Preparation method of flame-retardant anti-dripping colored polyester fiber

Abstract

The invention belongs to the technical field of flame-retardant polyester fibers, and discloses a flame-retardant anti-dripping colored polyester fiber preparation method, which comprises: blending a flame retardant PDI-MAC and a polyester chip powder matrix, and carrying out extrusion granulation to obtain a PET colored flame-retardant anti-dripping master batch; and blending the PET colored flame-retardant anti-dripping master batch with polyester chips, and carrying out melt spinning to obtain the flame-retardant anti-dripping colored polyester fiber. According to the invention, the MAC and the PDI are combined, so that the prepared flame retardant PDI-MAC has flame-retardant and anti-dripping effects and also has a color developing effect, the production procedures are reduced, the cost is reduced, and the problems caused by multi-step addition in the prior art are avoided.

Description

Technical Field

[0001] The invention belongs to the technical field of flame-retardant polyester fibers and relates to a method for preparing flame-retardant and anti-melting droplet colored polyester fibers. Background Art

[0002] As an indispensable and important material in modern production and life, polymer materials are increasingly widely used. However, the flammable nature of these materials not only threatens people's lives and property, but also is often accompanied by serious molten droplets during the combustion process. The molten droplets not only cause serious burns to the human body, but once they drip onto other flammable materials, they may also cause secondary combustion. Therefore, the combustion and molten droplet resistance of polymer materials has become the focus of attention.

[0003] In the field of chemical fibers, especially melt-spun fibers, the current flame retardant and anti-melt dripping performance is not satisfactory due to the particularity of its molding and processing. At the same time, colored fibers show broad application prospects in anti-counterfeiting technology, safety warnings, and product aesthetics. Unfortunately, most current technologies tend to only focus on the flame retardancy and color of fibers, while ignoring the importance of anti-melt dripping performance. Therefore, how to make PET fibers have color, high-efficiency flame retardancy, and anti-melt dripping performance is an urgent problem to be solved.

[0004] Patent CN117265689A discloses a regenerated colored flame-retardant fiber and a preparation method thereof. The method comprises preparing a flame retardant by mixing the 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.

[0005] Patent CN112481730A discloses a flame retardant, antiviral and antibacterial colored fiber and a production method thereof. The method comprises preparing a flame retardant / multifunctional agent, directly melt-blending it with colored polyester chips and masterbatches to obtain colored flame retardant masterbatches, and then melt-spinning.

[0006] Patent CN111893596A discloses a flame-retardant colored antistatic polyester fiber and a preparation method thereof, wherein the flame retardant, polyester chips and colored masterbatch are mixed and dried, and then melt-spinned.

[0007] In patent CN105525380A, the carrier and the flame retardant are stirred and mixed by a high-speed stirrer to obtain a mixture, which is then granulated by a twin-screw, and the colored masterbatch and the newly prepared masterbatch are mixed and stirred for a second time to obtain mixed pellets, which are finally melt-spun.

[0008] In summary, the prior art usually adopts multiple processes, including two main steps of coloring and flame retardant and anti-melting droplet treatment (at least two additions are required). In the process of spinning, the increase in the number of addition steps undoubtedly makes the process more complicated. In addition, step-by-step addition may also cause mutual influence between different functional additives. For example, the coloring substance and the flame retardant in the masterbatch may be coated with each other, which often causes problems such as uneven color development or decreased flame retardant performance. At the same time, the uneven distribution of the added substances will also affect the quality of the fiber after spinning. In severe cases, it may even cause discontinuity in the spinning process, resulting in quality problems such as floating silk and hairy silk.

[0009] Therefore, it is of great significance to study a method for preparing flame retardant and anti-melting droplet colored polyester fiber to solve the above problems. Summary of the invention

[0010] The purpose of the invention is to solve the problems existing in the prior art and provide a method for preparing flame-retardant and anti-melting droplet colored polyester fiber.

[0011] To achieve the above object, the technical solution adopted by the present invention is as follows:

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

[0013] A method for preparing flame-retardant and anti-melting droplet colored polyester fiber, comprising blending PET colored flame-retardant and anti-melting droplet masterbatch with polyester chips and then melt-spinning to prepare flame-retardant and anti-melting droplet colored polyester fiber;

[0014] PET colored flame retardant anti-melting masterbatch is obtained by blending the flame retardant PDI (perylene diimide)-MAC (melamine cyanurate salt) with the polyester chip powder matrix and extruding and granulating;

[0015] The chemical structure of flame retardant PDI-MAC is as follows:

[0016]

[0017] As the preferred technical solution:

[0018] The method for preparing the flame retardant and anti-drip colored polyester fiber as described above is based on the total amount of PET colored flame retardant and anti-drip masterbatch and polyester chips, and the mass percentage of PET colored flame retardant and anti-drip masterbatch is 30-45%.

[0019] In the method for preparing the flame retardant and anti-drip colored polyester fiber, the mass percentage of the flame retardant PDI-MAC is 5-15% based on the total mass of the flame retardant PDI-MAC and the polyester chip powder matrix.

[0020] The method for preparing the flame retardant and anti-drip colored polyester fiber as described above, the preparation steps of the flame retardant PDI-MAC are as follows:

[0021] (1) Preparation of MAC;

[0022] Add melamine and an equal molar amount of cyanuric acid into a reaction tank, react at 50°C for 5 to 6 hours, then heat to 115 to 120°C for 1 to 2 hours, cool to room temperature, filter press, and wash with deionized water until the pH of the washing liquid is 6.5 to 7.5 to obtain MAC (its chemical reaction formula is as follows: Figure 1 shown);

[0023] (2) Preparation of flame retardant PDI-MAC;

[0024] 3,4,9,10-perylenetetracarboxylic acid dianhydride and MAC in a molar amount twice that of 3,4,9,10-perylenetetracarboxylic acid dianhydride were heated in an imidazole solvent (whose volume in milliliters is 20 to 30 times the mass in grams of the product flame retardant PDI-MAC) at 140°C under a nitrogen atmosphere for reaction for 4.5 hours. After the reaction, the mixture was cooled to room temperature, deionized water was added, stirred, and filtered, and the filter cake was then rinsed with water and ethanol three times in sequence, and dried to obtain a flame retardant PDI-MAC (whose chemical reaction formula is as follows: Figure 2 shown).

[0025] The method for preparing the flame-retardant and anti-drip colored 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 275-290°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] The method for preparing a flame-retardant and anti-drip colored polyester fiber as described above has a limiting oxygen index of more than 29%, a vertical burning grade of V0, no dripping, a color fastness to light of 7 to 8, a color fastness to soaping of 4 to 5, a color fastness to washing with water of 4 to 5, a color fastness to rubbing of 4 to 5, and a color fastness to sweat of 4 to 5.

[0031] Principle of the invention:

[0032] Under high temperature conditions, materials containing MAC functions will preferentially form a layer of carbonized residue. This layer of carbonized material has good thermal insulation and barrier properties, which can effectively block the transfer of heat and oxygen, thereby inhibiting the spread of flames. The hydrogen bonds in MAC can enhance the overall structure of the polymer and form a more stable three-dimensional network. This network structure can improve the heat resistance and mechanical strength of the material, thereby improving the flame retardant properties. Due to its high nitrogen content, MCA flame retardant decomposes at high temperatures to produce non-combustible nitrogen gases, which dilute oxygen and combustible gases, thereby exerting a gas phase flame retardant mechanism. When MAC alone is used as a flame retardant functional additive, as the temperature further increases during the combustion process, MAC will increase the dripping phenomenon during the combustion of the material, thereby taking away a large amount of combustion heat. Although this phenomenon improves the flame retardant properties of the material, it also makes the molten drop phenomenon more obvious.

[0033] PTCDA 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 transparency and tinting strength, and can provide bright colors, solving the problem of dull colors and weak tinting strength of ordinary dyes and color pastes. However, it does not have flame retardant properties.

[0034] Introducing MAC into PDI, as an organic small molecule synthesized from PDI and MAC, not only combines the advantages of both, but also combines flame retardancy and coloring at the same time. At the same time, although PDI is a coloring small molecule, it can play a synergistic flame retardant and anti-melting dripping effect. The MAC unit not only has hydrogen bonds in its own structure, but it can also form hydrogen bonds with the carbonyl group in the polyester molecular structure. The interaction of hydrogen bonds can enhance the three-dimensional structural stability of the molecule, resulting in the copolyester having a double physical cross-linked network structure of hydrogen bonds and π-π stacking. The existence of this double physical network structure restricts the movement of polyester molecular chains, which can significantly increase the high-temperature melt viscosity and melt strength of the copolyester, thereby improving the flame retardant and anti-melting dripping properties of polyester. PDI has a large conjugated structure, and MAC also has a large number of aromatic heterocycles, which makes π-π interactions between PDI-MAC and between them and polymers, strengthening the interaction between molecular chains. On the one hand, the thermal stability of the material is improved; on the other hand, the π-π interaction limits the flow properties of MAC and the matrix. The graphitized structure formed during the heating and combustion process is more obvious than that of the system without π-π interaction. This phenomenon further strengthens the π-π interaction between the matrixes, inhibits the melt flow, and thus reduces the generation of droplets. At the same time, the carbonyl oxygen atoms in the imide matrix of the NC in MAC and the PDI molecule can strengthen the interaction network through hydrogen bonds, reduce the intermolecular mobility, and thus reduce the droplet reduction. In addition, the graphitization and carbonization phenomena also block the spread of heat and combustible gases, and play a role in enhancing the flame retardant properties. Therefore, PDI not only achieves the color of the composite material, but also synergistically improves the anti-melting droplet performance of MAC, achieving the synergistic flame retardant and anti-melting droplet of the material.

[0035] Beneficial effects:

[0036] (1) The flame retardant PDI-MAC prepared by the present invention can combine the advantages of MAC and PDI, so that there is a π-π interaction between PDI-MAC and between PDI and polymer, which strengthens the interaction between molecular chains, improves the thermal stability of the material, and inhibits melt flow, thereby reducing droplet generation.

[0037] (2) The present invention combines MAC and PDI to obtain a flame retardant PDI-MAC that has both flame retardant and anti-melting effect and color development effect, thereby reducing production processes, lowering costs, and avoiding the problems caused by multi-step addition in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 Schematic diagram of the chemical reaction formula of MAC of the present invention;

[0039] Figure 2 is the chemical reaction formula of the flame retardant PDI-MAC of the present invention;

[0040] Figure 3 It is the hydrogen nuclear magnetic resonance spectrum of the flame retardant PDI-MAC of the present invention. DETAILED DESCRIPTION

[0041] 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.

[0042] In order to ensure that the properties of the materials used in each embodiment and comparative example are fully disclosed, the manufacturers and brands of the materials are indicated, and products of other manufacturers and brands that meet the requirements of the present invention are also feasible.

[0043] The chemical structural formula of the flame retardant PDI-MAC prepared in the following examples is as follows:

[0044]

[0045] The testing methods of the relevant performance indicators in the following embodiments and comparative examples are as follows:

[0046] Limiting oxygen index: The flame retardant and anti-drip colored polyester fibers prepared in each embodiment and each comparative example were tested with reference to GB / T 2406.2-2009 standard.

[0047] Vertical burning grade: The flame retardant and drip-resistant colored polyester fibers prepared in each embodiment and each comparative example were tested with reference to GB / T 2408-2008 standard.

[0048] Color fastness to light: The flame-retardant and anti-drip colored polyester fibers prepared in each embodiment and each comparative example were tested with reference to GB / T 8427-2008 standard.

[0049] Color fastness to soaping: The flame-retardant and anti-drip colored polyester fibers prepared in each embodiment and each comparative example were tested with reference to GB / T 3921-2008 standard.

[0050] Color fastness to washing: The flame-retardant and anti-drip colored polyester fibers prepared in each embodiment and each comparative example were tested with reference to GB / T 5713-2013 standard.

[0051] Color fastness to rubbing: The flame-retardant and anti-drip colored polyester fibers prepared in each embodiment and each comparative example were tested with reference to GB / T 3920-2008 standard.

[0052] Color fastness to perspiration: The flame-retardant and anti-drip colored polyester fibers prepared in each embodiment and each comparative example were tested with reference to GB / T 3922-2013 standard.

[0053] Vertical burning grade: The flame retardant and drip-resistant colored polyester fibers prepared in each embodiment and each comparative example were tested with reference to GB / T 2408-2008 standard.

[0054] Whether there are molten droplets: The flame-retardant and molten-drip-resistant colored polyester fibers prepared in each embodiment and each comparative example are used as samples. The samples are continuously burned using a UL1581 combustion tester, and the molten droplets are collected at the bottom with water to detect whether there are molten droplets.

[0055] Example 1

[0056] A method for preparing flame-retardant and anti-drip colored polyester fiber, comprising the following steps:

[0057] (1) Preparation of MAC;

[0058] Add melamine and an equal molar amount of cyanuric acid into a reaction tank, react at 50°C for 5 hours, then heat to 115°C for 1 hour, cool to 25°C, filter through a plate and frame filter press, wash the obtained filter cake with deionized water until the pH of the washing liquid is 6.5, dry, and then pulverize to obtain MAC;

[0059] (2) Preparation of flame retardant PDI-MAC;

[0060] 3,4,9,10-perylenetetracarboxylic acid dianhydride and MAC in an amount twice the molar amount of 3,4,9,10-perylenetetracarboxylic acid dianhydride were heated in an imidazole solvent at 140°C under a nitrogen atmosphere for 4.5 hours. After the reaction, the mixture was cooled to 25°C, deionized water was added, stirred, and filtered, and the filter cake was washed with water and ethanol three times each, and dried to obtain a flame retardant PDI-MAC. The reaction was as follows: Figure 2 As shown, the product H NMR spectrum is as follows Figure 3 As shown, δ=6.92-7.04 ppm is the chemical shift of H at NH2 on the aromatic ring of MAC connected to 3,4,9,10-perylenetetracarboxylic dianhydride, δ=11.28-11.35 ppm is the chemical shift of hydrogen connected to oxygen on MAC connected to 3,4,9,10-perylenetetracarboxylic dianhydride, and δ=7.85-8.21 ppm is the chemical shift of H on the perylene ring; wherein, the volume milliliters of the imidazole solvent is 20 times the mass grams of the product flame retardant PDI-MAC;

[0061] (3) blending the flame retardant PDI-MAC obtained in step (2) with a polyester chip powder matrix (polyester fiber grade semi-matt chips, manufactured by China Petrochemical Corporation, brand TFW100) and extruding and granulating to obtain a PET colored flame retardant and anti-drip masterbatch with an average particle size of 0.1 mm; wherein the mass percentage of the flame retardant PDI-MAC is 30% based on the total mass of the flame retardant PDI-MAC and the polyester chip powder matrix;

[0062] (4) blending PET colored flame retardant and anti-melting droplet masterbatch with polyester chips and then melt spinning to obtain flame retardant and anti-melting droplet colored polyester fibers; wherein the mass percentage of the PET colored flame retardant and anti-melting droplet masterbatch is 5% based on the total amount of the PET colored flame retardant and anti-melting droplet masterbatch and the polyester chips;

[0063] 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:

[0064] 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;

[0065] The spinning temperature is 285°C;

[0066] The cooling conditions included: temperature of 15°C, relative humidity of 60%, and air velocity of 0.3 m / s;

[0067] The drafting ratio of the drafting is 3 times, the setting temperature is 80°C, and the winding speed is 2800m / min.

[0068] The final flame-retardant and anti-drip colored polyester fiber has a limiting oxygen index of 31%, a vertical burning grade of V-0, no dripping, 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 sweat of level 5.

[0069] Comparative Example 1

[0070] A method for preparing a flame-retardant polyester fiber is basically the same as that of Example 1, except that step (2) is not performed and the flame retardant PDI-MAC in step (3) is replaced by MAC of equal mass.

[0071] The flame retardant polyester fiber finally obtained has a limiting oxygen index of 29%, a vertical burning grade of V1, and has molten droplets.

[0072] By comparing Comparative Example 1 with Example 1, it can be seen that the limiting oxygen index and vertical combustion grade of the flame-retardant polyester fiber prepared in Comparative Example 1 are reduced, and droplets are generated, and the flame-retardant property is not possessed. This is because the MAC used in Comparative Example 1 can only impart flame-retardant properties to the polyester fiber through its own flame-retardant properties, and cannot impart colored properties to the polyester fiber. In addition, since the MAC in Comparative Example 1 cannot form a strong hydrogen bond interaction with PDI, and lacks the large conjugated structure provided by PDI, the π-π interaction formed by MAC and polyester is less, the interaction force is smaller, and a strong spatial network cannot be formed. During combustion, the melt fluidity becomes higher, and droplets are easily generated, so the limiting oxygen index and the vertical combustion grade are reduced, and droplets are generated.

[0073] Comparative Example 2

[0074] A method for preparing colored polyester fiber is basically the same as that of Example 1, except that steps (1) to (2) are not performed, and the flame retardant PDI-MA in step (3) is replaced by an equal mass of 3,4,9,10-perylenetetracarboxylic dianhydride.

[0075] The colored polyester fiber finally obtained has a limiting oxygen index of 21%, a vertical burning grade of NR, and has molten droplets.

[0076] By comparing Comparative Example 2 with Example 1, it can be seen that the limiting oxygen index and vertical combustion grade of the colored polyester fiber prepared in Comparative Example 2 are reduced, and molten droplets are generated. This is because although 3,4,9,10-perylenetetracarboxylic dianhydride can give the polyester fiber color characteristics, it has no flame retardant effect itself, so the obtained polyester fiber has no flame retardant properties.

[0077] Comparative Example 3

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

[0079] The colored flame-retardant polyester fiber finally obtained has a limiting oxygen index of 28%, a vertical burning grade of V1, the presence of molten droplets, a color fastness to light of level 7, a color fastness to soaping of level 4, a color fastness to washing with water of level 4, a color fastness to rubbing of level 4, and a color fastness to perspiration of level 4.

[0080] 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 droplets are generated, 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 PET colored flame-retardant anti-melt drop masterbatch used in Comparative Example 3 is only a simple mixture of 3,4,9,10-perylenetetracarboxylic dianhydride and MAC, which also makes the two unevenly dispersed, thereby affecting the flame retardant effect and color fastness effect; in addition, 3,4,9,10-perylenetetracarboxylic dianhydride does not form a strong chemical bond with MAC, which also reduces the strength of the spatial network to a certain extent, thereby reducing the stability of the system, and ultimately leading to a decrease in the limiting oxygen index and vertical burning grade, and resulting in the generation of droplets, and the color fastness grades of light resistance, soap washing resistance, water washing resistance, friction resistance, and sweat resistance are reduced.

[0081] Example 2

[0082] A method for preparing flame-retardant and anti-drip colored polyester fiber, comprising the following steps:

[0083] (1) Preparation of MAC;

[0084] Add melamine and an equal molar amount of cyanuric acid into a reaction tank, react at 50°C for 5.5 hours, then heat to 116°C for 1.5 hours, cool to 25°C, filter through a plate and frame filter press, wash the filter cake with deionized water until the pH of the washing liquid is 6.7, dry, and then pulverize to obtain MAC;

[0085] (2) Preparation of flame retardant PDI-MAC;

[0086] 3,4,9,10-perylenetetracarboxylic dianhydride and MAC in an amount twice the molar amount of 3,4,9,10-perylenetetracarboxylic dianhydride are heated in an imidazole solvent at 140°C under a nitrogen atmosphere for 4.5 hours, cooled to 25°C after the reaction, and then filtered after adding deionized water, stirring, and then the filter cake is washed with water and ethanol three times each, and dried to obtain a flame retardant PDI-MAC; wherein the volume of the imidazole solvent in milliliters is 25 times the mass of the product flame retardant PDI-MAC in grams;

[0087] (3) blending the flame retardant PDI-MAC obtained in step (2) with a polyester chip powder matrix (polyester fiber grade semi-matt chips, manufactured by China Petrochemical Corporation, brand TFW100) and extruding and granulating to obtain a PET colored flame retardant and anti-melting droplet masterbatch with an average particle size of 0.8 mm; wherein the mass percentage of the flame retardant PDI-MAC is 35% based on the total mass of the flame retardant PDI-MAC and the polyester chip powder matrix;

[0088] (4) blending PET colored flame retardant and anti-melting droplet masterbatch with polyester chips and then melt spinning to obtain flame retardant and anti-melting droplet colored polyester fibers; wherein the mass percentage of the PET colored flame retardant and anti-melting droplet masterbatch is 10% based on the total amount of the PET colored flame retardant and anti-melting droplet masterbatch and the polyester chips;

[0089] 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:

[0090] The temperature of the single screw extruder: Zone 1 temperature 283°C, Zone 2 temperature 288°C, Zone 3 temperature 286°C, Zone 4 temperature 289°C, Zone 5 temperature 291°C;

[0091] The spinning temperature is 295°C;

[0092] The cooling conditions included: temperature of 20°C, relative humidity of 67%, and air velocity of 0.5 m / s;

[0093] The drafting ratio is 5 times, the setting temperature is 95°C, and the winding speed is 3400m / min.

[0094] The final flame-retardant and anti-drip colored polyester fiber has a limiting oxygen index of 32%, a vertical burning grade of V-0, no dripping, a color fastness to light of level 8, a color fastness to soaping of level 5, a color fastness to washing with water of level 5, a color fastness to rubbing of level 5, and a color fastness to sweat of level 5.

[0095] Example 3

[0096] A method for preparing flame-retardant and anti-drip colored polyester fiber, comprising the following steps:

[0097] (1) Preparation of MAC;

[0098] Add melamine and an equal molar amount of cyanuric acid into a reaction tank, react at 50°C for 5.7 hours, then heat to 118°C for 1.7 hours, cool to 25°C, filter through a plate and frame filter press, wash the filter cake with deionized water until the pH of the washing liquid is 7, dry, and then pulverize to obtain MAC;

[0099] (2) Preparation of flame retardant PDI-MAC;

[0100] 3,4,9,10-perylenetetracarboxylic dianhydride and MAC in an amount twice the molar amount of 3,4,9,10-perylenetetracarboxylic dianhydride are heated in an imidazole solvent at 140°C under a nitrogen atmosphere for 4.5 hours, cooled to 25°C after the reaction, and then filtered after adding deionized water, stirring, and then the filter cake is washed with water and ethanol three times in sequence, and dried to obtain a flame retardant PDI-MAC; wherein the volume of the imidazole solvent in milliliters is 27 times the mass of the product flame retardant PDI-MAC in grams;

[0101] (3) blending the flame retardant PDI-MAC obtained in step (2) with a polyester chip powder matrix (polyester fiber grade semi-matt chips, manufactured by China Petrochemical Corporation, brand TFW100) and extruding and granulating to obtain a PET colored flame retardant and anti-melting droplet masterbatch with an average particle size of 1 mm; wherein the mass percentage of the flame retardant PDI-MAC is 38% based on the total mass of the flame retardant PDI-MAC and the polyester chip powder matrix;

[0102] (4) blending PET colored flame retardant and anti-melting droplet masterbatch with polyester chips and then melt spinning to obtain flame retardant and anti-melting droplet colored polyester fibers; wherein the mass percentage of the PET colored flame retardant and anti-melting droplet masterbatch is 10% based on the total amount of the PET colored flame retardant and anti-melting droplet masterbatch and the polyester chips;

[0103] 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:

[0104] The temperature of the single screw extruder: Zone 1 temperature 285°C, Zone 2 temperature 290°C, Zone 3 temperature 288°C, Zone 4 temperature 290°C, Zone 5 temperature 293°C;

[0105] The spinning temperature is 298°C;

[0106] The cooling conditions included: temperature of 22°C, relative humidity of 70%, and air velocity of 0.6 m / s;

[0107] The drafting ratio is 5 times, the setting temperature is 100°C, and the winding speed is 3800m / min.

[0108] The final flame-retardant and anti-drip colored polyester fiber has a limiting oxygen index of 33%, a vertical burning grade of V-0, no dripping, a color fastness to light of level 8, a color fastness to soaping of level 5, a color fastness to washing with water of level 5, a color fastness to rubbing of level 5, and a color fastness to sweat of level 5.

[0109] Example 4

[0110] A method for preparing flame-retardant and anti-drip colored polyester fiber, comprising the following steps:

[0111] (1) Preparation of MAC;

[0112] Add melamine and an equal molar amount of cyanuric acid into a reaction tank, react at 50°C for 5.8 hours, then heat to 119°C for 1.9 hours, then cool to 25°C, filter through a plate and frame filter press, wash the obtained filter cake with deionized water until the pH of the washing liquid is 7.2, dry, and then pulverize to obtain MAC;

[0113] (2) Preparation of flame retardant PDI-MAC;

[0114] 3,4,9,10-perylenetetracarboxylic dianhydride and MAC in an amount twice the molar amount of 3,4,9,10-perylenetetracarboxylic dianhydride are heated in an imidazole solvent at 140°C under a nitrogen atmosphere for 4.5 hours, cooled to 25°C after the reaction, and then filtered after adding deionized water, stirring, and then the filter cake is washed with water and ethanol three times each, and dried to obtain a flame retardant PDI-MAC; wherein the volume of the imidazole solvent in milliliters is 30 times the mass of the product flame retardant PDI-MAC in grams;

[0115] (3) blending the flame retardant PDI-MAC obtained in step (2) with a polyester chip powder matrix (polyester fiber grade semi-matt chips, manufactured by China Petrochemical Corporation, brand TFW100) and extruding and granulating to obtain a PET colored flame retardant and anti-melting droplet masterbatch with an average particle size of 1.5 mm; wherein the mass percentage of the flame retardant PDI-MAC is 40% based on the total mass of the flame retardant PDI-MAC and the polyester chip powder matrix;

[0116] (4) blending PET colored flame retardant and anti-melting droplet masterbatch with polyester chips and then melt spinning to obtain flame retardant and anti-melting droplet colored polyester fibers; wherein the mass percentage of the PET colored flame retardant and anti-melting droplet masterbatch is 15% based on the total amount of the PET colored flame retardant and anti-melting droplet masterbatch and the polyester chips;

[0117] 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:

[0118] The temperature of the single screw extruder: Zone 1 temperature 288°C, Zone 2 temperature 293°C, Zone 3 temperature 290°C, Zone 4 temperature 293°C, Zone 5 temperature 294°C;

[0119] The spinning temperature is 300°C;

[0120] The cooling conditions included: temperature of 25°C, relative humidity of 73%, and air velocity of 0.6 m / s;

[0121] The drafting ratio of the drawing is 6 times, the setting temperature is 105°C, and the winding speed is 4000m / min.

[0122] The final flame-retardant and anti-drip colored polyester fiber has a limiting oxygen index of 34%, a vertical burning grade of V-0, no dripping, 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 sweat of level 4.

[0123] Example 5

[0124] A method for preparing flame-retardant and anti-drip colored polyester fiber, comprising the following steps:

[0125] (1) Preparation of MAC;

[0126] Add melamine and an equal molar amount of cyanuric acid into a reaction tank, react at 50°C for 6 hours, then heat to 120°C for 2 hours and then cool to 25°C, filter through a plate and frame filter press, wash the obtained filter cake with deionized water until the pH of the washing liquid is 7.5, dry, and then pulverize to obtain MAC;

[0127] (2) Preparation of flame retardant PDI-MAC;

[0128] 3,4,9,10-perylenetetracarboxylic dianhydride and MAC in an amount twice the molar amount of 3,4,9,10-perylenetetracarboxylic dianhydride are heated in an imidazole solvent at 140°C under a nitrogen atmosphere for 4.5 hours, cooled to 25°C after the reaction, and then filtered after adding deionized water, stirring, and then the filter cake is washed with water and ethanol three times each, and dried to obtain a flame retardant PDI-MAC; wherein the volume of the imidazole solvent in milliliters is 30 times the mass of the product flame retardant PDI-MAC in grams;

[0129] (3) blending the flame retardant PDI-MAC obtained in step (2) with a polyester chip powder matrix (polyester fiber grade semi-matt chips, manufactured by China Petrochemical Corporation, brand TFW100) and extruding and granulating to obtain a PET colored flame retardant and anti-melting droplet masterbatch with an average particle size of 2 mm; wherein the mass percentage of the flame retardant PDI-MAC is 45% based on the total mass of the flame retardant PDI-MAC and the polyester chip powder matrix;

[0130] (4) blending PET colored flame retardant and anti-melting droplet masterbatch with polyester chips and then melt spinning to obtain flame retardant and anti-melting droplet colored polyester fibers; wherein the mass percentage of the PET colored flame retardant and anti-melting droplet masterbatch is 15% based on the total amount of the PET colored flame retardant and anti-melting droplet masterbatch and the polyester chips;

[0131] 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:

[0132] The temperature of the single screw extruder: Zone 1 temperature 290°C, Zone 2 temperature 295°C, Zone 3 temperature 290°C, Zone 4 temperature 295°C, Zone 5 temperature 295°C;

[0133] The spinning temperature is 305°C;

[0134] The cooling conditions included: temperature of 25°C, relative humidity of 75%, and air velocity of 0.7 m / s;

[0135] The drafting ratio was 6 times, the setting temperature was 110°C, and the winding speed was 4200 m / min.

[0136] The final flame-retardant and anti-drip colored polyester fiber has a limiting oxygen index of 34%, a vertical burning grade of V-0, no dripping, 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 sweat of level 4.

Claims

1. A method for preparing flame-retardant and anti-drip colored polyester fiber, characterized in that: PET colored flame retardant and anti-melting droplet masterbatch is blended with polyester chips and then melt-spun to obtain flame retardant and anti-melting droplet colored polyester fibers; PET colored flame retardant anti-melting masterbatch is obtained by blending the flame retardant PDI-MAC with the polyester chip powder matrix and extruding and granulating; The chemical structure of flame retardant PDI-MAC is as follows:

2. The method for preparing a flame retardant and drip-resistant colored polyester fiber according to claim 1, characterized in that: Based on the total amount of PET colored flame retardant anti-melting droplet masterbatch and polyester chips, the mass percentage of PET colored flame retardant anti-melting droplet masterbatch is 30-45%.

3. The method for preparing a flame-retardant and drip-resistant colored polyester fiber according to claim 1, characterized in that: Based on the total mass of the flame retardant PDI-MAC and the polyester chip powder matrix, the mass percentage of the flame retardant PDI-MAC is 5-15%.

4. The method for preparing a flame-retardant and drip-resistant colored polyester fiber according to claim 1, characterized in that: The preparation steps of flame retardant PDI-MAC are as follows: (1) Preparation of MAC; Add melamine and an equal molar amount of cyanuric acid into a reaction tank, react at 50° C. for 5 to 6 hours, then heat to 115 to 120° C. for 1 to 2 hours, filter press, and then wash with deionized water until the pH of the washing liquid is 6.5 to 7.5 to obtain MAC; (2) Preparation of flame retardant PDI-MAC; 3,4,9,10-perylenetetracarboxylic dianhydride and MAC in a molar amount twice that of 3,4,9,10-perylenetetracarboxylic dianhydride were heated in an imidazole solvent at 140°C under a nitrogen atmosphere for 4.5 hours. After the reaction, the mixture was cooled to room temperature, deionized water was added, stirred, and filtered, and the filter cake was washed with water and ethanol in turn, and dried to obtain the flame retardant PDI-MAC.

5. The method for preparing a flame-retardant and drip-resistant colored polyester fiber 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 285-290°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.

6. The method for preparing a flame-retardant and drip-resistant colored polyester fiber according to claim 1, characterized in that: The limiting oxygen index of colored flame-retardant polyester fiber is greater than 29%, the vertical burning grade is V0, there is no droplet, 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 sweat is 4 to 5.

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