Preparation method of flame-retardant polyester fiber products

Abstract

The present invention relates to a preparation method of a flame-retardant polyester fiber product, and the preparation method has the characteristics of good fiber mechanical properties and good flame-retardant properties. The technical solution is as follows: a preparation method of a flame-retardant polyester fiber product, comprising the following steps: (1) a polyester melt is subjected to spinning, drawing, and shaping to obtain primary polyester fibers; (2) the surface of the primary fiber product is subjected to alcoholysis treatment with an alcohol hydroxyl compound to obtain an object to be flame-retardant treated; the alcohol hydroxyl functionality of the alcohol hydroxyl compound is 2 or more; the primary fiber product is the primary polyester fiber described in step (1) or a fabric made of the primary polyester fiber described in step (1); (3) in the presence of an esterification reaction catalyst, the object to be flame-retardant treated is flame-retardant treated with a phosphorus-containing compound containing the following structural fragment:

Description

Technical Field

[0001] The present invention relates to a method for preparing flame-retardant polyester fiber products, and particularly to a method for preparing flame-retardant fibers or a method for preparing flame-retardant fabrics. Background Art

[0002] Polyester fiber is a basic textile raw material. Due to its comprehensive cost performance, it is widely used in fields such as clothing, home textiles, and industrial textiles. In 2021, the global production of polyester fiber reached 60 million tons, ranking first among all fiber varieties. With the continuous upgrading of terminal consumer demand, the performance requirements for polyester fiber products are getting higher and higher, and the functional improvement of polyester fiber has become increasingly urgent. Conventional polyester fibers have good mechanical properties, wear resistance, etc., but when used as a clothing fiber material, its moisture absorption is poor, and the moisture regain rate under standard conditions is only 0.4%; when used industrially, such as for paper strengthening, it often has a poor strengthening effect due to difficult uniform dispersion. To improve these disadvantages of polyester fibers, modification is very necessary. In view of the above disadvantages, essentially, polyester fibers lack reactive functional groups, especially the chemical properties of the fiber surface are inert, resulting in low moisture absorption rate and difficulty in surface modification of the fiber. How to achieve surface activation of polyester fiber materials and improve their further application or reaction ability is an important direction for enhancing the functionality of polyester fibers.

[0003] Chinese Patent CN110528109B discloses a high-strength flame-retardant polyester industrial yarn and its preparation method, which prepares a phosphorus-containing viscosity-increasing polyester chip by using low-temperature vacuum viscosity-increasing, high-temperature vacuum viscosity-increasing, and high-temperature solid-phase viscosity-increasing processes, and prepares a high-strength flame-retardant polyester industrial yarn by using the melt spinning process of the flame-retardant viscosity-increasing polyester chip.

[0004] Chinese Patent CN102102241A discloses a production method for directly manufacturing flame-retardant polyester staple fibers from recycled polyester bottle chips, and prepares flame-retardant polyester staple fibers by mixing and spinning the already dried polyester bottle chips and flame-retardant polyester masterbatch.

[0005] Chinese Patent CN112195532A discloses a flame-retardant polyester mother yarn and its preparation process, which includes steps of melt-blending a flame-retardant co-blending agent and a polyester fiber masterbatch, extruding and spinning to obtain a nascent fiber, and then performing post-treatment on the nascent fiber with a phosphate ester and a penetrant to obtain the flame-retardant polyester mother yarn.

[0006] From the perspective of the prior art, the flame retardant performance of polyester fibers is mainly achieved by introducing flame retardants for copolymerization in the polyester synthesis stage, introducing masterbatches containing flame retardants in the polyester melt spinning and forming stage, or performing flame retardant treatment on the fibers. Among them, the methods of copolymerization or blending will have a greater impact on the mechanical properties of the prepared flame retardant polyester fibers. In particular, the copolymerization method destroys the original molecular chain regularity of the polyester. For the method of post-treatment of fiber materials, although it is efficient, the surface of polyester fibers shows chemical inertness, making it difficult to achieve chemical grafting. It mostly adheres to the fiber surface by physical binding force and is not wash-resistant, and the flame retardant performance decreases significantly during use. Summary of the Invention

[0007] One of the technical problems to be solved by the present invention is to provide a new preparation method for flame retardant polyester fiber products, which has the characteristics of good mechanical properties and good flame retardant properties of the fibers.

[0008] To solve one of the above technical problems, the technical solution adopted by the present invention is as follows:

[0009] A preparation method for flame retardant polyester fiber products, comprising the following steps:

[0010] (1) The polyester melt is subjected to spinning, drawing, and shaping to obtain primary polyester fibers;

[0011] (2) The surface of the primary fiber product is subjected to alcoholysis treatment with an alcohol hydroxyl group-containing compound to obtain a material to be flame retardant-treated; the alcohol hydroxyl group functionality of the alcohol hydroxyl group-containing compound is 2 or more; the primary fiber product is the primary polyester fiber described in step (1) or a fabric made of the primary polyester fiber described in step (1), and preferably the fabric is knitted or woven;

[0012] (3) In the presence of an esterification reaction catalyst, the material to be flame retardant-treated is flame retardant-treated with a phosphorus-containing compound containing the following structural fragment:

[0013]

[0014] The alcoholysis treatment step in step (2) improves the effect of the flame retardant treatment in step (3).

[0015] In the above technical solution, it is preferred that the polyester described in step (1) includes at least one selected from the group consisting of PET (PET is the abbreviation of polyethylene terephthalate), PTT (PTT is the abbreviation of polytrimethylene terephthalate), and PBT (PBT is the abbreviation of polybutylene terephthalate).

[0016] In the above technical solution, preferably, the melt index (280 °C / 2.16 kg) of the polyester in step (1) is 10 to 120 g / 10 min. For example but not limited to, the melt index of the polyester is 15 g / 10 min, 20 g / 10 min, 25 g / 10 min, 30 g / 10 min, 35 g / 10 min, 40 g / 10 min, 45 g / 10 min, 50 g / 10 min, 55 g / 10 min, 60 g / 10 min, 65 g / 10 min, 70 g / 10 min, 75 g / 10 min, 80 g / 10 min, 85 g / 10 min, 90 g / 10 min, 95 g / 10 min, 100 g / 10 min, 105 g / 10 min, 110 g / 10 min, 115 g / 10 min, and so on.

[0017] In the above technical solution, preferably, the spinning temperature is preferably 260 to 295 °C. For example but not limited to, the spinning temperature is 265 °C, 270 °C, 275 °C, 280 °C, 285 °C, 290 °C. Only for comparison, the spinning temperature in the examples and comparative examples of the present invention is 285 °C.

[0018] In the above technical solution, preferably, the draw ratio is 3.0 to 5.0. For example but not limited to, the draw ratio is 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, and so on. Only for comparison, the fiber draw ratio in the examples and the comparison is 4.0.

[0019] In the above technical solution, preferably, the drawing temperature is 60 to 80 °C. For example but not limited to, the drawing temperature is 61 °C, 62 °C, 63 °C, 64 °C, 65 °C, 66 °C, 67 °C, 68 °C, 69 °C, 70 °C, 71 °C, 72 °C, 73 °C, 74 °C, 75 °C, 76 °C, 77 °C, 78 °C, 79 °C, and so on. Only for comparison, the drawing temperature of the fibers in the examples and the comparison is 65 °C.

[0020] In the above technical solution, preferably, the setting temperature is 140 to 160 °C. For example but not limited to, the setting temperature is 141 °C, 142 °C, 143 °C, 144 °C, 145 °C, 146 °C, 147 °C, 148 °C, 149 °C, 150 °C, 151 °C, 152 °C, 153 °C, 154 °C, 155 °C, 156 °C, 157 °C, 158 °C, 159 °C, and so on. Only for comparison, the setting temperature in the examples and the comparison is 150 °C.

[0021] In the above technical solution, as a non-limiting example, for instance but not limited to, the alcohol hydroxyl group-containing compound includes at least one selected from the group consisting of those with alcohol hydroxyl group functionality of 2, 3, 4, 5, 6, 7, 8, 9, and 10, or in other words, the average functionality of the alcohol hydroxyl group-containing compound is 2 to 10. Preferably, the alcohol hydroxyl group in the alcohol hydroxyl group-containing compound is a primary alcohol hydroxyl group. As a non-limiting example, specific compounds may be ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, mannitol, etc., or a mixture thereof, preferably including hydroxyl group-containing compounds with a hydroxyl functionality greater than 3. Those skilled in the art know that when using pentaerythritol, due to its high melting point, it is preferably used in the form of a pentaerythritol-ethylene glycol mixture by dissolving pentaerythritol in ethylene glycol. Only for the sake of comparison, in the examples of the present invention, the alcohol hydroxyl group-containing compound with an alcohol hydroxyl group functionality greater than 2 is represented by trimethylolpropane, and the alcohol hydroxyl group-containing compound with an alcohol hydroxyl group functionality of 2 is represented by ethylene glycol.

[0022] We found that the greater the alcohol hydroxyl group functionality of the alcohol hydroxyl group-containing compound, the better the flame retardant effect of the fabric product. For example, by comparison, the alcohol hydroxyl group-containing compound with an alcohol hydroxyl group functionality of 3 has a better effect than the alcohol hydroxyl group-containing compound with an alcohol hydroxyl group functionality of 2.

[0023] In the above technical solution, the preferred temperature for alcoholysis is 150 - 200 °C, for instance but not limited to, the temperature for alcoholysis is 155 °C, 160 °C, 165 °C, 170 °C, 175 °C, 180 °C, 185 °C, 190 °C, 195 °C, etc. Only for the sake of comparison, the temperature for alcoholysis in the examples and comparative examples of the present invention is both 190 °C.

[0024] In the above technical solution, the preferred time for alcoholysis is 10 - 100 seconds, for instance but not limited to 15 seconds, 20 seconds, 25 seconds, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 55 seconds, 60 seconds, 65 seconds, 70 seconds, 75 seconds, 80 seconds, 85 seconds, 90 seconds, 95 seconds, etc. Only for the sake of comparison, the time for alcoholysis in the examples and comparative examples of the present invention is both 50 seconds.

[0025] In the above technical solution, the preferred mass ratio of the primary fiber product to the hydroxyl group-containing compound is 0.02 - 0.2, for instance but not limited to, the mass ratio of the primary fiber product to the hydroxyl group-containing compound is 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, etc.

[0026] In the above technical solution, it is preferred that the alcoholysis process is carried out in the presence of an alcoholysis catalyst.

[0027] In the above technical solution, preferably, the amount of the alcoholysis catalyst is equivalent to 50 to 500 ppm of the weight of the hydroxyl group-containing compound, such as but not limited to 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, and so on.

[0028] In the above technical solution, the alcoholysis catalyst is not particularly limited, and those skilled in the art can reasonably select common alcoholysis catalysts (for example, basic substances, acidic substances, ionic liquids, etc. can be used as alcoholysis catalysts), which can all achieve comparable technical effects without any creative labor.

[0029] As a non-limiting example of the alcoholysis catalyst, for example, basic substances (which can be basic compounds or solid bases loaded with basic compounds) can be used as alcoholysis catalysts. Examples of basic compounds include but are not limited to hydroxides of alkali metals, alkali metal carbonates, bicarbonates of alkali metals, acetates of alkali metals, etc. More specifically, non-limiting examples of alcoholysis catalysts are sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium hydroxide, sodium acetate, potassium acetate, lithium acetate; solid bases loaded with basic compounds such as but not limited to magnesium oxide composite silica nanospheres, zinc oxide composite silica nanospheres, and so on.

[0030] As a non-limiting example of the alcoholysis catalyst, for example, acidic compounds (protic acids or non-protic acid Lewis acids) can be used as alcoholysis catalysts. For example, protic acids can be but are not limited to benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, solid acids (such as molecular sieves); metal salts in which metal (such as but not limited to lithium, magnesium, calcium, transition metals in the periodic table) ions can act as Lewis acids, and non-limiting examples of metal salts can be carboxylates (more commonly acetate salts), chlorides, sulfates, and so on. For example but not limited to lithium chloride, magnesium chloride, zinc acetate, manganese acetate, lead acetate, zinc chloride, and so on.

[0031] As a non-limiting example of the alcoholysis catalyst, for example, ionic liquids can also be used as alcoholysis catalysts. Non-limiting examples of specific ionic liquids used as alcoholysis catalysts are: [bmin]Cl, [bmin]OH, [bmin]ZnCl3, and so on.

[0032] Only for comparison, the alcoholysis catalyst used in the specific embodiments of the present invention is zinc acetate.

[0033] For non-limiting example only, alcoholysis is carried out in an alcoholysis tank which contains a hydroxy compound and a required amount of catalyst. The temperature of the alcoholysis tank is maintained at the alcoholysis temperature. The primary fiber product is immersed in the alcoholysis tank for the required impregnation time. To terminate the alcoholysis reaction, the temperature can be rapidly cooled. A convenient way to terminate the alcoholysis reaction is to wash the fiber product impregnated in the alcoholysis tank for the required alcoholysis time with water. Water washing can not only terminate the alcoholysis, but also reduce the residual hydroxy compound in the flame retardant treatment agent from entering the subsequent flame retardant treatment solution. Whether the water washing is continuous or intermittent is not particularly limited. When the water washing is in an intermittent mode, the number of water washing times is not particularly limited, such as 1 - 5 times (further non-limiting examples are 2 times, 3 times, 4 times, etc.); the amount of water used is not particularly limited. For example but not limited to, the amount of water used is 5 - 20 times the weight of the fiber product (more specific non-limiting examples are 6 times, 7 times, 8 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, 16 times, 17 times, 18 times, 19 times, etc.). The temperature of water washing is not particularly limited, such as 0 - 90°C, for example but not limited to 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, etc.; the time of water washing is not particularly limited, such as the time of each water washing is 5 - 60 minutes. Further examples of the water washing time are 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, etc. After the fiber product is washed with water, it is preferably dried to remove the water remaining on the fabric, which can prevent the dilution of the flame retardant treatment solution caused by the water on the fiber product entering the flame retardant treatment solution. The drying temperature is not particularly limited. For example but not limited to, the drying temperature is 60 - 200°C. Further non-limiting examples of the drying temperature are 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, etc.; the drying time is not particularly limited. For example but not limited to 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, etc. Only for comparison, the fiber product is washed with water twice, the amount of water used each time is 10 times the weight of the fiber product, the water washing temperature is 50°C, the time of each water washing is 30 minutes, and it is dried at 70°C for 4 hours after water washing.

[0034] In the above technical solution, preferably and for comparison, the phosphorus-containing compound includes cyclohexanehexol hexaphosphate.

[0035] In the above technical solution, preferably, the esterification reaction catalyst is a compound having a sulfonic acid group, such as but not limited to methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. For the sake of comparison only, the esterification catalyst used in the examples of the present invention is methanesulfonic acid.

[0036] In the above technical solution, preferably, the flame retardant treatment described in step (3) includes the following steps:

[0037] (i) The object to be flame retardant treated is impregnated with a flame retardant treatment liquid to obtain an object to be dried, and the flame retardant treatment liquid contains the above-mentioned phosphorus-containing compound and an esterification reaction catalyst;

[0038] (ii) Drying.

[0039] In the above technical solution, preferably, the solvent of the flame retardant treatment liquid in step (i) is water.

[0040] In the above technical solution, preferably, the weight content of the phosphorus-containing compound in the flame retardant treatment liquid in step (i) is 10-40%. For example but not limited to, the weight content of the phosphorus-containing compound in the flame retardant treatment liquid is 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, etc. For the sake of comparison only, the weight content of the phosphorus-containing compound in the flame retardant treatment liquid used in the examples and comparative examples is 30%.

[0041] In the above technical solution, preferably, the impregnation time in step (i) is 10-90 min, such as but not limited to the impregnation time in step (i) being 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, etc.

[0042] In the above technical solution, there is no special requirement for the impregnation temperature in step (i), and those skilled in the art can reasonably select it, and comparable technical effects can be achieved without creative labor. For example but not limited to, the impregnation temperature is 5-50 °C, and more specific examples of the impregnation temperature can be 10 °C, 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, etc. For the sake of convenient comparison, in the specific examples and comparative examples of the present invention, the impregnation temperature in step (i) is 25 °C.

[0043] In the above technical solution, preferably, the mass ratio of the object to be flame-retarded to the flame-retardant treatment liquid in step (i) is 0.01-0.1. For example but not limited to 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, etc. For the convenience of comparison, in the specific examples and comparative examples of the present invention, the mass ratio of the object to be flame-retarded to the flame-retardant treatment liquid is 0.05.

[0044] In the above technical solution, by weight, preferably, the liquid retention amount of the flame-retardant treatment liquid of the object to be dried in step (i) is 10-30%. Those skilled in the art can understand that here, the liquid retention amount of the flame-retardant treatment liquid of the object to be dried is based on weight and relative to the object to be flame-retarded. Those skilled in the art know that the liquid retention amount can be controlled according to the ability of the object to be flame-retarded to absorb the flame-retardant treatment liquid and whether and to what extent extrusion is performed after impregnation. As a non-limiting example, the liquid retention amount of the flame-retardant treatment liquid of the object to be dried in step (i) is, for example but not limited to, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, etc. Only for comparison, the liquid retention amount of the flame-retardant treatment liquid in the examples and comparative examples of the present invention is controlled at 20%.

[0045] In the above technical solution, preferably, the dosage of the esterification reaction catalyst is 100-1000 ppm by weight relative to the phosphorus-containing compound. For example but not limited to 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, 950 ppm, etc. Only for comparison, in the examples and comparative examples of the present invention, the dosage of the esterification catalyst is 200 ppm by weight relative to the phosphorus-containing compound.

[0046] In the above technical solution, preferably, the drying temperature in step (ii) is 120-180 °C. For example but not limited to the drying temperature being 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C, 155 °C, 160 °C, 165 °C, 170 °C, 175 °C, etc. Only for comparison, the drying temperature in step (ii) in the examples and comparative examples of the present invention is 150 °C.

[0047] In the above technical solution, it is preferred that the drying time in step (ii) is 3 to 15 minutes. For example, but not limited to, the drying time can be 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, etc. During the drying process of step (ii), the removal of water promotes the reaction between the hydroxyl groups on the surface of the object to be treated and the flame retardant groups, realizing the chemical bonding between the object to be treated and the flame retardant species. Only for comparison, the drying time in step (ii) in the examples and comparative examples of the present invention is both 10 minutes.

[0048] As is known to those skilled in the art, in the above technical solution, for the primary fiber product in step (2), whether in the form of fibers or fabrics, whether the fibers are long fibers or short fibers, and whether the fabrics are knitted or woven, comparable technical effects can be achieved; for the object to be flame retardant treated in step (3), whether in the form of fibers or fabrics, whether the fibers are long fibers or short fibers, and whether the fabrics are knitted or woven, comparable technical effects can be achieved. In the examples of the present invention, only for comparison, starting from step (2), a fabric made of primary polyester fibers is used as a representative of the primary fiber product. Similarly, only for comparison, the fabrics in the examples and comparative examples are both made in the most common way, spinning short fibers into yarns and then weaving the yarns into greige fabrics as representatives of the primary fiber products.

[0049] In the above technical solution, it is preferred that the polyester in step (1) includes low melt index PET and high melt index polyester.

[0050] In the above technical solution, it is preferred that the melt index (280 °C / 2.16 kg) of the low melt index PET is a g / 10 min, where a is 10 to 30. For example, but not limited to, a can be 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, etc. Only for comparison, the low melt index PET used in the specific embodiments of the present invention is all PET provided by Sinopec Yizheng Chemical Fiber Co., Ltd., with the grade FD501, marked with a melt index of 24 - 26 g / 10 min (280 °C / 2.16 kg), and the measured melt index is 25.7 g / 10 min (280 °C / 2.16 kg).

[0051] In the above technical solution, it is preferred that the melt index (280 °C / 2.16 kg) of the high melt index polyester is b g / 10 min, where b = a + c, c is greater than 0 and less than 90. For example, but not limited to, c can be 5, 10, 15, 20, 25, 33, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, etc. Further preferably, c is 30 to 60.

[0052] In the above technical solution, preferably, the high melt index polyester includes at least one selected from the group consisting of high melt index PET, high melt index PTT (PTT is the abbreviation of polytrimethylene terephthalate), and high melt index PBT (PBT is the abbreviation of polybutylene terephthalate).

[0053] We surprisingly found that when the polyester in step (1) includes low melt index PET and high melt index polyester, compared with the step of spinning using only low melt index PET, the limiting oxygen index of the flame retardant fiber product is increased. Especially when the high melt index polyester is PTT or PBT, there is an obvious mutual promotion effect between the low melt index PET and the high melt index polyester in terms of increasing the limiting oxygen index of the flame retardant fiber product.

[0054] When the high melt index polyester includes both high melt index PBT and high melt index PTT at the same time, there is a significant synergistic effect in terms of increasing the limiting oxygen index of the flame retardant fiber product.

[0055] When the high melt index polyester includes both high melt index PBT and high melt index PTT at the same time, the ratio between the high melt index PBT and the high melt index PTT is not limited, and comparable synergistic effects can be obtained. Only as a non-limiting example, the mass ratio between the high melt index PBT and the high melt index PTT is 0.1 to 10, such as but not limited to 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc. Only as an example, in the embodiment of using both high melt index PBT and high melt index PTT at the same time, the mass ratio between the high melt index PBT and the high melt index PTT is 1.

[0056] In the specific embodiment of the present invention, the high melt index PET is produced by Sinopec Yizheng Chemical Fiber Co., Ltd., with the grade of HS550, the marked melt index (280 °C / 2.16 kg) is 71 to 73 g / 10 min, and the measured melt index (280 °C / 2.16 kg) is 71.3 g / 10 min.

[0057] In the specific embodiment of the present invention, the high melt index PTT is produced by Zhangjiagang Meijingrong Chemical Industry Co., Ltd., with the grade of MJR101, the marked melt index (280 °C / 2.16 kg) is 71 to 74 g / 10 min, and the measured melt index (280 °C / 2.16 kg) is 72.7.

[0058] In the specific implementation mode of the present invention, the high melt index PBT is produced by Zhejiang Meiyuan New Materials Co., Ltd., with the brand number MY10, the marked melt index (280°C / 2.16 kg) is 72-75 g / 10 min, and the measured melt index (280°C / 2.16 kg) is 72.1 g / 10 min.

[0059] In the above technical solution, it is preferred that the mass ratio of the high melt index polyester to the low melt index PET is greater than 0 and 0.2 or less. For example, but not limited to, the mass ratio is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, etc., and more preferably 0.01-0.15. Only for comparison, in the embodiments of the present invention, the mass ratio of the high melt index polyester to the low melt index PET is 0.05.

[0060] In the specific implementation mode of the present invention, the melt index (280°C / 2.16 kg) complies with the provisions of GB / T 3682.1-2018. The content in the brackets following the melt index expression refers to the measurement under the conditions of a temperature of 280°C and a load of 2.16 kg.

[0061] In the examples and comparative examples of the present invention:

[0062] I. For the determination of the mechanical properties of the fabric, the dry state breaking strength and elongation at break of the fabric are determined according to the standard GB / T 3923.1-2013.

[0063] II. Test of the limiting oxygen index (LOI)

[0064] (1) Preparation of the fabric to be tested for LOI

[0065] The fabric products obtained in the examples and comparative examples of the present invention are subjected to 30 washing-drying cycles according to "GB / T 8629-2017 Textiles - Home laundering and drying procedures for testing", to obtain the fabric to be tested for LOI. Among them:

[0066] Washing: The washing machine uses the a) horizontal drum, front-loading washing machine in Section 1.2 of the standard document and the type A2 specified in Table A.1 of Appendix A; Companion wash: Refer to Type III in Table H.1 of Appendix H of the standard document, 100% polyester fiber; Detergent: Select the standard detergent 2 specified in Section 6.1.2 of the standard document; The washing procedure uses the procedure number 4N specified in Table B.1 of Appendix B of the standard document.

[0067] Drying: Select F - turnover drying in Section 1.4 of the standard document. The turnover dryer selects Type A2 turnover dryer specified in Section 5.2.2 of the turnover dryer selection standard document; the humidity setting of the turnover dryer refers to Table 2, Turnover Drying Program 2 in Section 10.2.4 of the standard document.

[0068] (2) Test the limiting oxygen index of the LOI test fabric obtained in step (1) according to the standard "GB / T 5454 - 1997 Textiles - Burning Performance - Determination of Oxygen Index Method". The higher the limiting oxygen index, the more difficult it is for the material to burn, or the better the flame - retardant performance.

[0069] The present invention will be described in detail below through specific embodiments and examples. Specific Embodiments

[0070]

Comparative Example 1

[0071] 1. Preparation of Primary Fiber Products

[0072] 1.1 Preparation of 2.22 dtex Polyester Fibers

[0073] The spinning raw material polyester is low - melt - index PET.

[0074] Melt the low - melt - index PET chips in a single - screw extruder to obtain a melt, and extrude the melt through a spinneret at 285°C; draw the filaments at 65°C with a draw ratio of 4.0, and set the filaments at 150°C; cut them into polyester staple fibers of 38 mm.

[0075] 1.2 Weaving of Grey Cloth

[0076] Spun the polyester staple fibers in step 1.1 into a 32S / 2 double - ply yarn, and then shuttle - weave the double - ply yarn into a grey cloth with a warp density of 170 ends / 10 cm, a weft density of 126 picks / 10 cm, a width of 160 cm, and a gram weight of 125 g / m 2 of grey cloth.

[0077] 2. Surface Alcoholysis Treatment of Primary Fiber Products

[0078] There is no such item.

[0079] 3. Flame - Retardant Treatment

[0080] (i) Immerse the grey cloth described in step 1.2 as the object to be flame - retardant - treated in the flame - retardant treatment liquid for 30 minutes, with an immersion temperature of 25°C. The mass ratio of the object to be flame - retardant - treated to the flame - retardant treatment liquid is 0.05. The flame - retardant treatment liquid is a mixed aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution is 30%, and the methanesulfonic acid is 200 ppmw relative to the weight of cyclohexanehexol hexaphosphate.

[0081] Then squeeze the impregnated fiber product to obtain the material to be dried (adjust the number of squeezing times and the intensity, and control the liquid holding amount of the flame retardant treatment liquid in the material to be dried to be 20%).

[0082] (ii) Dry the above material to be dried at 150 °C for 10 min to obtain a fabric product.

[0083] After measurement, the LOI of the fabric product is 21.2%, the breaking strength of the fabric product is 410.1 N, and the elongation at break of the fabric product is 30.3%.

[0084]

Example 1

[0085] 1. Preparation of primary fiber product

[0086] 1.1 Preparation of 2.22 dtex polyester fiber

[0087] The spinning raw material polyester is low melting index PET.

[0088] Melt the low melting index PET chips in a single screw extruder to obtain a melt. The melt is spun through a spinneret at 285 °C; the filaments are drawn at 65 °C with a draw ratio of 4.0 and are shaped at 150 °C; they are cut into 38 mm polyester staple fibers.

[0089] 1.2 Weaving of grey cloth

[0090] Spin the polyester staple fibers in step 1.1 into a 32S / 2 double yarn, and then shuttle weave the double yarn into a grey cloth with a warp density of 170 ends / 10 cm, a weft density of 126 picks / 10 cm, a width of 160 cm and a grammage of 125 g / m 2 of grey cloth.

[0091] 2. Surface alcoholysis treatment of primary fiber product

[0092] Use the grey cloth obtained in step 1.2 as the raw material grey cloth and immerse it in the alcoholysis treatment liquid at 190 °C for 50 s, then immediately take out the grey cloth and put it into water for washing. The washing is carried out 2 times in total. The washing temperature is 50 °C, and each washing lasts for 30 minutes. The amount of water used each time is 10 times the weight of the raw material grey cloth; then, take out the grey cloth, squeeze out the flowing water in the grey cloth, and place the grey cloth in a blast drying oven at 70 °C for drying for 4 hours to obtain an alcoholysis-treated fiber product. The mass ratio of the raw material grey cloth to the alcoholysis treatment liquid is 0.1. The alcoholysis treatment liquid is an alcohol solution of zinc acetate anhydrous, and the content of zinc acetate anhydrous relative to alcohol is 100 ppmw. The alcohol is trimethylolpropane.

[0093] 3. Flame retardant treatment

[0094] (i) The alcoholysis-treated fiber product described in step 2 was immersed in the flame retardant treatment liquid as the object to be flame retardant treated for 30 minutes at an immersion temperature of 25 °C. The mass ratio of the object to be flame retardant treated to the flame retardant treatment liquid was 0.05. The flame retardant treatment liquid was an aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution was 30%, and the methanesulfonic acid was 200 ppmw relative to the weight of cyclohexanehexol hexaphosphate.

[0095] Then, the impregnated fiber product was extruded to obtain the object to be dried (adjusting the extrusion times and force to control the liquid retention of the flame retardant treatment liquid in the object to be dried to 20%).

[0096] (ii) The above object to be dried was dried at 150 °C for 10 min to obtain the fabric product.

[0097] After measurement, the LOI of the fabric product was 29.7%, the breaking strength of the fabric product was 420.2 N, and the elongation at break of the fabric product was 31.8%.

[0098]

Comparative Example 2

[0099] 1. Preparation of the primary fiber product

[0100] 1.1 Preparation of 2.22 dtex polyester fiber

[0101] The spinning raw material polyester was high melt index PET.

[0102] The high melt index PET chips were melted in a single-screw extruder to obtain a melt. The melt was spun through a spinneret at 285 °C; the filaments were drawn at 65 °C with a draw ratio of 4.0 and were shaped at 150 °C; and were cut into 38 mm polyester staple fibers.

[0103] 1.2 Weaving of the greige fabric

[0104] The polyester staple fibers in step 1.1 were spun into a 32S / 2 two-ply yarn, and then the two-ply yarn was woven into a greige fabric with a warp density of 170 per 10 cm, a weft density of 126 per 10 cm, a width of 160 cm, and a grammage of 125 g / m 2 of the greige fabric.

[0105] 2. Surface alcoholysis treatment of the primary fiber product

[0106] This item was not carried out.

[0107] 3. Flame retardant treatment

[0108] (i) The embryo fabric described in step 1.2 was immersed in the flame retardant treatment liquid as the object to be flame retardant treated for 30 minutes, the immersion temperature was 25 °C, the mass ratio of the object to be flame retardant treated to the flame retardant treatment liquid was 0.05, the flame retardant treatment liquid was an aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate, and the weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution was 30%, and the methanesulfonic acid was 200 ppmw relative to the weight of cyclohexanehexol hexaphosphate.

[0109] Then, the impregnated fiber product was extruded to obtain the object to be dried (adjust the extrusion times and strength to control the liquid holding amount of the flame retardant treatment liquid in the object to be dried to 20%).

[0110] (ii) The above object to be dried was dried at 150 °C for 10 min to obtain a fabric product.

[0111] After measurement, the LOI of the fabric product was 21.6%, the breaking strength of the fabric product was 414.3 N, and the elongation at break of the fabric product was 32.2%.

[0112]

Example 2

[0113] 1. Preparation of primary fiber product

[0114] 1.1 Preparation of 2.22 dtex polyester fiber

[0115] The spinning raw material polyester was high melt index PET.

[0116] The high melt index PET chips were melted in a single screw extruder to obtain a melt, and the melt was spun through a spinneret at 285 °C; the filaments were drawn at 65 °C, the draw ratio was 4.0, and they were shaped at 150 °C; they were cut into polyester staple fibers of 38 mm.

[0117] 1.2 Weaving of embryo fabric

[0118] The polyester staple fibers in step 1.1 were spun into a double yarn of 32S / 2, and then the double yarn was shuttle woven into an embryo fabric with a warp density of 170 per 10 cm, a weft density of 126 per 10 cm, a width of 160 cm, and a gram weight of 125 g / m 2 of embryo fabric.

[0119] 2. Surface alcoholysis treatment of primary fiber product

[0120] Take the embryo fabric obtained in Step 1.2 as the raw embryo fabric and immerse it in the alcoholysis treatment solution at 190°C for 50 seconds. Then immediately take out the embryo fabric and put it into water for washing. Wash it twice in total. The washing temperature is 50°C, and each washing lasts for 30 minutes. The amount of water used each time is 10 times the weight of the raw embryo fabric. Then, take out the embryo fabric, squeeze out the flowing water in the embryo fabric, and place the embryo fabric in a blast drying oven to dry at 70°C for 4 hours to obtain the alcoholysis-treated fiber product. The mass ratio of the raw embryo fabric to the alcoholysis treatment solution is 0.1. The alcoholysis treatment solution is an alcohol solution of anhydrous zinc acetate, and the content of anhydrous zinc acetate relative to alcohol is 100 ppmw. The alcohol is trimethylolpropane.

[0121] 3. Flame Retardant Treatment

[0122] (i) Take the alcoholysis-treated fiber product described in Step 2 as the object to be flame retardant treated and immerse it in the flame retardant treatment solution for 30 minutes. The immersion temperature is 25°C. The mass ratio of the object to be flame retardant treated to the flame retardant treatment solution is 0.05. The flame retardant treatment solution is a mixed aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution is 30%, and the content of methanesulfonic acid relative to the weight of cyclohexanehexol hexaphosphate is 200 ppmw.

[0123] Then squeeze the impregnated fiber product to obtain the object to be dried (adjust the number of squeezes and the intensity to control the liquid holding amount of the flame retardant treatment solution in the object to be dried to 20%).

[0124] (ii) Dry the above object to be dried at 150°C for 10 min to obtain the fabric product.

[0125] After measurement, the LOI of the fabric product is 30.2%, the breaking strength of the fabric product is 421.8 N, and the breaking elongation of the fabric product is 31.9%.

[0126]

Comparative Example 3

[0127] 1. Preparation of Primary Fiber Product

[0128] 1.1. Preparation of 2.22 dtex Polyester Fiber

[0129] The spinning raw material polyester is high melt index PTT.

[0130] Melt the high melt index PTT chips in a single screw extruder to obtain a melt. The melt is spun through a spinneret at 285°C. The filaments are drawn at 65°C with a draw ratio of 4.0 and shaped at 150°C. Cut into polyester staple fibers of 38 mm.

[0131] 1.2. Weaving of Embryo Fabric

[0132] The polyester staple fibers in Step 1.1 are spun into a two-ply yarn of 32S / 2, and then the two-ply yarn is woven into a grey fabric with a warp density of 170 threads / 10 cm, a weft density of 126 threads / 10 cm, a width of 160 cm, and a weight of 125 g / m². 2 of the grey fabric.

[0133] 2. Surface alcoholysis treatment of the primary fiber product

[0134] There is no such item.

[0135] 3. Flame retardant treatment

[0136] (i) The grey fabric described in Step 1.2 is impregnated in the flame retardant treatment liquid for 30 minutes at an impregnation temperature of 25°C. The mass ratio of the object to be flame retardant treated to the flame retardant treatment liquid is 0.05. The flame retardant treatment liquid is a mixed aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution is 30%, and the methanesulfonic acid is 200 ppmw relative to the weight of cyclohexanehexol hexaphosphate.

[0137] Then, the impregnated fiber product is extruded to obtain the object to be dried (adjust the extrusion times and force to control the liquid retention of the flame retardant treatment liquid in the object to be dried at 20%).

[0138] (ii) The above object to be dried is dried at 150°C for 10 minutes to obtain a fabric product.

[0139] After measurement, the LOI of the fabric product is 22.1%, the breaking strength of the fabric product is 416.6 N, and the breaking elongation of the fabric product is 31.0%.

[0140]

Example 3

[0141] 1. Preparation of the primary fiber product

[0142] 1.1. Preparation of 2.22 dtex polyester fibers

[0143] The spinning raw material polyester is high melt index PTT.

[0144] The high melt index PTT chips are melted in a single screw extruder to obtain a melt. The melt is spun through a spinneret at 285°C; the filaments are drawn at 65°C with a draw ratio of 4.0 and are shaped at 150°C; and they are cut into polyester staple fibers of 38 mm.

[0145] 1.2. Weaving of the grey fabric

[0146] The polyester staple fibers in Step 1.1 are spun into a two-ply yarn of 32S / 2, and then the two-ply yarn is woven into a grey fabric with a warp density of 170 threads / 10 cm, a weft density of 126 threads / 10 cm, a width of 160 cm, and a weight of 125 g / m² 2 of the grey fabric.

[0147] 2. Surface alcoholysis treatment of primary fiber products

[0148] Use the embryo cloth obtained in step 1.2 as the raw material embryo cloth and immerse it in the alcoholysis treatment liquid at 190 °C for 50 seconds. Then immediately take out the embryo cloth and put it into water for washing. Wash it twice in total. The washing temperature is 50 °C, and each washing lasts for 30 minutes. The amount of water used each time is 10 times the weight of the raw material embryo cloth. Then, take out the embryo cloth, squeeze out the flowing water in the embryo cloth, and place the embryo cloth in a blast drying oven to dry at 70 °C for 4 hours to obtain the alcoholysis-treated fiber product. The mass ratio of the raw material embryo cloth to the alcoholysis treatment liquid is 0.1. The alcoholysis treatment liquid is an alcohol solution of zinc acetate anhydrous, and the content of zinc acetate anhydrous relative to alcohol is 100 ppmw, and the alcohol is trimethylolpropane.

[0149] 3. Flame retardant treatment

[0150] (i) Immerse the alcoholysis-treated fiber product described in step 2 as the object to be flame retardant treated in the flame retardant treatment liquid for 30 minutes. The immersion temperature is 25 °C. The mass ratio of the object to be flame retardant treated to the flame retardant treatment liquid is 0.05. The flame retardant treatment liquid is a mixed aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution is 30%, and the content of methanesulfonic acid relative to the weight of cyclohexanehexol hexaphosphate is 200 ppmw.

[0151] Then squeeze the impregnated fiber product to obtain the object to be dried (adjust the number of squeezes and the strength to control the liquid holding amount of the flame retardant treatment liquid in the object to be dried to 20%).

[0152] (ii) Dry the above object to be dried at 150 °C for 10 minutes to obtain the fabric product.

[0153] After measurement, the LOI of the fabric product is 30.5%, the breaking strength of the fabric product is 424.0 N, and the elongation at break of the fabric product is 32.3%.

[0154]

Comparative Example 4

[0155] 1. Preparation of primary fiber products

[0156] 1.1. Preparation of 2.22 dtex polyester fiber

[0157] The spinning raw material polyester is high melt index PBT.

[0158] Melt the high melt index PBT chips in a single screw extruder to obtain a melt. The melt is spun through a spinneret at 285 °C. The filaments are drawn at 65 °C with a draw ratio of 4.0 and are shaped at 150 °C. Cut into polyester staple fibers of 38 mm.

[0159] 1.2. Weaving of embryo cloth

[0160] The polyester staple fibers in Step 1.1 are spun into a two-ply yarn of 32S / 2, and then the two-ply yarn is woven into a grey fabric with a warp density of 170 threads per 10 cm, a weft density of 126 threads per 10 cm, a width of 160 cm, and a weight of 125 g / m 2 of grey fabric.

[0161] 2. Surface alcoholysis treatment of the primary fiber product

[0162] This item is not applicable.

[0163] 3. Flame retardant treatment

[0164] (i) The grey fabric described in Step 1.2 is immersed in a flame retardant treatment liquid for 30 minutes at an immersion temperature of 25°C. The mass ratio of the object to be flame retardant treated to the flame retardant treatment liquid is 0.05. The flame retardant treatment liquid is a mixed aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution is 30%, and the relative weight of methanesulfonic acid to cyclohexanehexol hexaphosphate is 200 ppmw.

[0165] Then, the impregnated fiber product is extruded to obtain an object to be dried (adjusting the number of extrusion times and the strength to control the retention amount of the flame retardant treatment liquid in the object to be dried to 20%).

[0166] (ii) The above object to be dried is dried at 150°C for 10 minutes to obtain a fabric product.

[0167] After measurement, the LOI of the fabric product is 23.0%, the breaking strength of the fabric product is 424.5 N, and the elongation at break of the fabric product is 32.7%.

[0168]

Example 4

[0169] 1. Preparation of the primary fiber product

[0170] 1.1. Preparation of 2.22 dtex polyester fibers

[0171] The spinning raw material polyester is high melting index PBT.

[0172] The high melting index PBT chips are melted in a single-screw extruder to obtain a melt. The melt is spun through a spinneret at 285°C; the filaments are drawn at 65°C with a draw ratio of 4.0 and are shaped at 150°C; they are cut into polyester staple fibers of 38 mm.

[0173] 1.2. Weaving of the grey fabric

[0174] The polyester staple fibers in Step 1.1 are spun into a two-ply yarn of 32S / 2, and then the two-ply yarn is woven into a grey fabric with a warp density of 170 threads per 10 cm, a weft density of 126 threads per 10 cm, a width of 160 cm, and a weight of 125 g / m2 Grey fabric

[0175] 2. Surface alcoholysis treatment of primary fiber products

[0176] Use the grey fabric obtained in Step 1.2 as the raw grey fabric and immerse it in the alcoholysis treatment solution at 190 °C for 50 seconds. Then immediately take out the grey fabric and put it into water for washing. Wash it twice in total. The washing temperature is 50 °C, and each washing lasts for 30 minutes. The amount of water used each time is 10 times the weight of the raw grey fabric. Then, take out the grey fabric, squeeze out the flowing water in the grey fabric, and place the grey fabric in a forced-air drying oven to dry at 70 °C for 4 hours to obtain the alcoholysis-treated fiber product. The mass ratio of the raw grey fabric to the alcoholysis treatment solution is 0.1. The alcoholysis treatment solution is an alcohol solution of zinc acetate anhydrous, and the content of zinc acetate anhydrous relative to alcohol is 100 ppmw. The alcohol is trimethylolpropane.

[0177] 3. Flame retardant treatment

[0178] (i) Immerse the alcoholysis-treated fiber product described in Step 2 in the flame retardant treatment solution for 30 minutes. The immersion temperature is 25 °C. The mass ratio of the object to be flame retardant treated to the flame retardant treatment solution is 0.05. The flame retardant treatment solution is a mixed aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution is 30%, and the content of methanesulfonic acid relative to the weight of cyclohexanehexol hexaphosphate is 200 ppmw.

[0179] Then squeeze the impregnated fiber product to obtain the object to be dried (adjust the number of squeezes and the intensity to control the liquid holding amount of the flame retardant treatment solution in the object to be dried to 20%).

[0180] (ii) Dry the above object to be dried at 150 °C for 10 minutes to obtain the fabric product.

[0181] After measurement, the LOI of the fabric product is 30.9%, the breaking strength of the fabric product is 426.1 N, and the elongation at break of the fabric product is 33.1%.

[0182]

Example 5

[0183] 1. Preparation of primary fiber products

[0184] 1.1. Preparation of 2.22 dtex polyester fiber

[0185] The spinning raw material polyester is low melting index PET and high melting index polyester. The high melting index polyester is high melting index PET, and the mass ratio of the high melting index polyester to the low melting index PET is 0.05.

[0186] Mix low melt index PET chips and high melt index PET chips, melt them in a single-screw extruder to obtain a melt, and extrude the melt through a spinneret at 285°C; stretch the filaments at 65°C with a draw ratio of 4.0, and set them at 150°C; cut them into polyester staple fibers 38 mm long.

[0187] 1.2 Weaving of the grey fabric

[0188] Spin the polyester staple fibers obtained in Step 1.1 into a two-ply yarn of 32S / 2, and then shuttle-weave the two-ply yarn into a grey fabric with a warp density of 170 ends / 10 cm, a weft density of 126 picks / 10 cm, a width of 160 cm, and a weight of 125 g / m². 2 of the grey fabric.

[0189] 2 Surface alcoholysis treatment of the primary fiber product

[0190] Use the grey fabric obtained in Step 1.2 as the raw material grey fabric, immerse it in the alcoholysis treatment solution at 190°C for 50 seconds, then immediately take out the grey fabric and put it into water for washing. Wash it twice in total, with the washing temperature being 50°C, 30 minutes for each wash, and the amount of water used each time being 10 times the weight of the raw material grey fabric; then, take out the grey fabric, squeeze to drain the flowing water in the grey fabric, place the grey fabric in a blast drying oven and dry it at 70°C for 4 hours to obtain the alcoholysis-treated fiber product. The mass ratio of the raw material grey fabric to the alcoholysis treatment solution is 0.1. The alcoholysis treatment solution is an alcohol solution of zinc acetate anhydrous, and the content of zinc acetate anhydrous relative to alcohol is 100 ppmw, and the alcohol is trimethylolpropane.

[0191] 3 Flame retardant treatment

[0192] (i) Immerse the alcoholysis-treated fiber product described in Step 2 as the object to be flame retardant treated in the flame retardant treatment solution for 30 minutes, with the immersion temperature being 25°C. The mass ratio of the object to be flame retardant treated to the flame retardant treatment solution is 0.05. The flame retardant treatment solution is a mixed aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution is 30%, and the content of methanesulfonic acid relative to the weight of cyclohexanehexol hexaphosphate is 200 ppmw.

[0193] Then squeeze the impregnated fiber product to obtain the object to be dried (adjust the number of squeezing times and the strength to control the liquid retention of the flame retardant treatment solution in the object to be dried to 20%).

[0194] (ii) Dry the above object to be dried at 150°C for 10 minutes to obtain the fabric product.

[0195] After measurement, the LOI of the fabric product is 30.0%, the breaking strength of the fabric product is 420.5 N, and the breaking elongation of the fabric product is 31.7%.

[0196]

Example 6

[0197] 1. Preparation of primary fiber products

[0198] 1.1 Preparation of 2.22 dtex polyester fiber

[0199] The spinning raw material polyester is low melting index PET and high melting index polyester. The high melting index polyester is high melting index PTT, and the mass ratio of high melting index polyester to low melting index PET is 0.05.

[0200] Mix the low melting index PET chips and high melting index PTT chips, melt them in a single screw extruder to obtain a melt. The melt is spun through a spinneret at 285 °C; the filaments are drawn at 65 °C with a draw ratio of 4.0 and set at 150 °C; cut into polyester staple fibers of 38 mm.

[0201] 1.2 Weaving of grey fabric

[0202] Spin the polyester staple fibers obtained in step 1.1 into a 32S / 2 double yarn, and then shuttle weave the double yarn into a grey fabric with a warp density of 170 per 10 cm, a weft density of 126 per 10 cm, a width of 160 cm and a grammage of 125 g / m 2 of grey fabric.

[0203] 2. Surface alcoholysis treatment of primary fiber products

[0204] Use the grey fabric obtained in step 1.2 as the raw material grey fabric, immerse it in the alcoholysis treatment solution at 190 °C for 50 seconds, then immediately take out the grey fabric and put it into water for soaking and washing. Soak and wash a total of 2 times, the soaking and washing temperature is 50 °C, each soaking and washing is 30 minutes, and the amount of water used each time is 10 times the weight of the raw material grey fabric; then, take out the grey fabric, squeeze out the flowing water in the grey fabric, and place the grey fabric in a blast drying oven at 70 °C for drying for 4 hours to obtain an alcoholysis-treated fiber product. The mass ratio of the raw material grey fabric to the alcoholysis treatment solution is 0.1. The alcoholysis treatment solution is an alcohol solution of zinc acetate anhydrous, and the content of zinc acetate anhydrous relative to alcohol is 100 ppmw, and the alcohol is trimethylolpropane.

[0205] 3. Flame retardant treatment

[0206] (i) Immerse the alcoholysis-treated fiber product described in step 2 as the object to be flame retardant treated in the flame retardant treatment solution for 30 minutes, the immersion temperature is 25 °C, the mass ratio of the object to be flame retardant treated to the flame retardant treatment solution is 0.05, and the flame retardant treatment solution is a mixed aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution is 30%, and the content of methanesulfonic acid relative to the weight of cyclohexanehexol hexaphosphate is 200 ppmw.

[0207] Then squeeze the impregnated fiber product to obtain the object to be dried (adjust the number of squeezing times and the strength to control the liquid holding amount of the flame retardant treatment solution in the object to be dried to 20%).

[0208] (ii) The above-mentioned material to be dried is dried at 150°C for 10 min to obtain a fabric product.

[0209] After measurement, the LOI of the fabric product is 32.2%, the breaking strength of the fabric product is 426.6 N, and the elongation at break of the fabric product is 33.9%.

[0210]

Example 7

[0211] 1. Preparation of primary fiber product

[0212] 1.1 Preparation of 2.22 dtex polyester fiber

[0213] The spinning raw material polyester is low melting index PET and high melting index polyester. The high melting index polyester is high melting index PBT, and the mass ratio of the high melting index polyester to the low melting index PET is 0.05.

[0214] The low melting index PET chips and high melting index PBT chips are mixed and melted in a single-screw extruder to obtain a melt. The melt is spun through a spinneret at 285°C; the filaments are drawn at 65°C with a draw ratio of 4.0 and are shaped at 150°C; they are cut into polyester staple fibers of 38 mm.

[0215] 1.2 Weaving of grey fabric

[0216] The polyester staple fibers obtained in step 1.1 are spun into a double yarn of 32S / 2, and then the double yarn is shuttle-woven into a grey fabric with a warp density of 170 ends / 10 cm, a weft density of 126 picks / 10 cm, a width of 160 cm, and a weight of 125 g / m 2 of grey fabric.

[0217] 2. Surface alcoholysis treatment of primary fiber product

[0218] The grey fabric obtained in step 1.2 is used as the raw material grey fabric and is immersed in the alcoholysis treatment solution at 190°C for 50 seconds, then immediately taken out and immersed in water for washing. It is washed a total of 2 times, the washing temperature is 50°C, and each washing time is 30 minutes. The amount of water used each time is 10 times the weight of the raw material grey fabric; then, the grey fabric is taken out, squeezed to drain the flowing water in the grey fabric, and the grey fabric is placed in a forced-air drying oven and dried at 70°C for 4 hours to obtain an alcoholysis-treated fiber product. The mass ratio of the raw material grey fabric to the alcoholysis treatment solution is 0.1. The alcoholysis treatment solution is an alcohol solution of zinc acetate anhydrous, and the content of zinc acetate anhydrous relative to alcohol is 100 ppmw, and the alcohol is trimethylolpropane.

[0219] 3. Flame retardant treatment

[0220] (i) Impregnate the alcoholysis-treated fiber product described in step 2 as the object to be flame-retarded in the flame-retardant treatment liquid for 30 minutes at an impregnation temperature of 25°C. The mass ratio of the object to be flame-retarded to the flame-retardant treatment liquid is 0.05. The flame-retardant treatment liquid is a mixed aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution is 30%, and the methanesulfonic acid is 200 ppmw relative to the weight of cyclohexanehexol hexaphosphate.

[0221] Then, extrude the impregnated fiber product to obtain the object to be dried (adjust the extrusion times and strength to control the liquid holding amount of the flame-retardant treatment liquid in the object to be dried to 20%).

[0222] (ii) Dry the above object to be dried at 150°C for 10 minutes to obtain a fabric product.

[0223] After measurement, the LOI of the fabric product is 32.8%, the breaking strength of the fabric product is 427.0 N, and the elongation at break of the fabric product is 33.9%.

[0224]

Example 8

[0225] 1. Preparation of primary fiber product

[0226] 1.1 Preparation of 2.22 dtex polyester fiber

[0227] The spinning raw material polyester is low melting index PET and high melting index polyester. The high melting index polyester is high melting index PTT and high melting index PBT. The mass ratio of the high melting index polyester to the low melting index PET is 0.05, and the mass ratio between the high melting index PBT and the high melting index PTT is 1.

[0228] Mix the low melting index PET chips, high melting index PTT chips and high melting index PBT chips, melt them in a single-screw extruder to obtain a melt. The melt is spun through a spinneret at 285°C; the filaments are drawn at 65°C with a draw ratio of 4.0 and are set at 150°C; they are cut into polyester staple fibers of 38 mm.

[0229] 1.2 Weaving of greige fabric

[0230] Spun the polyester staple fibers in step 1.1 into a 32S / 2 double yarn, and then shuttle-weave the double yarn into a greige fabric with a warp density of 170 ends / 10 cm, a weft density of 126 picks / 10 cm, a width of 160 cm and a grammage of 125 g / m 2 of greige fabric.

[0231] 2. Surface alcoholysis treatment of primary fiber product

[0232] Use the greige fabric obtained in Step 1.2 as the raw greige fabric, immerse it in the alcoholysis treatment solution at 190 °C for 50 seconds, then immediately take out the greige fabric and immerse it in water for washing. Wash it twice in total. The washing temperature is 50 °C, and each washing lasts for 30 minutes. The amount of water used each time is 10 times the weight of the raw greige fabric. Then, take out the greige fabric, squeeze out the flowing water in the greige fabric, place the greige fabric in a blast drying oven and dry it at 70 °C for 4 hours to obtain the alcoholysis-treated fiber product. The mass ratio of the raw greige fabric to the alcoholysis treatment solution is 0.1. The alcoholysis treatment solution is an alcohol solution of anhydrous zinc acetate, and the content of anhydrous zinc acetate relative to alcohol is 100 ppmw. The alcohol is ethylene glycol.

[0233] 3. Flame Retardant Treatment

[0234] (i) Immerse the alcoholysis-treated fiber product described in Step 2 as the object to be flame retardant treated in the flame retardant treatment solution for 30 minutes. The immersion temperature is 25 °C. The mass ratio of the object to be flame retardant treated to the flame retardant treatment solution is 0.05. The flame retardant treatment solution is a mixed aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution is 30%, and the content of methanesulfonic acid relative to the weight of cyclohexanehexol hexaphosphate is 200 ppmw.

[0235] Then squeeze the impregnated fiber product to obtain the object to be dried (adjust the number of squeezing times and the strength to control the liquid holding amount of the flame retardant treatment solution in the object to be dried to 20%).

[0236] (ii) Dry the above object to be dried at 150 °C for 10 minutes to obtain the fabric product.

[0237] After measurement, the LOI of the fabric product is 33.4%, the breaking strength of the fabric product is 428.5 N, and the elongation at break of the fabric product is 34.1%.

[0238]

Example 9

[0239] 1. Preparation of Primary Fiber Product

[0240] 1.1 Preparation of 2.22 dtex Polyester Fiber

[0241] The spinning raw material polyester is low melting index PET and high melting index polyester. The high melting index polyester is high melting index PTT and high melting index PBT. The mass ratio of the high melting index polyester to the low melting index PET is 0.05, and the mass ratio between the high melting index PBT and the high melting index PTT is 1.

[0242] Mix the low melting index PET chips, high melting index PTT chips and high melting index PBT chips, melt them in a single screw extruder to obtain a melt. The melt is spun through a spinneret at 285 °C. The filaments are drawn at 65 °C with a draw ratio of 4.0 and shaped at 150 °C. Cut into 38 mm polyester staple fibers.

[0243] 1.2 Weaving of grey fabric

[0244] The polyester staple fibers in Step 1.1 are spun into 32S / 2 double yarns, and then the double yarns are shuttle woven into grey fabric with a warp density of 170 per 10 cm, a weft density of 126 per 10 cm, a width of 160 cm and a grammage of 125 g / m 2 of grey fabric.

[0245] 2 Surface alcoholysis treatment of primary fiber products

[0246] Taking the grey fabric obtained in Step 1.2 as the raw material grey fabric, it is impregnated in the alcoholysis treatment solution at 190°C for 50 seconds, and then immediately taken out and immersed in water for washing. The washing is carried out 2 times in total. The washing temperature is 50°C, and each washing lasts for 30 minutes. The amount of water used each time is 10 times the weight of the raw material grey fabric; then, the grey fabric is taken out, and the flowing water in the grey fabric is squeezed out. The grey fabric is placed in a blast drying oven and dried at 70°C for 4 hours to obtain the alcoholysis treated fiber product. The mass ratio of the raw material grey fabric to the alcoholysis treatment solution is 0.1. The alcoholysis treatment solution is an alcohol solution of zinc acetate anhydrous, and the content of zinc acetate anhydrous relative to alcohol is 100 ppmw, and the alcohol is trimethylolpropane.

[0247] 3 Flame retardant treatment

[0248] (i) Taking the alcoholysis treated fiber product described in Step 2 as the object to be flame retardant treated, it is impregnated in the flame retardant treatment solution for 30 minutes. The impregnation temperature is 25°C. The mass ratio of the object to be flame retardant treated to the flame retardant treatment solution is 0.05. The flame retardant treatment solution is a mixed aqueous solution of methanesulfonic acid and cyclohexanehexol hexaphosphate. The weight content of cyclohexanehexol hexaphosphate in the mixed aqueous solution is 30%, and the content of methanesulfonic acid relative to the weight of cyclohexanehexol hexaphosphate is 200 ppmw.

[0249] Then, the impregnated fiber product is squeezed to obtain the object to be dried (adjusting the number of squeezing times and the strength to control the liquid holding amount of the flame retardant treatment solution in the object to be dried to be 20%).

[0250] (ii) Drying the above object to be dried at 150°C for 10 min to obtain the fabric product.

[0251] It is measured that the LOI of the fabric product is 35.0%, the breaking strength of the fabric product is 429.3 N, and the elongation at break of the fabric product is 34.5%.

Claims

1. Preparation method of flame-retardant polyester fiber products, comprising the following steps: (1) The polyester melt is subjected to spinning, drawing, and shaping to obtain primary polyester fibers; (2) The surface of the primary fiber product is subjected to alcoholysis treatment with an alcohol hydroxyl group-containing compound to obtain an object to be flame-retardant treated; the alcohol hydroxyl group functionality of the alcohol hydroxyl group-containing compound is 2 or more; the primary fiber product is the primary polyester fiber described in step (1) or a fabric made of the primary polyester fiber described in step (1); (3) In the presence of an esterification reaction catalyst, the object to be flame-retardant treated is flame-retardant treated with a phosphorus-containing compound having the following structural fragment: ； The polyester described in step (1) includes low melt index PET and high melt index polyester, and the high melt index polyester simultaneously includes high melt index PBT and high melt index PTT; The melt index of the low melt index PET is a g / 10 min, where a is 10 to 30, and the melt index test condition of the low melt index PET is 280 °C / 2.16 kg; The melt index of the high melt index polyester is b g / 10 min, b = a + c, c is greater than 0 and less than 90, and the melt index test condition of the high melt index polyester is 280 °C / 2.16 kg.

2. The preparation method according to claim 1, characterized in that c is 30 to 60.

3. The preparation method according to claim 1, characterized in that The fabric described in step (2) is knitted or woven.

4. The preparation method according to claim 1, characterized in that The temperature of alcoholysis is 150~200 °C.

5. The preparation method according to claim 1, characterized in that The time of alcoholysis is 10~100 seconds.

6. The preparation method according to claim 1, characterized in that The mass ratio of the primary fiber product to the alcohol hydroxyl group-containing compound is 0.02~0.

2.

7. The preparation method according to claim 1, characterized in that The alcoholysis process is carried out in the presence of an alcoholysis catalyst.

8. The preparation method according to claim 7, characterized in that The dosage of the alcoholysis catalyst is equivalent to 50~500 ppm of the weight of the alcohol hydroxyl group-containing compound.

9. The preparation method according to claim 7, characterized in that The alcoholysis catalyst is an acidic substance, a basic substance, or an ionic liquid.

10. The preparation method according to claim 1, characterized in that The phosphorus-containing compound includes cyclohexanehexol hexaphosphate.

11. The preparation method according to claim 1, characterized in that The esterification reaction catalyst is a compound having a sulfonic acid group.

12. The preparation method according to claim 11, characterized in that The esterification reaction catalyst is methanesulfonic acid, benzenesulfonic acid, or p-toluenesulfonic acid.

13. The preparation method according to claim 1, characterized in that: The flame-retardant treatment described in step (3) includes the following steps: (i) The object to be flame-retardant treated is impregnated with a flame-retardant treatment liquid to obtain an object to be dried, and the flame-retardant treatment liquid contains the above phosphorus-containing compound and an esterification reaction catalyst; (ii) Drying.

14. The preparation method according to claim 13, characterized in that: The solvent of the flame-retardant treatment liquid in step (i) is water.

15. The preparation method according to claim 13, characterized in that: The weight content of the phosphorus-containing compound in the flame-retardant treatment liquid in step (i) is 10~40%.

16. The preparation method according to claim 13, characterized in that: The mass ratio of the object to be flame-retardant treated to the flame-retardant treatment liquid in step (i) is 0.01~0.

1.

17. The preparation method according to claim 13, characterized in that: The dosage of the esterification reaction catalyst is 100~1000 ppm by weight relative to the phosphorus-containing compound.

18. The preparation method according to claim 13, characterized in that: The drying temperature in step (ii) is 120~180 °C.

19. The preparation method according to claim 13, characterized in that: The drying time in step (ii) is 3~15 min.

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