Colored flame-retardant master batch and preparation method of colored flame-retardant fiber

Abstract

The invention belongs to the technical field of flame-retardant fibers, and discloses a colored flame-retardant master batch and a preparation method of colored flame-retardant fibers.The preparation method of the colored flame-retardant master batch comprises the steps that a flame retardant PDI-MA and a polyester chip powder matrix are blended, extruded and granulated, and the colored flame-retardant master batch is prepared; the preparation method of the colored flame-retardant fiber comprises the following steps: blending the prepared colored flame-retardant master batch and polyester chips, and carrying out melt spinning to obtain the colored flame-retardant polyester fiber. The pigment and the flame retardant in the flame retardant PDI-MA prepared by the invention are carriers for each other, and the advantages of MA and PTCDA are combined, so that the colored flame-retardant polyester fiber prepared from the flame retardant PDI-MA has colored and flame-retardant properties, and the overall flame retardance is improved synergistically.

Description

Technical Field

[0001] The invention belongs to the technical field of flame-retardant fibers and relates to a preparation method of a colored flame-retardant masterbatch and a colored flame-retardant fiber. Background Art

[0002] Polyester fiber, as a fusible and combustible fiber, will continue to burn once it encounters a flame source, which limits its application in certain special fields. However, due to the lack of color-developing groups in its molecular structure, coupled with the characteristics of high crystallinity and high orientation, traditional polyester fiber presents a single white color and is difficult to dye by conventional means.

[0003] The traditional dyeing process not only consumes a lot of energy, but also causes serious environmental pollution. It also has problems such as low color fastness and uneven coloring, and also has adverse effects on the mechanical properties of the fiber. However, in the fields of clothing and decoration, the vividness of color is crucial. It can quickly catch people's attention and convey specific emotions and atmosphere. Therefore, combining color with flame retardant properties can not only protect people's lives and property, but also meet the public's demand for color diversity.

[0004] However, in the current process of preparing colored flame-retardant fibers, in addition to adding flame retardants, it is also necessary to prepare flame-retardant colored masterbatches by adding color pastes or colored masterbatches / chips.

[0005] For example, patent CN117265689A discloses a regenerated colored flame-retardant fiber and a preparation method thereof, wherein the preparation method comprises preparing a flame retardant by mixing a flame retardant and a color paste to obtain a flame-retardant liquid color paste, mixing the color paste with a powder, performing melt granulation, obtaining a colored flame-retardant masterbatch, and then performing melt spinning.

[0006] Patent CN112481730A discloses a flame retardant, antiviral and antibacterial colored fiber and its production method. The preparation method is to prepare a flame retardant / multifunctional agent, directly melt blend it with colored polyester chips and masterbatches to obtain colored flame retardant masterbatches, and then melt spinning.

[0007] Patent CN111893596A discloses a flame-retardant colored antistatic polyester fiber and a preparation method thereof. The preparation method comprises mixing and drying a flame retardant, polyester chips and a colored masterbatch, and then melt-spinning.

[0008] Patent CN105525380A discloses an antibacterial and flame-retardant polypropylene colored filament and a preparation method thereof. The preparation method comprises the following steps of mixing a carrier and a flame retardant by a high-speed mixer to obtain a mixture, and then granulating the mixture by a twin-screw extruder. The colored masterbatch and the newly prepared masterbatch are then mixed and granulated for a second time to obtain mixed pellets, and finally melt-spinning is performed.

[0009] The above existing technology usually involves multiple complex processes, i.e., two steps of coloring and flame retardant (at least two additions are required). This multiple addition method not only increases the complexity of the process, but also easily leads to uneven dispersion of dyes and flame retardants in the fiber, which in turn leads to the material not being protected by flame retardants in certain areas, local heat concentration during combustion, and flame retardants being unable to exert their expected effects, thereby reducing flame retardant properties. The uneven distribution of dyes can also directly lead to uneven product color at the same time, which is particularly obvious in textiles and may cause negative reactions from consumers. In addition, the dyes used in the prior art are common dyes, which have weak tinting power and are generally compatible with polyester substrates.

[0010] Therefore, it is of great significance to study a method for preparing a colored flame retardant masterbatch and a colored flame retardant fiber to solve the above problems. Summary of the invention

[0011] The purpose of the present invention is to solve the problems existing in the prior art and provide a method for preparing a colored flame retardant masterbatch and a colored flame retardant fiber.

[0012] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0013] A method for preparing a colored flame retardant masterbatch, comprising blending a flame retardant PDI-MA with a polyester chip powder matrix and extruding and granulating the mixture to obtain a colored flame retardant masterbatch;

[0014] The chemical structure of flame retardant PDI (perylene diimide)-MA (melamine) is as follows:

[0015]

[0016] The sublimation, volatilization, evaporation and decomposition of MA are all endothermic, which can significantly reduce the temperature of the combustion zone. When MA decomposes, it can generate gaseous products such as MA vapor, water vapor, N2, CO2, NH3, etc., which can not only dilute the concentration of combustible gas and oxygen in the combustion zone to below the ignition limit, playing a gas phase flame retardant role, but also has a covering effect (blanket effect). MA can form a variety of cross-linked polycondensates when decomposed at high temperatures. The char generated by plastics containing MA and its salts at high temperatures is a good protective layer, and the charring rate itself is also high. Generally speaking, there is a certain quantitative relationship between the charring rate of flame-retardant plastics and their flame retardancy (such as oxygen index). The higher the charring rate, the better the flame retardancy, but MA does not have a color-developing group and cannot provide color for polyester. PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) is a dye and pigment intermediate with excellent chemical resistance, color bleed resistance, and extreme weather resistance. Due to its good compatibility, it also has the characteristics of transparency and strong tinting power, which solves the problem of weak tinting power of ordinary dyes and color pastes, but it does not have flame retardant properties.

[0017] In the process of synthesizing the flame retardant, the present invention connects MA to the colored group PTCDA, that is, the pigment and the flame retardant serve as carriers for each other, and two functions are obtained by adding an auxiliary agent, thereby eliminating the subsequent steps of adding color paste or adding a colored masterbatch and a flame retardant masterbatch for blending. At the same time, it is unexpectedly found that PDI also has a synergistic flame retardant effect on the original flame retardant.

[0018] Specifically, PDI-MA, as an organic small molecule synthesized from PTCDA and MA, not only combines the advantages of both, combining flame retardancy and color at the same time, but also, although PDI is a color-developing small molecule, it provides more aromatic rings. During combustion and heating, molecular motion intensifies the π-π interaction between PDI and the aromatic heterocyclic rings of MA itself in the composite system, forming a denser and wider stacking. At this time, the density and range of carbonization will be significantly increased compared to when MA and PDI exist alone (through Figures 1 to 3 The SEM image can confirm this), so it can block heat and prevent the diffusion of flammable gases. The synergistic effect of charring can further improve the flame retardant properties of the material, making the composite material colorful and flame retardant while synergistically improving the overall flame retardancy.

[0019] As the preferred technical solution:

[0020] In the method for preparing the colored flame retardant masterbatch as described above, the mass percentage of the flame retardant PDI-MA is 30-45% based on the total mass of the flame retardant PDI-MA and the polyester chip powder matrix.

[0021] The preparation method of the colored flame retardant masterbatch as described above, the synthesis method of the flame retardant PDI-MA is as follows: 3,4,9,10-perylenetetracarboxylic dianhydride and 2 times the molar amount of melamine relative to 3,4,9,10-perylenetetracarboxylic dianhydride are heated in an imidazole solvent (whose volume in milliliters is 20 to 30 times the mass in grams of the product flame retardant PDI-MA) at 140°C in a nitrogen atmosphere for reaction for 4.5 hours, and after the reaction is completed, the mixture is cooled to room temperature, and then deionized water is added, stirred, and then filtered, and then the filter cake is rinsed with water and ethanol three times in sequence, and the flame retardant PDI-MA is obtained after drying.

[0022] The present invention also provides a method for preparing colored flame-retardant polyester fibers, wherein the colored flame-retardant masterbatch prepared by any of the above methods is blended with polyester chips and then melt-spun to prepare the colored flame-retardant polyester fibers.

[0023] As the preferred technical solution:

[0024] In the method for preparing colored flame-retardant polyester fiber as described above, based on the total amount of colored flame-retardant masterbatch and polyester chips, the mass percentage of the colored flame-retardant masterbatch is 5-15%.

[0025] The preparation method of the colored flame-retardant polyester fiber 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:

[0026] The temperature of the single screw extruder: Zone 1 temperature 275-285°C, Zone 2 temperature 285-295°C, Zone 3 temperature 285-290°C, Zone 4 temperature 285-295°C, Zone 5 temperature 285-295°C;

[0027] The spinning temperature is 285-305°C;

[0028] 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;

[0029] 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.

[0030] A method for preparing colored flame-retardant polyester fiber as described in any of the above items, wherein the colored flame-retardant polyester fiber has a limiting oxygen index of >28%, a vertical burning grade of V0, a ​​color fastness to light of 7 to 8, a color fastness to soaping of 4 to 5, a color fastness to washing of 4 to 5, a color fastness to rubbing of 4 to 5, and a color fastness to perspiration of 4 to 5. Because 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) is a dye and pigment intermediate, belonging to perylene pigments, the pigment molecules have good planarity and strong rigidity, so they have both high chemical stability and special optical properties, and perylene pigments have extremely high resistance to organic solvents and thermal stability, as well as high light and weather fastness.

[0031] Beneficial effects:

[0032] (1) In the flame retardant PDI-MA prepared by the present invention, the pigment and the flame retardant serve as carriers for each other, so that the flame retardant prepared can combine the advantages of PTCDA and MA. At the same time, PDI also has a synergistic flame retardant effect on the original flame retardant. The colored flame retardant polyester fiber prepared by the present invention has color and flame retardant properties, and also synergistically improves the overall flame retardancy and has higher color fastness.

[0033] (2) In the process of synthesizing the flame retardant, the present invention connects MA to the colored group PTCDA, thereby eliminating the subsequent steps of adding color paste or adding a colored masterbatch to blend with a flame retardant masterbatch. The preparation process is simple and the cost is low.

[0034] (3) The flame retardant PDI-MA prepared by the present invention is easy to be evenly dispersed in the polyester matrix, thereby achieving flame retardancy and improving the overall performance of the fiber, and making the fiber have a bright color. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is a SEM image of the carbon layer of the colored polyester fiber obtained in Comparative Example 2 of the present invention after combustion;

[0036] Figure 2 This is a SEM image of the carbon layer of the flame-retardant polyester fiber obtained in Comparative Example 1 of the present invention after combustion;

[0037] Figure 3 This is a SEM image of the carbon layer of the colored flame-retardant polyester fiber after combustion obtained in Example 5 of the present invention;

[0038] Figure 4 is the chemical reaction formula of the flame retardant PDI-MA of the present invention;

[0039] Figure 5 It is the hydrogen nuclear magnetic resonance spectrum of the flame retardant PDI-MA of the present invention. DETAILED DESCRIPTION

[0040] 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.

[0041] In order to ensure that the properties of the materials used in the embodiments and comparative examples are fully disclosed, the manufacturers and brands of some materials are specified, and products of other manufacturers and brands that meet the requirements of the present invention are also feasible.

[0042] The chemical structural formula of the flame retardant PDI-MA obtained in the following examples is:

[0043]

[0044] The testing methods of the relevant performance indicators in the following embodiments and comparative examples are as follows:

[0045] Limiting oxygen index: the polyester fibers prepared in the embodiments and comparative examples were tested according to GB / T 2406.2-2009 standard.

[0046] Vertical burning grade: The polyester fibers prepared in the embodiments and comparative examples were tested according to GB / T 2408-2008 standard.

[0047] Color fastness to light: The polyester fibers prepared in the embodiments and comparative examples were tested according to GB / T 8427-2008.

[0048] Color fastness to soaping: The polyester fibers prepared in the embodiments and comparative examples were tested according to GB / T 3921-2008.

[0049] Color fastness to washing: The polyester fibers prepared in the embodiments and comparative examples were tested with reference to GB / T 5713-2013.

[0050] Color fastness to rubbing: The polyester fibers prepared in the embodiments and comparative examples were tested according to GB / T 3920-2008.

[0051] Color fastness to perspiration: The polyester fibers prepared in the embodiments and comparative examples were tested with reference to GB / T 3922-2013.

[0052] Example 1

[0053] A method for preparing a colored flame retardant masterbatch, the steps are as follows:

[0054] (1) Preparation of flame retardant PDI-MA;

[0055] 3,4,9,10-perylenetetracarboxylic acid dianhydride and melamine in an amount twice the molar amount of 3,4,9,10-perylenetetracarboxylic acid dianhydride were heated in imidazole at 140°C in a nitrogen atmosphere for 4.5 hours. After the reaction, the mixture was cooled to 25°C, deionized water was added, stirred for 24 hours, and then filtered. The filter cake was then washed with water and ethanol for 3 times each, and dried to obtain the flame retardant PDI-MA. The reaction was as follows: Figure 4 As shown, the product H NMR spectrum is as follows Figure 5 As shown, δ = 7.29-7.27 ppm is the chemical shift of H at NH2 on melamine connected to 3,4,9,10-perylenetetracarboxylic dianhydride, and δ = 8.88-8.72 ppm is the chemical shift of H on the perylene ring; wherein, the volume milliliters of imidazole is 20 times the mass grams of the product flame retardant PDI-MA;

[0056] (2) The flame retardant PDI-MA prepared in step (1) is blended with a polyester chip powder matrix (polyester fiber grade semi-matt chips, manufactured by China Petrochemical Corporation, brand TFW100) and extruded into granules to prepare a colored flame retardant masterbatch with an average particle size of 2 mm; wherein the mass percentage of the flame retardant PDI-MA is 30% based on the total mass of the flame retardant PDI-MA and the polyester chip powder matrix.

[0057] A method for preparing colored flame-retardant polyester fiber, comprising the following steps:

[0058] The colored flame-retardant masterbatch prepared above is blended with polyester chips and then melt-spinned to prepare colored flame-retardant polyester fibers;

[0059] Wherein, based on the total amount of colored flame retardant masterbatch and polyester chips, the mass percentage of colored flame retardant masterbatch is 5%;

[0060] The process flow of melt spinning is: single screw extruder melt extrusion, spinning, cooling, drawing, shaping and winding;

[0061] The process parameters of melt spinning are as follows:

[0062] 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 288°C;

[0063] The spinning temperature is 285°C;

[0064] The cooling conditions included: temperature of 20°C, relative humidity of 60%, and air velocity of 0.3 m / s;

[0065] The drafting ratio of the drafting is 3 times, the setting temperature is 90°C, and the winding speed is 4200m / min.

[0066] The colored flame-retardant polyester fiber finally obtained has a limiting oxygen index of 31%, a vertical burning grade of V0, a ​​color fastness to light of level 8, a color fastness to soaping of level 5, a color fastness to washing of level 5, a color fastness to rubbing of level 5, and a color fastness to perspiration of level 5.

[0067] Comparative Example 1

[0068] A method for preparing a flame retardant masterbatch is basically the same as that of Example 1, except that step (1) is not performed and the flame retardant PDI-MA in step (2) is replaced by an equal mass of melamine.

[0069] A method for preparing a flame-retardant polyester fiber is basically the same as that of Example 1, except that the flame-retardant masterbatch used is prepared in the comparative example.

[0070] The final flame retardant polyester fiber has a limiting oxygen index of 28%, a vertical combustion grade of V1, and a SEM image of the carbon layer after combustion. Figure 2 shown.

[0071] By comparing Comparative Example 1 with Example 1, it can be seen that the flame-retardant polyester fiber prepared in Comparative Example 1 has a reduced limiting oxygen index and a vertical combustion grade, and does not have a colored property. This is because the flame-retardant masterbatch prepared in Comparative Example 1 contains only melamine. When it is used to prepare polyester fibers, it can only impart flame-retardant properties to the polyester fibers through its own flame-retardant properties, and cannot impart colored properties to the polyester fibers. In addition, when the flame-retardant polyester fiber prepared in Comparative Example 1 is burned and heated, due to the lack of the addition of PDI, it cannot form a Π-Π interaction with the aromatic heterocyclic rings of MA itself in the composite system, resulting in reduced density and range of carbonization, and ultimately reduced flame retardant properties.

[0072] Comparative Example 2

[0073] A method for preparing a colored masterbatch is basically the same as that of Example 1, except that step (1) is not performed and the flame retardant PDI-MA in step (2) is replaced by an equal mass of 3,4,9,10-perylenetetracarboxylic dianhydride.

[0074] A method for preparing colored polyester fiber is basically the same as that of Example 1, except that the colored masterbatch used is prepared in the comparative example.

[0075] The resulting colored polyester fiber has a limiting oxygen index of 21% and a vertical combustion grade of NR (the SEM image of the carbon layer after combustion is shown in FIG. Figure 1 shown).

[0076] By comparing Comparative Example 2 with Example 1, it can be seen that the limiting oxygen index of the colored polyester fiber prepared in Comparative Example 2 is reduced, and the vertical burning grade fails to reach the lowest flame retardant grade in the test standard. This is because the colored masterbatch of Comparative Example 2 contains only 3,4,9,10-perylenetetracarboxylic dianhydride, and the colored polyester fiber prepared therefrom can only give the polyester fiber the characteristic of color, but has no flame retardant effect itself, which ultimately leads to a reduction in the limiting oxygen index of the prepared colored polyester fiber, and the vertical burning grade also fails to reach the lowest flame retardant grade in the test standard.

[0077] Comparative Example 3

[0078] A method for preparing a colored flame retardant masterbatch is basically the same as that of Example 1, except that step (1) is not performed, and the flame retardant PDI-MA in step (2) is replaced by a mixture of equal masses of 3,4,9,10-perylenetetracarboxylic dianhydride and melamine, wherein the molar ratio of 3,4,9,10-perylenetetracarboxylic dianhydride to melamine is 1:3.

[0079] A method for preparing colored flame-retardant polyester fiber is basically the same as that of Example 1, except that the colored flame-retardant masterbatch used is prepared in the comparative example.

[0080] The colored flame-retardant polyester fiber finally obtained has a limiting oxygen index of 27%, a vertical burning grade of V1, a color fastness to light of level 7, a color fastness to soaping of level 4, a color fastness to washing of level 4, a color fastness to rubbing of level 4, and a color fastness to perspiration of level 4.

[0081] By comparing Comparative Example 3 with Example 1, it can be seen that the limiting oxygen index and vertical burning grade of the colored flame-retardant polyester fiber prepared in Comparative Example 3 are reduced, and the color fastness grades of light resistance, soap washing resistance, water washing resistance, friction resistance and sweat resistance are reduced. This is because the colored flame-retardant masterbatch of this comparative example is just a simple mixture of 3,4,9,10-perylenetetracarboxylic dianhydride and MA, which also leads to uneven dispersion of the two, thereby affecting the flame retardant effect and color fastness effect; in addition, this simple mixing will also cause 3,4,9,10-perylenetetracarboxylic dianhydride to not be connected to melamine, so that a strong chemical bond cannot be formed, and the interaction of the system cannot be enhanced, thereby reducing stability, and ultimately leading to a decrease in the limiting oxygen index and vertical burning grade, and a decrease in the color fastness grades of light resistance, soap washing resistance, water washing resistance, friction resistance and sweat resistance.

[0082] Example 2

[0083] A method for preparing a colored flame retardant masterbatch, the steps are as follows:

[0084] (1) Preparation of flame retardant PDI-MA;

[0085] 3,4,9,10-perylenetetracarboxylic acid dianhydride and melamine in an amount twice the molar amount of 3,4,9,10-perylenetetracarboxylic acid dianhydride are heated in imidazole at 140°C in a nitrogen atmosphere for 4.5 hours, cooled to 25°C after the reaction, and then added with deionized water and stirred for 24 hours before suction filtration, and then the filter cake is washed with water and ethanol three times each, and dried to obtain a flame retardant PDI-MA; wherein the volume of imidazole in milliliters is 22 times the mass of the product flame retardant PDI-MA in grams;

[0086] (2) The flame retardant PDI-MA prepared in step (1) is blended with a polyester chip powder matrix (polyester fiber grade semi-matt chips, manufactured by China Petrochemical Corporation, with a brand name of TFW100) and extruded into granules to prepare a colored flame retardant masterbatch with an average particle size of 2.5 mm; wherein the mass percentage of the flame retardant PDI-MA is 35% based on the total mass of the flame retardant PDI-MA and the polyester chip powder matrix.

[0087] A method for preparing colored flame-retardant polyester fiber, comprising the following steps:

[0088] The colored flame-retardant masterbatch prepared above is blended with polyester chips and then melt-spinned to prepare colored flame-retardant polyester fibers;

[0089] Wherein, based on the total amount of colored flame retardant masterbatch and polyester chips, the mass percentage of colored flame retardant masterbatch is 10%;

[0090] The process flow of melt spinning is: single screw extruder melt extrusion, spinning, cooling, drawing, shaping and winding;

[0091] The process parameters of melt spinning are as follows:

[0092] The temperature of the single screw extruder: Zone 1 temperature 278°C, Zone 2 temperature 288°C, Zone 3 temperature 287°C, Zone 4 temperature 288°C, Zone 5 temperature 290°C;

[0093] The spinning temperature is 290°C;

[0094] The cooling conditions included: temperature of 15°C, relative humidity of 75%, and air velocity of 0.4 m / s;

[0095] The drafting ratio of the drafting is 4 times, the setting temperature is 95°C, and the winding speed is 3500m / min.

[0096] The colored flame-retardant polyester fiber finally obtained has a limiting oxygen index of 31%, a vertical burning grade of V0, a ​​color fastness to light of level 8, a color fastness to soaping of level 5, a color fastness to washing of level 5, a color fastness to rubbing of level 5, and a color fastness to perspiration of level 5.

[0097] Example 3

[0098] A method for preparing a colored flame retardant masterbatch, the steps are as follows:

[0099] (1) Preparation of flame retardant PDI-MA;

[0100] 3,4,9,10-perylenetetracarboxylic acid dianhydride and melamine in an amount twice the molar amount of 3,4,9,10-perylenetetracarboxylic acid dianhydride are heated in imidazole at 140°C in a nitrogen atmosphere for 4.5 hours, cooled to 25°C after the reaction, and then added with deionized water and stirred for 24 hours before suction filtration, and then the filter cake is washed with water and ethanol three times each, and dried to obtain a flame retardant PDI-MA; wherein the volume of imidazole in milliliters is 24 times the mass of the product flame retardant PDI-MA in grams;

[0101] (2) The flame retardant PDI-MA prepared in step (1) is blended with a polyester chip powder matrix (polyester fiber grade semi-matt chips, manufactured by China Petrochemical Corporation, brand TFW100) and extruded into granules to prepare a colored flame retardant masterbatch with an average particle size of 3 mm; wherein the mass percentage of the flame retardant PDI-MA is 38% based on the total mass of the flame retardant PDI-MA and the polyester chip powder matrix.

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

[0103] The colored flame-retardant masterbatch prepared above is blended with polyester chips and then melt-spinned to prepare colored flame-retardant polyester fibers;

[0104] Wherein, based on the total amount of colored flame retardant masterbatch and polyester chips, the mass percentage of colored flame retardant masterbatch is 10%;

[0105] The process flow of melt spinning is: single screw extruder melt extrusion, spinning, cooling, drawing, shaping and winding;

[0106] The process parameters of melt spinning are as follows:

[0107] The temperature of the single screw extruder: Zone 1 temperature 280°C, Zone 2 temperature 290°C, Zone 3 temperature 288°C, Zone 4 temperature 292°C, Zone 5 temperature 292°C;

[0108] The spinning temperature is 295°C;

[0109] The cooling conditions included: temperature of 15°C, relative humidity of 67%, and air velocity of 0.5 m / s;

[0110] The drafting ratio of the drafting is 5 times, the setting temperature is 100°C, and the winding speed is 2800m / min.

[0111] The colored flame-retardant polyester fiber finally obtained has a limiting oxygen index of 32%, a vertical burning grade of V0, a ​​color fastness to light of level 8, a color fastness to soaping of level 5, a color fastness to washing of level 5, a color fastness to rubbing of level 5, and a color fastness to perspiration of level 5.

[0112] Example 4

[0113] A method for preparing a colored flame retardant masterbatch, the steps are as follows:

[0114] (1) Preparation of flame retardant PDI-MA;

[0115] 3,4,9,10-perylenetetracarboxylic acid dianhydride and melamine in an amount twice the molar amount of 3,4,9,10-perylenetetracarboxylic acid dianhydride are heated in imidazole at 140°C in a nitrogen atmosphere for 4.5 hours, cooled to 25°C after the reaction, and then added with deionized water and stirred for 24 hours before suction filtration, and then the filter cake is washed with water and ethanol three times in sequence, and dried to obtain a flame retardant PDI-MA; wherein the volume of imidazole in milliliters is 27 times the mass of the product flame retardant PDI-MA in grams;

[0116] (2) The flame retardant PDI-MA prepared in step (1) is blended with a polyester chip powder matrix (polyester fiber grade semi-matt chips, manufactured by China Petrochemical Corporation, brand TFW100) and extruded into granules to prepare a colored flame retardant masterbatch with an average particle size of 3.5 mm; wherein the mass percentage of the flame retardant PDI-MA is 40% based on the total mass of the flame retardant PDI-MA and the polyester chip powder matrix.

[0117] A method for preparing colored flame-retardant polyester fiber, comprising the following steps:

[0118] The colored flame-retardant masterbatch prepared above is blended with polyester chips and then melt-spinned to prepare colored flame-retardant polyester fibers;

[0119] Among them, based on the total amount of colored flame retardant masterbatch and polyester chips, the mass percentage of colored flame retardant masterbatch is 15%;

[0120] The process flow of melt spinning is: single screw extruder melt extrusion, spinning, cooling, drawing, shaping and winding;

[0121] The process parameters of melt spinning are as follows:

[0122] The temperature of the single screw extruder: Zone 1 temperature 282°C, Zone 2 temperature 293°C, Zone 3 temperature 289°C, Zone 4 temperature 294°C, Zone 5 temperature 293°C;

[0123] The spinning temperature is 300°C;

[0124] The cooling conditions included: temperature of 20°C, relative humidity of 68%, and air velocity of 0.7 m / s;

[0125] The drafting ratio of the drafting is 6 times, the setting temperature is 105°C, and the winding speed is 3000m / min.

[0126] The colored flame-retardant polyester fiber finally obtained has a limiting oxygen index of 33%, a vertical burning grade of V0, a ​​color fastness to light of level 7, a color fastness to soaping of level 4, a color fastness to washing of level 4, a color fastness to rubbing of level 4, and a color fastness to perspiration of level 4.

[0127] Example 5

[0128] A method for preparing a colored flame retardant masterbatch, the steps are as follows:

[0129] (1) Preparation of flame retardant PDI-MA;

[0130] 3,4,9,10-perylenetetracarboxylic acid dianhydride and melamine in an amount twice the molar amount of 3,4,9,10-perylenetetracarboxylic acid dianhydride are heated in imidazole at 140°C in a nitrogen atmosphere for 4.5 hours, cooled to 25°C after the reaction, and then added with deionized water and stirred for 24 hours before suction filtration, and then the filter cake is washed with water and ethanol three times each, and dried to obtain a flame retardant PDI-MA; wherein the volume of imidazole in milliliters is 30 times the mass of the product flame retardant PDI-MA in grams;

[0131] (2) The flame retardant PDI-MA prepared in step (1) is blended with a polyester chip powder matrix (polyester fiber grade semi-matt chips, manufactured by China Petrochemical Corporation, brand TFW100) and extruded into granules to prepare a colored flame retardant masterbatch with an average particle size of 4 mm; wherein the mass percentage of the flame retardant PDI-MA is 45% based on the total mass of the flame retardant PDI-MA and the polyester chip powder matrix.

[0132] A method for preparing colored flame-retardant polyester fiber, comprising the following steps:

[0133] The colored flame retardant masterbatch prepared above is blended with polyester chips and then melt-spun to prepare colored flame retardant polyester fibers; wherein the mass percentage of the colored flame retardant masterbatch is 15% based on the total amount of the colored flame retardant masterbatch and the polyester chips;

[0134] The process flow of melt spinning is: single screw extruder melt extrusion, spinning, cooling, drawing, shaping and winding;

[0135] The process parameters of melt spinning are as follows:

[0136] The temperature of the single screw extruder: Zone 1 temperature 285°C, Zone 2 temperature 295°C, Zone 3 temperature 290°C, Zone 4 temperature 295°C, Zone 5 temperature 295°C;

[0137] The spinning temperature is 305°C;

[0138] The cooling conditions included: temperature of 25°C, relative humidity of 75%, and air velocity of 0.8 m / s;

[0139] The drafting ratio was 6 times, the setting temperature was 110°C, and the winding speed was 4200 m / min.

[0140] The resulting colored flame-retardant polyester fiber has a limiting oxygen index of 33% and a vertical combustion rating of V0 (the SEM image of the carbon layer after combustion is shown in FIG. Figure 3 The color fastness to light is level 7, the color fastness to soap washing is level 4, the color fastness to water washing is level 4, the color fastness to rubbing is level 4, and the color fastness to perspiration is level 4.

Claims

1. A method for preparing a colored flame retardant masterbatch, characterized in that: The flame retardant PDI-MA is blended with the polyester chip powder matrix and extruded into granules to prepare a colored flame retardant masterbatch; The chemical structure of flame retardant PDI-MA is as follows:

2. The method for preparing a colored flame retardant masterbatch according to claim 1, characterized in that: Based on the total mass of the flame retardant PDI-MA and the polyester chip powder matrix, the mass percentage of the flame retardant PDI-MA is 30-45%.

3. The method for preparing a colored flame retardant masterbatch according to claim 1, characterized in that: The synthesis method of the flame retardant PDI-MA is as follows: 3,4,9,10-perylenetetracarboxylic dianhydride and 2 times the molar amount of melamine relative to 3,4,9,10-perylenetetracarboxylic dianhydride are heated in an imidazole solvent under a nitrogen atmosphere at 140°C for reaction for 4.5 hours, and after the reaction is completed, the mixture is cooled to room temperature, and then deionized water is added, stirred, and then filtered, and then the filter cake is rinsed with water and ethanol in turn, and the flame retardant PDI-MA is obtained after drying.

4. A method for preparing colored flame-retardant polyester fiber, characterized in that: The colored flame-retardant masterbatch prepared by the method according to any one of claims 1 to 3 is blended with polyester chips and then melt-spun to prepare colored flame-retardant polyester fibers.

5. The method for preparing a colored flame-retardant polyester fiber according to claim 4, characterized in that: Based on the total amount of colored flame retardant masterbatch and polyester chips, the mass percentage of colored flame retardant masterbatch is 5-15%.

6. The method for preparing colored flame-retardant polyester fiber according to claim 4, 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 275-285°C, Zone 2 temperature 285-295°C, Zone 3 temperature 285-290°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.

7. A method for preparing colored flame-retardant polyester fiber according to any one of claims 4 to 6, characterized in that: The limiting oxygen index of colored flame-retardant polyester fiber is greater than 28%, the vertical burning grade is V0, the color fastness to light is 7 to 8, the color fastness to soaping is 4 to 5, the color fastness to washing is 4 to 5, the color fastness to rubbing is 4 to 5, and the color fastness to perspiration is 4 to 5.

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