation;

[0042] Figure 3 This is the infrared spectrum of the α-ZrP-PDI anti-dripping colored flame retardant molecule in Example 1. DETAILED DESCRIPTION

[0043] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0044] The test methods involved in the performance indicators in the embodiments and comparative examples of the present invention are as follows:

[0045] Limiting oxygen index: tested according to GB / T 2406.2-2009.

[0046] Vertical burning grade: tested according to GB / T 2408-2008.

[0047] Breaking strength: tested according to GB / T 14344-2008.

[0048] Color fastness to washing: tested according to GB / T3921-2008.

[0049] Droplet amount: Referring to the description and test method of droplet in patent CN202411077402.1, the present invention adopts a UL1581 combustion tester to continuously burn the sample, collects the droplet at the bottom with water, and weighs and detects the droplet amount.

[0050] The polyester chips of the present invention are sourced from: manufacturer: Yizheng Chemical Fiber, brand: polyester fiber grade semi-dull chips TFW100.

[0051] Example 1

[0052] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0053] (1) Perylene tetracarboxylic dianhydride and ethylenediamine were heated to react in an imidazole solvent at 100° C. under a nitrogen atmosphere for 6 hours. Ethanol was then added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, the molecular structure of which is as follows:

[0054]

[0055] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:1; the amount of ethanol added is 10 times the mass of imidazole; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:25;

[0056] (2) Figure 1 As shown, α-ZrP was stirred evenly in ethanol solvent, and then ethylamine was added and reacted for 1.5 hours to achieve the pre-supported intercalation treatment of α-ZrP;

[0057] The molar ratio of α-ZrP to ethanol solvent is 1:20, and the molar ratio of α-ZrP to small molecule amine is 4:1;

[0058] like Figure 2 As shown in the figure, the characteristic diffraction peak 2θ of α-ZrP shifts from 11.62° to 6.03°. By calculation, it can be concluded that the interlayer spacing increases from 0.76nm to 1.46nm, proving that the interlayer spacing increases after α-zirconium phosphate intercalation.

[0059] (3) adding the PDI amino derivative obtained in step (1) to the system after the reaction in step (2), stirring and reacting for 8 hours, filtering and drying to obtain α-ZrP-PDI anti-melting colored flame retardant molecules;

[0060] The molar ratio of PDI amino derivative to α-ZrP was 1:0.5;

[0061] (4) blending the α-ZrP-PDI colored high-efficiency flame retardant molecule with the polyester chip powder matrix to obtain an anti-drip colored flame retardant masterbatch;

[0062] Based on the total mass of the α-ZrP-PDI anti-dripping colored flame retardant component and the polyester chip powder matrix, the mass percentage of the α-ZrP-PDI anti-dripping colored flame retardant molecule is 30%;

[0063] like Figure 3 The infrared spectrum shown, 1235cm -1The characteristic peak of α-zirconium phosphate is 1595 cm -1 is the characteristic peak of PDI, 1483 cm -1 The peak is -NH3 + The peak of PDI was confirmed to be successfully grafted onto α-zirconium phosphate.

[0064] (5) The anti-melt drip colored flame retardant masterbatch is blended with polyester chips and then sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain the anti-melt drip colored flame retardant polyester fiber; the specific process parameters are as follows:

[0065] The temperature of the single-screw extruder: Zone 1 temperature 275°C, Zone 2 temperature 285°C, Zone 3 temperature 285°C, Zone 4 temperature 285°C, Zone 5 temperature 285°C;

[0066] The spinning temperature is 285°C;

[0067] Cooling conditions included: temperature of 15°C, relative humidity of 60%, and air velocity of 0.3 m / s;

[0068] The drafting ratio is 3 times, the setting temperature is 80°C, and the winding speed is 2800m / min;

[0069] Based on the total amount of the anti-dripping colored flame retardant masterbatch and the polyester chips, the mass percentage of the anti-dripping colored flame retardant masterbatch is 5%.

[0070] The resulting anti-drip colored flame-retardant polyester fiber has a limiting oxygen index of 28%, a vertical burning grade of V0, a ​​droplet amount of 38 mg, a breaking strength of 5.5 cN / dtex, and a color fastness to washing at 60°C of level 4.

[0071] Comparative Example 1

[0072] A method for preparing polyester fiber is basically the same as that in Example 1, except that step (1) of preparing a PDI amino derivative is omitted, that is, step (3) of replacing the PDI amino derivative with PDI, and step (4) of blending a mixture of α-ZrP and PDI with a polyester chip powder matrix to prepare a masterbatch.

[0073] The polyester fiber produced has a limiting oxygen index of 28%, a vertical burning grade of V0, a ​​droplet amount of 145 mg, a breaking strength of 4.8 cN / dtex, and a color fastness to washing at 60°C of grade 2.

[0074] Comparing Comparative Example 1 with Example 1, it can be found that the water washing color fastness of Comparative Example 1 decreases, the droplet amount increases, and the breaking strength decreases. This is because PDI cannot form a chemical bond interaction with α-ZrP, and the PDI molecules are small and easily washed away and discolored after washing; the separate addition of multiple substances can easily lead to uneven mixing, resulting in some parts of the material having no PDI distribution, causing the droplet amount to increase; at the same time, the uneven mixing of multiple substances will cause the mechanical properties of the material to decrease, resulting in a decrease in breaking strength.

[0075] Comparative Example 2

[0076] A method for preparing polyester fiber is basically the same as that of Example 1, except that the pre-support intercalation treatment of α-ZrP in step (2) is omitted, that is, in step (3), a PDI amino derivative is added to an ethanol dispersion of α-ZrP for reaction.

[0077] The polyester fiber obtained has a limiting oxygen index of 28%, a vertical burning grade of V0, a ​​melt drop amount of 215 mg, a breaking strength of 5.5 cN / dtex, and a color fastness to washing at 60°C of grade 4.

[0078] Comparing Comparative Example 2 with Example 1, it can be found that the droplet amount in Comparative Example 2 increases. This is because α-ZrP has not undergone pre-support intercalation treatment, so the molecular layer spacing of α-ZrP is small, and the PDI amino derivative cannot be grafted between the molecular layers of α-ZrP, but can only be grafted to the molecular surface of α-ZrP, which makes the grafting amount of PDI amino derivatives less, resulting in an increase in the droplet amount.

[0079] Comparative Example 3

[0080] A method for preparing polyester fiber is basically the same as Example 1, except that steps (2) and (3) are omitted, and step (4) directly blends the PDI amino derivative with the polyester chip powder matrix to prepare a masterbatch.

[0081] The polyester fiber obtained has a limiting oxygen index of 23%, a vertical burning grade of NR, a droplet amount of 178 mg, a breaking strength of 5.8 cN / dtex, and a color fastness to washing at 60°C of grade 2.

[0082] Comparing Comparative Example 3 with Example 1, it can be found that the limiting oxygen index of Comparative Example 3 decreases, the vertical burning level decreases, the droplet amount increases, the breaking strength increases slightly, and the water washing color fastness decreases. This is because when α-ZrP is not added, the flame retardant performance of the material is poor and the anti-droplet effect decreases, so the limiting oxygen index decreases, the vertical burning level decreases, and the droplet amount increases; at the same time, the addition of inorganic powder such as α-ZrP will lead to a decrease in breaking strength, and the absence of α-ZrP will slightly increase the breaking strength; in addition, the PDI amino derivative molecules are small, and when the inorganic powder α-ZrP is not fixed in the polyester fiber, it is easily washed away and discolored after washing.

[0083] Example 2

[0084] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0085] (1) Perylene tetracarboxylic dianhydride and ethylenediamine were heated to react in an imidazole solvent at 105° C. under a nitrogen atmosphere for 5 hours. Ethanol was then added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, the molecular structure of which is as follows:

[0086]

[0087] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:2; the amount of ethanol added is 10 times the mass of imidazole; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:25;

[0088] (2) After α-ZrP is stirred evenly in ethanol solvent, propylamine is added and reacted for 1.75 hours to achieve pre-supported intercalation treatment of α-ZrP;

[0089] The molar ratio of α-ZrP to ethanol solvent is 1:25, and the molar ratio of α-ZrP to small molecule amine is 4:1;

[0090] (3) adding the PDI amino derivative obtained in step (1) to the system after the reaction in step (2), stirring and reacting for 9 hours, filtering and drying to obtain α-ZrP-PDI anti-melting colored flame retardant molecules;

[0091] The molar ratio of PDI amino derivative to α-ZrP was 1:0.6;

[0092] (4) blending the α-ZrP-PDI colored high-efficiency flame retardant molecule with the polyester chip powder matrix to obtain an anti-drip colored flame retardant masterbatch;

[0093] Based on the total mass of α-ZrP-PDI anti-dripping colored flame retardant and polyester chip powder matrix, the mass percentage of α-ZrP-PDI anti-dripping colored flame retardant molecules is 32%;

[0094] (5) The anti-melt drip colored flame retardant masterbatch is blended with polyester chips and then sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain the anti-melt drip colored flame retardant polyester fiber; the specific process parameters are as follows:

[0095] The temperature of the single-screw extruder: Zone 1 temperature 278°C, Zone 2 temperature 287°C, Zone 3 temperature 287°C, Zone 4 temperature 288°C, Zone 5 temperature 288°C;

[0096] The spinning temperature is 290°C;

[0097] Cooling conditions included: temperature of 18°C, relative humidity of 63%, and air velocity of 0.4 m / s;

[0098] The drafting ratio is 4 times, the setting temperature is 85°C, and the winding speed is 3000m / min;

[0099] Based on the total amount of the anti-dripping colored flame retardant masterbatch and the polyester chips, the mass percentage of the anti-dripping colored flame retardant masterbatch is 7%.

[0100] The resulting anti-drip colored flame-retardant polyester fiber has a limiting oxygen index of 31%, a vertical burning grade of V0, a ​​droplet amount of 35 mg, a breaking strength of 5.3 cN / dtex, and a color fastness to washing at 60°C of level 4.

[0101] Example 3

[0102] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0103] (1) Perylene tetracarboxylic dianhydride and ethylenediamine were heated to react in an imidazole solvent at 110° C. under a nitrogen atmosphere for 4 hours. Ethanol was then added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, the molecular structure of which is as follows:

[0104]

[0105] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:2; the amount of ethanol added is 15 times the mass of imidazole; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:30;

[0106] (2) After α-ZrP is stirred evenly in ethanol solvent, butylamine is added and reacted for 2 hours to achieve pre-supported intercalation treatment of α-ZrP;

[0107] The molar ratio of α-ZrP to ethanol solvent is 1:25, and the molar ratio of α-ZrP to small molecule amine is 4:2;

[0108] (3) adding the PDI amino derivative obtained in step (1) to the system after the reaction in step (2), stirring and reacting for 10 hours, filtering and drying to obtain α-ZrP-PDI anti-drip colored flame retardant molecules;

[0109] The molar ratio of PDI amino derivative to α-ZrP was 1:0.6;

[0110] (4) blending the α-ZrP-PDI colored high-efficiency flame retardant molecule with the polyester chip powder matrix to obtain an anti-drip colored flame retardant masterbatch;

[0111] Based on the total mass of α-ZrP-PDI anti-dripping colored flame retardant and polyester chip powder matrix, the mass percentage of α-ZrP-PDI anti-dripping colored flame retardant molecules is 36%;

[0112] (5) The anti-melt drip colored flame retardant masterbatch is blended with polyester chips and then sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain the anti-melt drip colored flame retardant polyester fiber; the specific process parameters are as follows:

[0113] The temperature of the single-screw extruder: zone 1 temperature 281°C, zone 2 temperature 289°C, zone 3 temperature 289°C, zone 4 temperature 290°C, zone 5 temperature 290°C;

[0114] The spinning temperature is 295°C;

[0115] Cooling conditions included: temperature of 20°C, relative humidity of 65%, and air velocity of 0.5 m / s;

[0116] The drafting ratio is 4.5 times, the setting temperature is 90°C, and the winding speed is 3400m / min;

[0117] Based on the total amount of the anti-dripping colored flame retardant masterbatch and the polyester chips, the mass percentage of the anti-dripping colored flame retardant masterbatch is 10%.

[0118] The resulting anti-drip colored flame-retardant polyester fiber has a limiting oxygen index of 32%, a vertical burning grade of V0, a ​​droplet amount of 34 mg, a breaking strength of 5.2 cN / dtex, and a color fastness to washing at 60°C of level 4.

[0119] Example 4

[0120] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0121] (1) Perylene tetracarboxylic dianhydride and ethylenediamine were heated to react in an imidazole solvent at 102°C under a nitrogen atmosphere for 4.5 hours. Ethanol was then added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, the molecular structure of which is as follows:

[0122]

[0123] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:3; the amount of ethanol added is 15 times the mass of imidazole; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:40;

[0124] (2) After α-ZrP is stirred evenly in ethanol solvent, ethylamine is added and reacted for 2 h to achieve pre-supported intercalation treatment of α-ZrP;

[0125] The molar ratio of α-ZrP to ethanol solvent is 1:25, and the molar ratio of α-ZrP to small molecule amine is 4:3;

[0126] (3) adding the PDI amino derivative obtained in step (1) to the system after the reaction in step (2), stirring and reacting for 11 hours, filtering and drying to obtain α-ZrP-PDI anti-drip colored flame retardant molecules;

[0127] The molar ratio of PDI amino derivative to α-ZrP was 1:0.8;

[0128] (4) blending the α-ZrP-PDI colored high-efficiency flame retardant molecule with the polyester chip powder matrix to obtain an anti-drip colored flame retardant masterbatch;

[0129] Based on the total mass of the α-ZrP-PDI anti-dripping colored flame retardant component and the polyester chip powder matrix, the mass percentage of the α-ZrP-PDI anti-dripping colored flame retardant molecule is 40%;

[0130] (5) The anti-melt drip colored flame retardant masterbatch is blended with polyester chips and then sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain the anti-melt drip colored flame retardant polyester fiber; the specific process parameters are as follows:

[0131] The temperature of the single-screw extruder: zone 1 temperature 284°C, zone 2 temperature 291°C, zone 3 temperature 291°C, zone 4 temperature 292°C, zone 5 temperature 293°C;

[0132] The spinning temperature is 298°C;

[0133] Cooling conditions included: temperature of 22°C, relative humidity of 68%, and air velocity of 0.6 m / s;

[0134] The drafting ratio is 5 times, the setting temperature is 95°C, and the winding speed is 3800m / min;

[0135] Based on the total amount of the anti-dripping colored flame retardant masterbatch and the polyester chips, the mass percentage of the anti-dripping colored flame retardant masterbatch is 12%.

[0136] The final anti-drip colored flame-retardant polyester fiber has a limiting oxygen index of 35%, a vertical burning grade of V0, a ​​droplet amount of 30 mg, a breaking strength of 5 cN / dtex, and a color fastness to washing at 60°C of level 4.

[0137] Example 5

[0138] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0139] (1) Perylene tetracarboxylic dianhydride and ethylenediamine were heated to react in an imidazole solvent at 104°C under a nitrogen atmosphere for 4.75 hours. Ethanol was then added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, the molecular structure of which is as follows:

[0140]

[0141] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:3; the amount of ethanol added is 20 times the mass of imidazole; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:45;

[0142] (2) After α-ZrP is stirred evenly in ethanol solvent, propylamine is added and reacted for 1.75 hours to achieve pre-supported intercalation treatment of α-ZrP;

[0143] The molar ratio of α-ZrP to ethanol solvent is 1:30, and the molar ratio of α-ZrP to small molecule amine is 4:3;

[0144] (3) adding the PDI amino derivative obtained in step (1) to the system after the reaction in step (2), stirring and reacting for 12 hours, filtering and drying to obtain α-ZrP-PDI anti-melting colored flame retardant molecules;

[0145] The molar ratio of PDI amino derivative to α-ZrP was 1:0.8;

[0146] (4) blending the α-ZrP-PDI colored high-efficiency flame retardant molecule with the polyester chip powder matrix to obtain an anti-drip colored flame retardant masterbatch;

[0147] Based on the total mass of α-ZrP-PDI anti-dripping colored flame retardant and polyester chip powder matrix, the mass percentage of α-ZrP-PDI anti-dripping colored flame retardant molecules is 42%;

[0148] (5) The anti-melt drip colored flame retardant masterbatch is blended with polyester chips and then sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain the anti-melt drip colored flame retardant polyester fiber; the specific process parameters are as follows:

[0149] The temperature of the single-screw extruder: Zone 1 temperature 287°C, Zone 2 temperature 293°C, Zone 3 temperature 293°C, Zone 4 temperature 294°C, Zone 5 temperature 294°C;

[0150] The spinning temperature is 300°C;

[0151] Cooling conditions included: temperature of 24°C, relative humidity of 70%, and air velocity of 0.7 m / s;

[0152] The drafting ratio is 5.5 times, the setting temperature is 100°C, and the winding speed is 4000m / min;

[0153] Based on the total amount of the anti-dripping colored flame retardant masterbatch and the polyester chips, the mass percentage of the anti-dripping colored flame retardant masterbatch is 13%.

[0154] The final anti-drip colored flame-retardant polyester fiber has a limiting oxygen index of 37%, a vertical burning grade of V0, a ​​droplet amount of 25 mg, a breaking strength of 4.9 cN / dtex, and a color fastness to washing at 60°C of level 4.

[0155] Example 6

[0156] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0157] (1) Perylene tetracarboxylic dianhydride and ethylenediamine were heated to react in an imidazole solvent at 108° C. under a nitrogen atmosphere for 5.5 hours. Ethanol was then added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, the molecular structure of which is as follows:

[0158]

[0159] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:3; the amount of ethanol added is 20 times the mass of imidazole; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:50;

[0160] (2) After α-ZrP is stirred evenly in ethanol solvent, butylamine is added and reacted for 1.5 hours to achieve pre-supported intercalation treatment of α-ZrP;

[0161] The molar ratio of α-ZrP to ethanol solvent is 1:30, and the molar ratio of α-ZrP to small molecule amine is 4:4;

[0162] (3) adding the PDI amino derivative obtained in step (1) to the system after the reaction in step (2), stirring and reacting for 10 hours, filtering and drying to obtain α-ZrP-PDI anti-drip colored flame retardant molecules;

[0163] The molar ratio of PDI amino derivative to α-ZrP was 1:1;

[0164] (4) blending the α-ZrP-PDI colored high-efficiency flame retardant molecule with the polyester chip powder matrix to obtain an anti-drip colored flame retardant masterbatch;

[0165] Based on the total mass of the α-ZrP-PDI anti-dripping colored flame retardant component and the polyester chip powder matrix, the mass percentage of the α-ZrP-PDI anti-dripping colored flame retardant molecule is 45%;

[0166] (5) The anti-melt drip colored flame retardant masterbatch is blended with polyester chips and then sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain the anti-melt drip colored flame retardant polyester fiber; the specific process parameters are as follows:

[0167] The temperature of the single-screw extruder: zone 1 temperature 290°C, zone 2 temperature 295°C, zone 3 temperature 295°C, zone 4 temperature 295°C, zone 5 temperature 295°C;

[0168] The spinning temperature is 305°C;

[0169] Cooling conditions included: temperature of 25°C, relative humidity of 75%, and air velocity of 0.8 m / s;

[0170] The drafting ratio is 6 times, the setting temperature is 110°C, and the winding speed is 4500m / min;

[0171] Based on the total amount of the anti-dripping colored flame retardant masterbatch and the polyester chips, the mass percentage of the anti-dripping colored flame retardant masterbatch is 15%.

[0172] The resulting anti-drip colored flame-retardant polyester fiber has a limiting oxygen index of 38%, a vertical burning grade of V0, a ​​droplet amount of 21 mg, a breaking strength of 4.8 cN / dtex, and a color fastness to washing at 60°C of level 4.

Claims

1. A method for preparing a drip-resistant colored flame-retardant polyester fiber, characterized by: First, α-ZrP treated with a small molecule amine pre-support intercalation layer is reacted with a PDI amino derivative to obtain an α-ZrP-PDI anti-drip colored flame retardant molecule, then the α-ZrP-PDI anti-drip colored flame retardant molecule is blended with a polyester chip powder matrix to obtain an anti-drip colored flame retardant masterbatch, and finally the anti-drip colored flame retardant masterbatch and the polyester chips are blended and melt-spun to obtain an anti-drip colored flame retardant polyester fiber. PDI amino derivatives refer to PDI derivatives with -NH2 terminal groups; The preparation steps of α-ZrP-PDI anti-drip colored flame retardant molecules are as follows: (1) Perylenetetracarboxylic dianhydride and ethylenediamine were heated in an imidazole solvent at 100-110°C under a nitrogen atmosphere for 4-6 hours, and then ethanol was added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative; (2) After α-ZrP is stirred evenly in ethanol solvent, a small molecular amine is added and reacted for 1.5-2 hours to achieve pre-supported intercalation treatment of α-ZrP; (3) Add the PDI amino derivative obtained in step (1) to the system after the reaction in step (2), stir and react for 8 to 12 hours, and obtain α-ZrP-PDI anti-melting colored flame retardant molecules after filtering and drying.

2. The method for preparing a drip-resistant colored flame-retardant polyester fiber according to claim 1, characterized in that: The molecular structure of PDI amino derivatives is as follows: 。 3. The method for preparing a drip-resistant colored flame-retardant polyester fiber according to claim 1, characterized in that: The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:1-3, the molar ratio of α-ZrP to small molecular amine is 4:1-4, and the molar ratio of PDI amino derivative to α-ZrP is 1:0.5-1.

4. The method for preparing a drip-resistant colored flame-retardant polyester fiber according to claim 1, characterized in that: The small molecule amine is ethylamine, propylamine or butylamine.

5. The method for preparing a drip-resistant colored flame-retardant polyester fiber according to claim 1, characterized in that: Based on the total mass of the α-ZrP-PDI anti-dripping colored flame retardant molecules and the polyester chip powder matrix, the mass percentage of the α-ZrP-PDI anti-dripping colored flame retardant molecules is 30-45%.

6. The method for preparing a drip-resistant colored flame-retardant polyester fiber according to claim 1, characterized in that: Based on the total amount of the anti-dripping colored flame retardant masterbatch and the polyester chips, the mass percentage of the anti-dripping colored flame retardant masterbatch is 5-15%.

7. The method for preparing a drip-resistant colored flame-retardant polyester fiber according to claim 1, characterized in that: Melt spinning includes the process of melt extrusion, spinning, cooling, drawing, shaping and winding through a single screw extruder. The specific process parameters are as follows: The temperature of the single-screw extruder: Zone 1 temperature 275~290℃, Zone 2 temperature 285~295℃, Zone 3 temperature 285~295℃, Zone 4 temperature 285~295℃, Zone 5 temperature 285~295℃; Spinning temperature is 285~305℃; Cooling conditions include: temperature of 15-25°C, relative humidity of 60-75%, and air speed of 0.3-0.8 m / s; The drafting ratio is 3 to 6 times, the setting temperature is 80 to 110°C, and the winding speed is 2800 to 4200 m / min.

8. The method for preparing a drip-resistant colored flame-retardant polyester fiber according to claim 1, characterized in that: The limiting oxygen index of the anti-drip colored flame-retardant polyester fiber is ≥31%, the vertical burning grade is V0, the droplet amount is ≤38mg, the breaking strength is ≥4.9cN / dtex, and the color fastness to washing at 60℃ is above level 4.

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