Colored flame-retardant polyester fiber with efficient flame-retardant characteristic and preparation method of colored flame-retardant polyester fiber

Abstract

The invention relates to a colored flame-retardant polyester fiber with efficient flame-retardant characteristic and a preparation method thereof.The preparation method comprises the steps that firstly, a PDI derivative with the end group being-NH2 is added into ethyl alcohol dispersion liquid of alpha-ZrP, alpha-ZrP-PDI colored efficient flame-retardant molecules obtained through a reaction are blended with a polyester chip powder matrix, and colored efficient flame-retardant master batches are obtained; and finally, blending the colored high-efficiency flame-retardant master batch and polyester chips, and carrying out melt spinning to obtain the colored flame-retardant polyester fiber. The limit oxygen index of the colored flame-retardant polyester fiber is greater than or equal to 32%, the vertical combustion grade is V0, the breaking strength is greater than or equal to 4.7 cN / dtex, and the washing color fastness at 60 DEG C is above grade 4. The alpha-ZrP and the PDI amino derivative react to form an ordered layered stacking structure, so that the flame-retardant effect is remarkably improved; the prepared colored flame-retardant polyester fiber not only has excellent flame retardance, 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 the advancement of science and technology, people have higher and higher requirements for the functionality of textiles. As an important type of functional fiber, flame retardant fiber has attracted widespread attention because it can effectively protect human safety in emergency situations such as fire. Traditional polyester fibers have problems such as poor flame retardant effect or the addition of multi-component masterbatch affects other properties of the fiber. Therefore, the development of a polyester fiber with both bright colors and excellent flame retardant properties is of great significance to improving 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 is to add multiple components to the conventional matrix, including flame retardant components and colored masterbatch components. Most of the colored flame-retardant fibers made from conventional polyester add at least two components in addition to polyester chips. For example, patent CN202211327836.3 discloses a liquid-dyed regenerated colored flame-retardant polyester flat filament and its preparation method, the raw materials of which include by weight: 100 parts of PET recycled powder, 5-12 parts of halogen-free flame retardant, 1-3 parts of oxidized polyethylene wax, 9-16 parts of liquid color paste; the liquid color paste includes 2-3 parts of modified inorganic pigments, 2-5 parts of additives and 5-8 parts of solvents; the additives include modified sol-type additives; the modified sol-type additives are pseudo-boehmite sols modified by nano-magnesium hydroxide and C6-C12 aromatic diamines. However, multi-component addition is prone to uneven mixing, resulting in decreased mechanical strength; and multi-component addition 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] The other is to add a colored masterbatch component to the phosphorus-containing copolyester. When using flame-retardant polyesters such as phosphorus-containing copolyesters, which have flame-retardant effects, to make colored flame-retardant fibers, only colored components are added, but this also limits the type of matrix, which requires the matrix itself to be flame-retardant. For example, patent CN202311096994.7 discloses a method for producing high dry heat and high elongation flame-retardant blue polyester industrial yarn, which takes bright 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 drop, and the cooling time is controlled at about 4-5h, and the viscosity increase is terminated by cooling; the bright 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 the characteristics of 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 lost 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 obtained lacks color properties and can only be achieved through post-dyeing. The color fastness of the colored flame retardant fiber made 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] 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 fiber with high-efficiency flame-retardant properties, firstly, adding a PDI (perylene diimide) amino derivative to an ethanol dispersion of α-ZrP (α-zirconium phosphate) to react and obtain α-ZrP-PDI colored high-efficiency flame-retardant molecules; then, blending the α-ZrP-PDI colored high-efficiency flame-retardant molecules 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 then melt-spinning to obtain a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties;

[0011] PDI amino derivatives refer to PDI derivatives with -NH2 as the terminal group; the amino group in the PDI amino derivatives will have a strong interaction with the hydroxyl group in α-ZrP; in addition, the size of the PDI amino derivatives (nanoscale) is smaller than the size of α-ZrP (microscale), so it will not change the layered structure of α-ZrP. PDI is an organic dye, and the perylene ring is the core structure of the PDI molecule, making it appear red. After it is prepared into a PDI amino derivative, the perylene ring is not affected, and the formed PDI amino derivative still has a bright color. Therefore, the substance formed after the two interact is a colored and efficient flame retardant molecule;

[0012] During the spinning process, the stretching effect will cause the α-ZrP sheets to be oriented along the fiber direction, and the α-ZrP sheets will be stacked. 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, so that the fiber can 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 method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties as described above, 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, the synthesis method of PDI amino derivatives is: 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 at 100-110°C 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 colored flame-retardant polyester fiber with high-efficiency flame-retardant properties as described above, 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, in the method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, after adding a PDI amino derivative to an ethanol dispersion of α-ZrP, stirring and reacting at room temperature for 8 to 12 hours, PDI will be grafted onto the surface of the α-ZrP sheet, and then filtered and dried to obtain an α-ZrP-PDI colored high-efficiency flame-retardant molecule.

[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 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, melt spinning includes a process flow of melt extrusion by a single screw extruder, spinning, cooling, drawing, shaping and winding, and 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] The spinning temperature is 285-305°C;

[0025] The cooling conditions include: temperature of 15-25°C, relative humidity of 60-75%, and air blowing 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 as described in any of the above items, with a limiting oxygen index of ≥32%, a vertical burning grade of V0, a ​​breaking strength of ≥4.7 cN / dtex, and a 60°C water washing color fastness of above level 4. The reason why it has high water washing color fastness is that: on the one hand, the colored molecules are introduced by blending, and the color fastness is higher than that by dyeing; on the other hand, the colored molecules in the present invention are grafted on the inorganic powder, are not easy to migrate, and are not easy to decolorize after rinsing like conventional organic colored molecules.

[0028] Principle of the invention:

[0029] The present invention forms colored α-ZrP-PDI high-efficiency flame-retardant molecules with a layered structure by reacting α-ZrP with PDI amino derivatives; blending the obtained α-ZrP-PDI molecules with a polyester chip powder matrix to prepare colored high-efficiency flame-retardant masterbatch containing flame-retardant molecules; finally, the colored high-efficiency flame-retardant masterbatch is blended and spun with polyester chips through a spinning process to obtain colored flame-retardant polyester fibers with high-efficiency 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 derivatives form an orderly layered stacking structure, which significantly improves the flame-retardant effect; and, since the PDI amino derivatives themselves have colors, the prepared fibers can have bright colors without an additional coloring step, simplifying the production process, and also avoiding the problem of a significant decrease in the mechanical strength of the fibers due to 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, releases crystal water, absorbs heat, and reduces the temperature of the polyester fiber, thereby slowing down the thermal decomposition and combustion rate. The PO* free radicals generated by the decomposition can react with the O and OH free radicals in the air, reduce the concentration of combustibles, reduce the oxygen content, and terminate 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, which can not only block the mass transfer process of volatile products generated by polymer degradation to the gas phase, but also block the feedback of heat generated by gas phase combustion to the condensed phase, playing a role of heat insulation and oxygen isolation, thereby achieving the purpose of high-efficiency flame retardancy.

[0031] Beneficial effects:

[0032] (1) The invention discloses 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, the problem of decreased fiber mechanical properties due to the addition of multi-component flame retardants and colored masterbatches is solved. The colored flame-retardant fibers prepared by adding a single synthetic colored high-efficiency flame-retardant molecule have broad market application prospects and important practical value.

[0033] (2) The colored flame-retardant polyester fiber with high-efficiency flame-retardant properties of the present invention 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 This is a 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] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it 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 within the scope limited by the appended claims of the application equally.

[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] Washing color fastness: 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, the specific steps are as follows:

[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, and then ethanol was added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, whose molecular structure is as follows:

[0047]

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

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

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

[0051] (3) blending the α-ZrP-PDI colored high-efficiency flame-retardant molecule with the polyester chip powder matrix to obtain a 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) After the colored high-efficiency flame-retardant masterbatch is blended with the polyester chips, the mixture is sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain 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] The 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 grade 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 molecules binding sites.

[0061] like Figure 2 The infrared spectrum shown, 1235cm -1 It is the characteristic peak of α-ZrP 1, 1595cm -1 The characteristic peak of PDI amino derivative 2, 1483 cm -1 The peak is -NH3 + The peak of α-ZrP 1 was obtained, 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 of Example 1, except that the operation of preparing a PDI amino derivative in step (1) is omitted, that is, the PDI amino derivative is replaced with PDI in step (2), and the masterbatch is prepared by blending a mixture of α-ZrP and PDI with a polyester chip powder matrix in step (3).

[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] By 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 becomes worse. This is because PDI cannot react with α-ZrP to form a microscopic lamellar stacking structure on the surface of α-ZrP, which reduces the flame retardant effect, and the PDI molecules not connected to the surface of α-ZrP are smaller and cannot be fixed inside the fiber, and are easily discolored under water washing, resulting in reduced 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 the operation of 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] By 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 level fails to reach any specific flame retardant level, and the water washing color fastness becomes poor. 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 under water washing, resulting in a decrease in the 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 the operation of step (2) is omitted and step (3) directly blends a mixture of PDI amino derivative 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] By 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 becomes worse. This is because the PDI amino derivative cannot combine with α-ZrP during the subsequent processing, 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, and are easily discolored under water washing, resulting in reduced water washing color fastness.

[0074] Example 2

[0075] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, the specific steps are as follows:

[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, and then ethanol was added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, whose molecular structure is as follows:

[0077]

[0078] The molar ratio of perylene tetracarboxylic dianhydride to ethylenediamine is 1:1; the mass ratio of perylene tetracarboxylic dianhydride to imidazole is 1:25; 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 efficient 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) blending the α-ZrP-PDI colored high-efficiency flame-retardant molecule with the polyester chip powder matrix to obtain a 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) After the colored high-efficiency flame-retardant masterbatch is blended with the polyester chips, the mixture is sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain 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] The 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 grade 4.

[0090] Example 3

[0091] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, the specific steps are as follows:

[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, and then ethanol was added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, whose molecular structure is as follows:

[0093]

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

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

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

[0097] (3) blending the α-ZrP-PDI colored high-efficiency flame-retardant molecule with the polyester chip powder matrix to obtain a 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) After the colored high-efficiency flame-retardant masterbatch is blended with the polyester chips, the mixture is sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain 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] The 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 grade 4.

[0106] Example 4

[0107] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, the specific steps are as follows:

[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, and then ethanol was added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, whose molecular structure is as follows:

[0109]

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

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

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

[0113] (3) blending the α-ZrP-PDI colored high-efficiency flame-retardant molecule with the polyester chip powder matrix to obtain a 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) After the colored high-efficiency flame-retardant masterbatch is blended with the polyester chips, the mixture is sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain 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] The 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 grade 4.

[0122] Example 5

[0123] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, the specific steps are as follows:

[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, and then ethanol was added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, whose molecular structure is as follows:

[0125]

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

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

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

[0129] (3) blending the α-ZrP-PDI colored high-efficiency flame-retardant molecule with the polyester chip powder matrix to obtain a 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) After the colored high-efficiency flame-retardant masterbatch is blended with the polyester chips, the mixture is sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain 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] The 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 grade 4.

[0138] Example 6

[0139] A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, the specific steps are as follows:

[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, and then ethanol was added to precipitate the product. The solid was filtered and dried to obtain a PDI amino derivative, whose molecular structure is as follows:

[0141]

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

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

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

[0145] (3) blending the α-ZrP-PDI colored high-efficiency flame-retardant molecule with the polyester chip powder matrix to obtain a 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) After the colored high-efficiency flame-retardant masterbatch is blended with the polyester chips, the mixture is sequentially subjected to a process of melt extrusion, spinning, cooling, drawing, shaping and winding by a single screw extruder to finally obtain 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] The 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 grade 4.

Claims

1. A method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties, characterized in that: Firstly, PDI amino derivatives are added to an ethanol dispersion of α-ZrP to react and obtain α-ZrP-PDI colored high-efficiency flame-retardant molecules; then, the α-ZrP-PDI colored high-efficiency flame-retardant molecules 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 chip and melt-spun to obtain a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties; PDI amino derivatives refer to PDI derivatives with -NH2 terminal groups.

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 2, characterized in that: The synthesis method of the PDI amino derivative is as follows: heating perylene tetracarboxylic dianhydride and ethylenediamine in an imidazole solvent at 100-110° C. in a nitrogen atmosphere for 4-6 hours, then adding ethanol to precipitate the product, filtering the solid and drying to obtain the PDI amino derivative.

4. The method for preparing a colored flame-retardant polyester fiber with high-efficiency flame-retardant properties according to claim 3, characterized in that: The molar ratio of perylene tetracarboxylic dianhydride to ethylenediamine is 1:1-3, and the amount of ethanol added is 10-20 times the mass of imidazole.

5. 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 into the ethanol dispersion of α-ZrP, the mixture is stirred for reaction for 8 to 12 hours, and then filtered and dried to obtain the α-ZrP-PDI colored high-efficiency flame retardant molecule.

6. 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%.

7. The method for preparing colored flame-retardant polyester fiber with high-efficiency flame-retardant properties according to claim 1, characterized in that: 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%; 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%.

8. The method for preparing 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 by a single screw extruder. The specific process parameters are as follows: 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; The spinning temperature is 285-305°C; The cooling conditions include: temperature of 15-25°C, relative humidity of 60-75%, and air blowing speed of 0.3-0.8 m / s; 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.

9. 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 8, 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 grade 4.

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