Colored flame-retardant polyester fiber with high-efficiency flame-retardant properties and preparation method thereof

Abstract

The present invention relates to a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties and a preparation method thereof. First, a PDI derivative having an NH2 terminal group is added to an ethanol dispersion of α-ZrP, and the α-ZrP-PDI colored high-efficiency flame-retardant molecules obtained by the reaction are blended with a polyester chip powder matrix to obtain a colored high-efficiency flame-retardant masterbatch; finally, the colored high-efficiency flame-retardant masterbatch is blended with the polyester chips and melt-spun to obtain a colored flame-retardant polyester fiber; the colored flame-retardant polyester fiber has a limiting oxygen index of ≥32%, a vertical burning grade of V0, a ​​breaking strength of ≥4.7 cN / dtex, and a color fastness to water washing at 60°C of grade 4 or above. The present invention significantly improves the flame retardant effect by reacting α-ZrP with a PDI amino derivative to form an ordered layered stacking structure; the obtained colored flame-retardant polyester fiber not only has excellent flame retardant properties, but also has uniform color distribution and good mechanical strength.

Description

Technical Field

[0001] The invention belongs to the technical field of functional textile materials and relates to a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties and a preparation method thereof. Background Art

[0002] With the development of society and advancements in technology, people are increasingly demanding higher functionality from textiles. Flame-retardant fibers, as an important type of functional fiber, have garnered widespread attention due to their ability to effectively protect people in emergency situations like fires. Traditional polyester fibers suffer from issues such as poor flame retardancy or the impact of adding multi-component masterbatches on other fiber properties. Therefore, developing a polyester fiber with both vibrant colors and excellent flame retardancy is crucial for enhancing the added value and market competitiveness of textiles.

[0003] The existing technology mainly achieves the purpose of colored flame retardancy by adding multiple components into a conventional matrix and adding a colored masterbatch component into a phosphorus-containing copolyester.

[0004] One method involves adding multiple components to a conventional matrix, including a flame retardant component and a colored masterbatch component. Conventional polyester fibers typically incorporate at least two additional components in addition to polyester chips. Patent CN202211327836.3, for example, discloses a solution-dyed, regenerated colored flame-retardant polyester flat filament and its preparation method. The raw materials, by weight, include: 100 parts PET recycled powder, 5-12 parts halogen-free flame retardant, 1-3 parts oxidized polyethylene wax, and 9-16 parts liquid color paste. The liquid color paste includes 2-3 parts modified inorganic pigment, 2-5 parts additive, and 5-8 parts solvent. The additive includes a modified sol-type additive, which is a pseudo-boehmite sol modified with nano-magnesium hydroxide and a C6-C12 aromatic diamine. However, the addition of multiple components is prone to uneven mixing, resulting in a decrease in mechanical strength; and the addition of multiple components increases the complexity of mixing because different components may have different physical and chemical properties, such as density, particle size, fluidity, etc., which will affect their dispersion and mixing in the matrix.

[0005] Another method is to add a color masterbatch component to phosphorus-containing copolyester. When using flame-retardant polyesters such as phosphorus-containing copolyester, which are inherently flame-retardant, to make colored flame-retardant fibers, only the color component is added. However, this also limits the type of matrix, which must be flame-retardant itself. For example, patent CN202311096994.7 discloses a method for producing high-dry heat and high-elongation flame-retardant blue polyester industrial yarn, which uses large-gloss flame-retardant polyester chips as the processing object, and performs pre-crystallization, crystallization, solid-phase polymerization and cooling in four stages under vacuum conditions to complete catalytic viscosity increase. The temperature is first raised from room temperature to 100-110°C to complete pre-crystallization, then raised to 160-190°C for crystallization, and finally raised to 200-210°C for solid-phase polymerization. When the viscosity reaches 1.016±0.01dl / g, the temperature begins to cool down, and the cooling time is controlled at about 4-5h, and the viscosity increase is ended by cooling down; the large-gloss flame-retardant polyester chips with a viscosity of 1.033±0.02dl / g are mixed with masterbatches in proportion, and melt-spun to obtain colored flame-retardant polyester industrial yarn, which has high dry heat, high elongation and flame retardant properties. However, the mechanical properties of phosphorus-containing copolyesters are lower than those of conventional polyesters, and the overall strength is further reduced after the addition of masterbatch.

[0006] In addition, patent CN202210403063.6 discloses a flame-retardant and smoke-suppressing polylactic acid fiber and a preparation method thereof. First, a two-dimensional inorganic micron material (including zirconium phosphate) is intercalated with a small molecule amine, and then organically modified with a long-chain alkane phosphate to prepare an organically modified two-dimensional inorganic micron flame retardant; then, a smoke suppressant (inorganic metal oxide or stannate) is deposited on the surface of the two-dimensional inorganic micron flame retardant to obtain a flame-retardant and smoke-suppressing synergistic functional unit; then, the flame-retardant and smoke-suppressing synergistic functional unit is physically blended with a polylactic acid resin to prepare a flame-retardant and smoke-suppressing polylactic acid resin (denoted as FR-PLA-P1); the flame-retardant and smoke-suppressing polylactic acid resin FR-PLA-P1 is melt-spun to prepare a flame-retardant and smoke-suppressing polylactic acid fiber (denoted as FR-PLA-F1). This patent improves the flame retardant and smoke suppression effects by combining other molecules (ions, oxides) on the surface of zirconium phosphate. However, the flame retardant and smoke suppression polylactic acid fiber produced lacks color properties and can only be achieved through post-dyeing. The color fastness of the colored flame retardant fiber produced in this way is insufficient.

[0007] Therefore, it is of great significance to study a colored flame retardant polyester fiber with high efficiency flame retardant properties and a preparation method thereof 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 colored flame retardant polyester fiber with high-efficiency flame retardant properties and a preparation method thereof.

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

[0010] A method for preparing colored flame-retardant polyester fibers with high-efficiency flame-retardant properties comprises: firstly, adding a PDI (perylene diimide) amino derivative to an ethanol dispersion of α-ZrP (α-zirconium phosphate) to react and obtain an α-ZrP-PDI colored high-efficiency flame-retardant molecule; then, blending the α-ZrP-PDI colored high-efficiency flame-retardant molecule with a polyester chip powder matrix to obtain a colored high-efficiency flame-retardant masterbatch; finally, blending the colored high-efficiency flame-retardant masterbatch with the polyester chips and melt-spinning the blended masterbatch to obtain a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties;

[0011] PDI amino derivatives are PDI derivatives with -NH2 as the terminal group. The amino groups in PDI amino derivatives strongly interact with the hydroxyl groups in α-ZrP. Furthermore, the size of PDI amino derivatives (nanoscale) is smaller than that of α-ZrP (microscale), so they do not change the layered structure of α-ZrP. PDI is an organic dye. The perylene ring is the core structure of the PDI molecule, giving it a red color. When it is prepared into a PDI amino derivative, the perylene ring is not affected, and the resulting PDI amino derivative still has a bright color. Therefore, the substance formed by the interaction of the two is a colored and highly effective flame retardant molecule.

[0012] During the spinning process, the stretching effect will cause the α-ZrP sheets to be oriented along the fiber direction, forming sheet stacks between the α-ZrP. At the same time, the microscopic sheets of PDI amino derivatives grafted on the α-ZrP will also form an orderly stack along the stretching direction. Such a multi-level sheet stacking structure is very beneficial for forming a dense carbon layer, which enables the fiber to quickly form a dense carbon layer when encountering flames, effectively isolating oxygen and heat, thereby achieving the purpose of efficient flame retardancy.

[0013] As the preferred technical solution:

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

[0015]

[0016] As described above, a method for preparing a colored flame-retardant polyester fiber with high-efficiency flame retardant properties is provided, and the synthesis method of the PDI amino derivative is as follows: 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, and then ethanol is added to wash away the imidazole precipitated product, and the solid is filtered and dried to obtain the PDI amino derivative.

[0017] In the method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, the molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:1-3, and the amount of ethanol added is 10-20 times the mass of imidazole.

[0018] As described above, a method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties is described. After a PDI amino derivative is added to an ethanol dispersion of α-ZrP, the mixture is stirred at room temperature for 8 to 12 hours. PDI will be grafted onto the surface of the α-ZrP layer, and the α-ZrP-PDI colored high-efficiency flame-retardant molecule is obtained by filtration and drying.

[0019] In the method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, the molar ratio of PDI amino derivative to α-ZrP is 1:2-4, and the mass concentration of α-ZrP ethanol dispersion is 15-35%.

[0020] The method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties as described above, based on the total mass of the α-ZrP-PDI colored high-efficiency flame-retardant molecules and the polyester chip powder matrix, the mass percentage of the α-ZrP-PDI colored high-efficiency flame-retardant molecules is 30-45%;

[0021] Based on the total amount of colored high-efficiency flame-retardant masterbatch and polyester chips, the mass percentage of the colored high-efficiency flame-retardant masterbatch is 5-15%.

[0022] The method for preparing the colored flame-retardant polyester fiber with high-efficiency flame-retardant properties as described above includes melt spinning, which includes a process flow of melt extrusion through a single-screw extruder, spinning, cooling, drawing, shaping, and winding. The specific process parameters are as follows:

[0023] 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;

[0024] Spinning temperature is 285-305°C;

[0025] Cooling conditions include: temperature of 15-25°C, relative humidity of 60-75%, and air speed of 0.3-0.8 m / s;

[0026] 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.

[0027] The present invention also provides a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, prepared by the preparation method described in any of the above items, with a limiting oxygen index ≥32%, a vertical burning grade of V0, a ​​breaking strength ≥4.7 cN / dtex, and a color fastness to water washing at 60°C of level 4 or above. The high color fastness to water washing is due to the following reasons: on the one hand, the colored molecules are introduced by blending, which has higher color fastness than dyeing; on the other hand, the colored molecules in the present invention are grafted onto the inorganic powder, are not easy to migrate, and are not easily discolored after rinsing like conventional organic colored molecules.

[0028] Principle of the invention:

[0029] The present invention involves reacting α-ZrP with a PDI amino derivative to form a colored, highly efficient flame-retardant α-ZrP-PDI molecule with a layered structure; blending the resulting α-ZrP-PDI molecule with a polyester chip powder matrix to prepare a colored, highly efficient flame-retardant masterbatch containing the flame-retardant molecule; and finally, spinning the colored, highly efficient flame-retardant masterbatch with the polyester chips through a spinning process to obtain a colored, flame-retardant polyester fiber with highly efficient flame-retardant properties. Under the action of the spinning and drawing stress field, the microscopic layers of the α-ZrP lamellae and the grafted PDI amino derivative form an orderly layered stacking structure, significantly improving the flame-retardant effect. Furthermore, because the PDI amino derivative itself is colored, the prepared fiber can have a bright color without the need for an additional coloring step, simplifying the production process and avoiding the significant reduction in fiber mechanical strength caused by the addition of multiple components.

[0030] The α-ZrP unit in the α-ZrP-PDI molecule designed by the present invention decomposes under high temperature conditions, releasing crystal water, absorbing heat, and lowering the temperature of the polyester fiber, thereby slowing thermal decomposition and combustion. The PO* free radicals produced by the decomposition can react with O and OH free radicals in the air, reducing the concentration of combustibles, lowering the oxygen content, and terminating the chain reaction of combustion. The layered structure of the α-ZrP-PDI molecule can quickly form a dense carbon layer when the composite material burns. This not only blocks the mass transfer process of volatile products produced by polymer degradation to the gas phase, but also blocks the feedback of heat generated by gas-phase combustion to the condensed phase, providing heat insulation and oxygen isolation, thereby achieving the purpose of high-efficiency flame retardancy.

[0031] Beneficial effects:

[0032] (1) The present invention provides a method for preparing colored flame-retardant polyester fibers with high-efficiency flame-retardant properties. The microscopic layers of α-ZrP sheets and grafted PDI amino derivatives form an orderly layered stacking structure, which significantly improves the flame-retardant effect. At the same time, it solves the problem of decreased fiber mechanical properties due to the addition of multi-component flame retardants and colored masterbatches in colored flame-retardant fibers. The colored flame-retardant fibers prepared by single-addition synthetic colored high-efficiency flame-retardant molecules have broad market application prospects and important practical value.

[0033] (2) The colored flame-retardant polyester fiber of the present invention has high-efficiency flame-retardant properties, which not only has excellent flame-retardant properties, but also has uniform color distribution and good mechanical strength, and is suitable for textile products that require high flame-retardant standards and aesthetic requirements. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 Schematic diagram of the distribution of colored high-efficiency flame retardant molecules in colored flame retardant polyester fibers;

[0035] Figure 2 This is the infrared spectrum of the α-ZrP-PDI colored high-efficiency flame retardant molecule of Example 1;

[0036] Among them, 1 is α-ZrP, 2 is a PDI amino derivative, and 3 is a colored flame retardant polyester fiber with high-efficiency flame retardant properties. DETAILED DESCRIPTION

[0037] 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.

[0038] The test methods involved in the performance indicators in the embodiments and comparative examples of the present invention are as follows:

[0039] Limiting oxygen index: tested according to GB / T 2406.2-2009.

[0040] Vertical burning grade: tested according to GB / T 2408-2008.

[0041] Breaking strength: tested according to GB / T 14344-2008.

[0042] Color fastness to washing: tested according to GB / T3921-2008.

[0043] The polyester chips of the present invention are sourced from: manufacturer: Yizheng Chemical Fiber, brand: polyester fiber grade semi-dull chips TFW100.

[0044] Example 1

[0045] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0046] (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:

[0047]

[0048] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:1; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:25; and the amount of ethanol added is 10 times the mass of imidazole.

[0049] (2) adding the PDI amino derivative to the ethanol dispersion of α-ZrP, stirring and reacting at room temperature for 8 hours, filtering and drying to obtain the α-ZrP-PDI colored high-efficiency flame retardant molecule;

[0050] The molar ratio of the PDI amino derivative to α-ZrP is 1:2, and the mass concentration of the ethanol dispersion of α-ZrP is 15%;

[0051] (3) α-ZrP-PDI colored high-efficiency flame retardant molecules are blended with polyester chip powder matrix to obtain colored high-efficiency flame retardant masterbatch;

[0052] Based on the total mass of the α-ZrP-PDI colored high-efficiency flame retardant molecules and the polyester chip powder matrix, the mass percentage of the α-ZrP-PDI colored high-efficiency flame retardant molecules is 30%;

[0053] (4) The colored high-efficiency 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 produce a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties; the specific process parameters are as follows:

[0054] 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;

[0055] The spinning temperature is 285°C;

[0056] Cooling conditions included: temperature of 15°C, relative humidity of 60%, and air velocity of 0.3 m / s;

[0057] The drafting ratio is 3 times, the setting temperature is 80°C, and the winding speed is 2800m / min;

[0058] Based on the total amount of colored high-efficiency flame retardant masterbatch and polyester chips, the mass percentage of colored high-efficiency flame retardant masterbatch is 5%.

[0059] The colored flame-retardant polyester fiber with high-efficiency flame-retardant properties finally obtained has a limiting oxygen index of 33%, a vertical burning grade of V0, a ​​breaking strength of 5.2 cN / dtex, and a color fastness to washing at 60°C of level 4.

[0060] like Figure 1 As shown, the α-ZrP-PDI colored high-efficiency flame retardant molecules in the colored flame retardant polyester fiber 3 with high-efficiency flame retardant properties have a molecular microscopic large lamellar structure, and -NH2 at both ends of the molecule provides subsequent synthesis of α-ZrP-PDI colored high-efficiency flame retardant molecule binding sites.

[0061] like Figure 2 The infrared spectrum shown, 1235cm -1 Characteristic peak of α-ZrP 1, 1595 cm -1 The characteristic peak of PDI amino derivative 2, 1483 cm -1 The peak is -NH3 + The peak of α-ZrP 1 was confirmed, proving that the PDI amino derivative 2 was successfully grafted onto α-ZrP 1.

[0062] Comparative Example 1

[0063] 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 (2) of replacing the PDI amino derivative with PDI, and step (3) of blending a mixture of α-ZrP and PDI with a polyester chip powder matrix to prepare a masterbatch.

[0064] The polyester fiber has a limiting oxygen index of 28%, a vertical burning grade of V0, a ​​breaking strength of 5.2 cN / dtex, and a color fastness to washing at 60°C of grade 2.

[0065] Comparing Comparative Example 1 with Example 1, it can be found that the limiting oxygen index of Comparative Example 1 decreases and the water washing color fastness deteriorates. This is because PDI cannot react with α-ZrP and forms a microscopic lamellar stacking structure on the surface of α-ZrP, which reduces the flame retardant effect. In addition, the PDI molecules not attached to the surface of α-ZrP are small and cannot be fixed inside the fiber. They are easily discolored under water washing, resulting in a decrease in water washing color fastness.

[0066] Comparative Example 2

[0067] A method for preparing polyester fiber is basically the same as that of Example 1, except that step (2) is omitted and step (3) directly blends the PDI amino derivative with the polyester chip powder matrix to prepare a masterbatch.

[0068] The polyester fiber has a limiting oxygen index of 23%, a vertical burning grade of NR, a breaking strength of 5.2 cN / dtex, and a color fastness to washing at 60°C of grade 2.

[0069] Comparing Comparative Example 2 with Example 1, it can be found that the limiting oxygen index of Comparative Example 2 is greatly reduced, the vertical burning grade fails to reach any specific flame retardant grade, and the water washing color fastness deteriorates. This is because the PDI amino derivatives in the absence of α-ZrP cannot achieve the flame retardant effect; at the same time, the PDI amino derivatives are too small to be fixed inside the fiber, and are easily discolored by water washing, resulting in a decrease in water washing color fastness.

[0070] Comparative Example 3

[0071] A method for preparing polyester fiber is basically the same as that of Example 1, except that step (2) is omitted and step (3) directly blends a mixture of PDI amino derivatives and α-ZrP with a polyester chip powder matrix to prepare a masterbatch.

[0072] The polyester fiber has a limiting oxygen index of 27%, a vertical burning grade of V0, a ​​breaking strength of 5.2 cN / dtex, and a color fastness to washing at 60°C of grade 2.

[0073] Comparing Comparative Example 3 with Example 1, it can be found that the limiting oxygen index of Comparative Example 3 decreases and the water washing color fastness deteriorates. This is because the PDI amino derivative cannot combine with α-ZrP during the subsequent processing process, and the PDI amino derivative cannot form a microscopic lamellar stacking structure on the surface of α-ZrP, which reduces the flame retardant effect. At the same time, the PDI amino derivative molecules are small and cannot be fixed inside the fiber. They are easily discolored when washed with water, resulting in a decrease in water washing color fastness.

[0074] Example 2

[0075] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0076] (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:

[0077]

[0078] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:1; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:25; and the amount of ethanol added is 10 times the mass of imidazole.

[0079] (2) adding the amino derivative of PDI to the ethanol dispersion of α-ZrP, stirring and reacting at room temperature for 9 hours, filtering and drying to obtain the colored and highly effective flame retardant α-ZrP-PDI molecule;

[0080] The molar ratio of the PDI amino derivative to α-ZrP is 1:2, and the mass concentration of the ethanol dispersion of α-ZrP is 18%;

[0081] (3) α-ZrP-PDI colored high-efficiency flame retardant molecules are blended with polyester chip powder matrix to obtain colored high-efficiency flame retardant masterbatch;

[0082] Based on the total mass of α-ZrP-PDI colored high-efficiency flame retardant molecules and polyester chip powder matrix, the mass percentage of α-ZrP-PDI colored high-efficiency flame retardant molecules is 32%;

[0083] (4) The colored high-efficiency 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 produce a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties; the specific process parameters are as follows:

[0084] 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;

[0085] The spinning temperature is 290°C;

[0086] Cooling conditions included: temperature of 18°C, relative humidity of 63%, and air velocity of 0.4 m / s;

[0087] The drafting ratio is 4 times, the setting temperature is 85°C, and the winding speed is 3000m / min;

[0088] Based on the total amount of colored high-efficiency flame retardant masterbatch and polyester chips, the mass percentage of colored high-efficiency flame retardant masterbatch is 5%.

[0089] The colored flame-retardant polyester fiber with high-efficiency flame-retardant properties finally obtained has a limiting oxygen index of 35%, a vertical burning grade of V0, a ​​breaking strength of 4.9 cN / dtex, and a color fastness to washing at 60°C of level 4.

[0090] Example 3

[0091] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0092] (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:

[0093]

[0094] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:2; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:30; and the amount of ethanol added is 12 times the mass of imidazole.

[0095] (2) adding the PDI amino derivative to the ethanol dispersion of α-ZrP, stirring and reacting at room temperature for 10 hours, filtering and drying to obtain the α-ZrP-PDI colored high-efficiency flame retardant molecule;

[0096] The molar ratio of the PDI amino derivative to α-ZrP is 1:2, and the mass concentration of the ethanol dispersion of α-ZrP is 22%;

[0097] (3) α-ZrP-PDI colored high-efficiency flame retardant molecules are blended with polyester chip powder matrix to obtain colored high-efficiency flame retardant masterbatch;

[0098] Based on the total mass of α-ZrP-PDI colored high-efficiency flame retardant molecules and polyester chip powder matrix, the mass percentage of α-ZrP-PDI colored high-efficiency flame retardant molecules is 34%;

[0099] (4) The colored high-efficiency 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 produce a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties; the specific process parameters are as follows:

[0100] 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;

[0101] The spinning temperature is 295°C;

[0102] Cooling conditions included: temperature of 20°C, relative humidity of 65%, and air velocity of 0.5 m / s;

[0103] The drafting ratio is 4.5 times, the setting temperature is 90°C, and the winding speed is 3400m / min;

[0104] Based on the total amount of colored high-efficiency flame retardant masterbatch and polyester chips, the mass percentage of colored high-efficiency flame retardant masterbatch is 10%.

[0105] The colored flame-retardant polyester fiber with high-efficiency flame-retardant properties finally obtained has a limiting oxygen index of 36%, a vertical burning grade of V0, a ​​breaking strength of 4.7 cN / dtex, and a color fastness to washing at 60°C of level 4.

[0106] Example 4

[0107] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0108] (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:

[0109]

[0110] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:2; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:40; and the amount of ethanol added is 14 times the mass of imidazole.

[0111] (2) adding the PDI amino derivative to the ethanol dispersion of α-ZrP, stirring and reacting at room temperature for 11 hours, filtering and drying to obtain the α-ZrP-PDI colored high-efficiency flame retardant molecule;

[0112] The molar ratio of the PDI amino derivative to α-ZrP is 1:3, and the mass concentration of the α-ZrP ethanol dispersion is 25%;

[0113] (3) α-ZrP-PDI colored high-efficiency flame retardant molecules are blended with polyester chip powder matrix to obtain colored high-efficiency flame retardant masterbatch;

[0114] Based on the total mass of α-ZrP-PDI colored high-efficiency flame retardant molecules and polyester chip powder matrix, the mass percentage of α-ZrP-PDI colored high-efficiency flame retardant molecules is 38%;

[0115] (4) The colored high-efficiency 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 produce a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties; the specific process parameters are as follows:

[0116] 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;

[0117] The spinning temperature is 298°C;

[0118] Cooling conditions included: temperature of 22°C, relative humidity of 68%, and air velocity of 0.6 m / s;

[0119] The drafting ratio is 5 times, the setting temperature is 95°C, and the winding speed is 3800m / min;

[0120] Based on the total amount of colored high-efficiency flame retardant masterbatch and polyester chips, the mass percentage of colored high-efficiency flame retardant masterbatch is 10%.

[0121] The colored flame-retardant polyester fiber with high-efficiency flame-retardant properties finally obtained has a limiting oxygen index of 37%, a vertical burning grade of V0, a ​​breaking strength of 4.6 cN / dtex, and a color fastness to washing at 60°C of level 4.

[0122] Example 5

[0123] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0124] (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:

[0125]

[0126] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:2; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:45; and the amount of ethanol added is 16 times the mass of imidazole.

[0127] (2) adding the PDI amino derivative to the ethanol dispersion of α-ZrP, stirring and reacting at room temperature for 12 hours, filtering and drying to obtain the α-ZrP-PDI colored high-efficiency flame retardant molecule;

[0128] The molar ratio of the PDI amino derivative to α-ZrP is 1:3, and the mass concentration of the α-ZrP ethanol dispersion is 30%;

[0129] (3) α-ZrP-PDI colored high-efficiency flame retardant molecules are blended with polyester chip powder matrix to obtain colored high-efficiency flame retardant masterbatch;

[0130] Based on the total mass of α-ZrP-PDI colored high-efficiency flame retardant molecules and polyester chip powder matrix, the mass percentage of α-ZrP-PDI colored high-efficiency flame retardant molecules is 42%;

[0131] (4) The colored high-efficiency 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 produce a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties; the specific process parameters are as follows:

[0132] 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;

[0133] The spinning temperature is 300°C;

[0134] Cooling conditions included: temperature of 24°C, relative humidity of 70%, and air velocity of 0.7 m / s;

[0135] The drafting ratio is 5.5 times, the setting temperature is 100°C, and the winding speed is 4000m / min;

[0136] Based on the total amount of colored high-efficiency flame retardant masterbatch and polyester chips, the mass percentage of colored high-efficiency flame retardant masterbatch is 15%.

[0137] The colored flame-retardant polyester fiber with high-efficiency flame-retardant properties finally obtained has a limiting oxygen index of 39%, a vertical burning grade of V0, a ​​breaking strength of 4.6 cN / dtex, and a color fastness to washing at 60°C of level 4.

[0138] Example 6

[0139] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, comprising the following steps:

[0140] (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:

[0141]

[0142] The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:3; the mass ratio of perylenetetracarboxylic dianhydride to imidazole is 1:50; and the amount of ethanol added is 20 times the mass of imidazole.

[0143] (2) adding the PDI amino derivative to the ethanol dispersion of α-ZrP, stirring and reacting at room temperature for 10 hours, filtering and drying to obtain the α-ZrP-PDI colored high-efficiency flame retardant molecule;

[0144] The molar ratio of the PDI amino derivative to α-ZrP is 1:4, and the mass concentration of the α-ZrP ethanol dispersion is 35%;

[0145] (3) α-ZrP-PDI colored high-efficiency flame retardant molecules are blended with polyester chip powder matrix to obtain colored high-efficiency flame retardant masterbatch;

[0146] Based on the total mass of the α-ZrP-PDI colored high-efficiency flame retardant molecules and the polyester chip powder matrix, the mass percentage of the α-ZrP-PDI colored high-efficiency flame retardant molecules is 45%;

[0147] (4) The colored high-efficiency 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 produce a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties; the specific process parameters are as follows:

[0148] 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;

[0149] The spinning temperature is 305°C;

[0150] Cooling conditions included: temperature of 25°C, relative humidity of 75%, and air velocity of 0.8 m / s;

[0151] The drafting ratio is 6 times, the setting temperature is 110°C, and the winding speed is 4500m / min;

[0152] Based on the total amount of colored high-efficiency flame retardant masterbatch and polyester chips, the mass percentage of colored high-efficiency flame retardant masterbatch is 15%.

[0153] The colored flame-retardant polyester fiber with high-efficiency flame-retardant properties finally obtained has a limiting oxygen index of 40%, a vertical burning grade of V0, a ​​breaking strength of 4.5 cN / dtex, and a color fastness to washing at 60°C of level 4.

Claims

1. A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, characterized by: First, a PDI amino derivative is added to an ethanol dispersion of α-ZrP to react and obtain a colored, highly efficient flame-retardant α-ZrP-PDI molecule. Then, the colored, highly efficient flame-retardant α-ZrP-PDI molecule is blended with a polyester chip powder matrix to obtain a colored, highly efficient flame-retardant masterbatch. Finally, the colored, highly efficient flame-retardant masterbatch and polyester chips are blended and melt-spun to produce a colored, flame-retardant polyester fiber with highly efficient flame-retardant properties. PDI amino derivatives refer to PDI derivatives with -NH2 terminal groups; The synthesis method of the PDI amino derivative is as follows: perylene tetracarboxylic dianhydride and ethylenediamine are heated in an imidazole solvent under a nitrogen atmosphere at 100-110° C. for reaction for 4-6 hours, ethanol is then added to precipitate the product, and the solid is filtered and dried to obtain the PDI amino derivative.

2. The method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties according to claim 1, characterized in that: The molecular structure of PDI amino derivatives is as follows: 。 3. The method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties according to claim 1, characterized in that: The molar ratio of perylenetetracarboxylic dianhydride to ethylenediamine is 1:1-3, and the amount of ethanol added is 10-20 times the mass of imidazole.

4. The method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties according to claim 1, characterized in that: After the PDI amino derivative is added to the ethanol dispersion of α-ZrP, the reaction is stirred for 8 to 12 hours, and the α-ZrP-PDI colored and efficient flame retardant molecule is obtained by filtering and drying.

5. The method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties according to claim 1, characterized in that: The molar ratio of the PDI amino derivative to α-ZrP is 1:2-4, and the mass concentration of the α-ZrP ethanol dispersion is 15-35%.

6. The method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties according to claim 1, characterized in that: Based on the total mass of α-ZrP-PDI colored high-efficiency flame retardant molecules and polyester chip powder matrix, the mass percentage of α-ZrP-PDI colored high-efficiency flame retardant molecules is 30-45%; Based on the total amount of colored high-efficiency flame retardant masterbatch and polyester chips, the mass percentage of colored high-efficiency flame retardant masterbatch is 5~15%.

7. The method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties 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℃, relative humidity of 60~75%, and air speed of 0.3~0.8m / 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. A colored flame-retardant polyester fiber with high-efficiency flame-retardant properties obtained by the preparation method according to any one of claims 1 to 7, characterized in that: The limiting oxygen index is ≥32%, the vertical burning grade is V0, the breaking strength is ≥4.7cN / dtex, and the color fastness to washing at 60℃ is above level 4.

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