Impact-resistant flame-retardant polyamide cable tie and preparation method thereof

Abstract

The present invention relates to the technical field of polymer materials, and specifically to an impact-resistant flame-retardant polyamide cable tie and a preparation method thereof. The present invention fully mixes polyamide 6 and a flame retardant, and obtains a flame-retardant fiber through melt extrusion, pelletizing, and melt spinning. Then, by adding magnesium-aluminum hydrotalcite material, γ-aminopropyltriethoxysilane, 4-hydroxybenzaldehyde, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and cyanuric chloride, a hydrotalcite flame-retardant material is prepared. Polyamide resin, flame-retardant fiber, and hydrotalcite flame-retardant material are pre-mixed, and then toughening agent, plasticizer, antioxidant, and heat stabilizer are added and mixed to obtain a mixture; the mixture is sequentially subjected to extrusion granulation and injection molding to obtain a finished product. The finished product prepared by the present invention has good flame retardancy and impact resistance, and therefore has broad application prospects in the technical field of polymer materials.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to an impact-resistant and flame-retardant polyamide cable tie and a preparation method thereof. Background Art

[0002] Despite their seemingly ordinary appearance, polyamide cable ties play an irreplaceable and vital role in numerous areas of modern industry and life, demonstrating their multifaceted modern value. Polyamide cable ties offer excellent chemical and heat resistance. Industries like the chemical and food processing industries often face complex production environments, often involving a variety of chemicals and high temperatures. Polyamide cable ties are resistant to corrosion from a wide range of chemicals and maintain stable performance within a certain temperature range. They resist rapid aging and damage from exposure to chemicals or high temperatures, thus ensuring the long-term effectiveness of the tie and reducing maintenance costs. Furthermore, their ease of use is a key value proposition. Polyamide cable ties are simple to use: simply thread the tie through the item to be tied and tighten the buckle, eliminating the need for complex tools or techniques. This convenience allows for rapid application in a variety of situations, improving work efficiency. Whether on large-scale factory production lines or for routine household maintenance, polyamide cable ties easily handle tie-down tasks.

[0003] However, during transportation and use, if the polyamide cable ties used to bind goods lack impact resistance, they are prone to breakage. This can cause the tied items to scatter, potentially damaging them and leading to safety accidents. On industrial production lines, vibrations from mechanical equipment and the installation and removal of parts can also impact cable ties. Furthermore, in certain areas, such as electronics and electrical appliances, electrical equipment generates heat during operation. If a short circuit or other fault occurs, it can cause a fire. Polyamide cable ties, a common tool for binding wires and cables, will burn rapidly if they come into contact with fire if they lack flame retardancy, further spreading the fire and increasing the risk of fire.

[0004] In order to overcome the defects of the prior art, the present invention provides an impact-resistant and flame-retardant polyamide cable tie and a preparation method thereof. Summary of the Invention

[0005] The object of the present invention is to provide an impact-resistant flame-retardant polyamide cable tie and a preparation method thereof, so as to solve the problems in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] A method for preparing an impact-resistant flame-retardant polyamide cable tie comprises the following steps:

[0008] Step 1: fully mixing polyamide 6 and flame retardant, and then melt-extruding, pelletizing, and melt-spinning to obtain flame-retardant fiber;

[0009] Step 2: adding magnesium aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to a mixed solvent, fully dispersing them evenly, adjusting the pH to 9.0-9.2, stirring and reacting at 65-70° C. for 3-4 hours, and filtering, washing, drying, and grinding after the reaction to obtain a modified hydrotalcite material; adding the modified hydrotalcite material and 4-hydroxybenzaldehyde to ethanol, stirring and reacting at 70-75° C. for 4-5 hours, and then adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution dropwise, continuing the reaction for 5-8 hours, and cooling, filtering, washing, and vacuum drying after the reaction to obtain an intermediate product;

[0010] Under a nitrogen environment, the intermediate product is dissolved in tetrahydrofuran, and triethylamine is added and stirred thoroughly to obtain a reaction solution; cyanuric chloride is dissolved in tetrahydrofuran to obtain a cyanuric chloride solution; the reaction solution is allowed to stand at 0-3°C for 5-8 minutes, and the cyanuric chloride solution is added dropwise. After the addition is completed, the reaction solution is refluxed at 60-65°C for 8-12 hours. After the reaction is completed, the solution is filtered, rotary evaporated, dissolved, washed, dried, and filtered to obtain a hydrotalcite flame retardant material;

[0011] Step 3: pre-mix the polyamide resin, flame retardant fiber, and hydrotalcite flame retardant material, fully disperse them for 20-30 minutes, then add the toughening agent, plasticizer, antioxidant, and heat stabilizer and mix them evenly to obtain a mixture; the mixture is sequentially extruded and granulated, and injection molded to obtain a finished product.

[0012] More optimally, in step 1, the melt extrusion parameters are: temperature of 210-240°C, screw speed of 50-70 rpm / min; melt spinning parameters are: temperature of 250-270°C, winding speed of 550-650 m / min.

[0013] More optimally, in step 1, the amount of flame retardant added is 7-9 wt % of polyamide 6.

[0014] More optimally, the preparation process of the flame retardant is:

[0015] S1: Eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are uniformly mixed, and then azobisisobutyronitrile is added, and the mixture is stirred and reacted at 85-90° C. for 13-15 hours. After the reaction is completed, the mixture is purified by rotary evaporation to obtain a modified phosphaphenanthrene; the modified phosphaphenanthrene is dissolved in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; sodium hydride is dissolved in tetrahydrofuran to obtain a sodium hydride solution; under a nitrogen environment, the modified phosphaphenanthrene solution is added to the sodium hydride solution, and the mixture is refluxed at 65-70° C. for 12-14 hours. After the reaction is completed, the mixture is filtered to obtain a sodium alcohol nucleophilic solution;

[0016] S2: Under a nitrogen atmosphere, dissolving hexachlorocyclotriphosphazene in 1,2,4-trichlorobenzene, adding sulfamic acid and calcium sulfate dihydrate, and reacting at 200-220° C. for 4-5 hours. After the reaction is completed, cooling, precipitating, filtering, and washing to obtain a linear polyphosphazene; dissolving the linear polyphosphazene in tetrahydrofuran to obtain a linear polyphosphazene solution;

[0017] S3: slowly dropwise adding the sodium alcohol nucleophilic solution into the linear polyphosphazene solution, and reflux reacting at 65-70° C. for 12-14 hours. After the reaction is completed, the flame retardant is obtained by precipitation, dissolution, and vacuum drying.

[0018] More optimally, when preparing the modified phosphaphenanthrene solution, the reaction molar ratio of eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:(1.1-1.3); when preparing the sodium alcohol nucleophilic solution, the reaction molar ratio of the modified phosphaphenanthrene and sodium hydride is 1:(1.3-1.5); when preparing the linear polyphosphazene, the reaction mass ratio of hexachlorocyclotriphosphazene, aminosulfonic acid, and calcium sulfate dihydrate is (35-40):0.4:0.04; when preparing the flame retardant, the reaction mass ratio of the solute of the sodium alcohol nucleophilic solution and the linear polyphosphazene is (1.0-1.2):4.

[0019] More optimally, in step 2, the mixed solvent consists of ethylene glycol and deionized water in a volume ratio of (1.0-1.2):10; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dissolved in ethanol to obtain a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution.

[0020] More optimally, in step 2, when preparing the modified hydrotalcite material, the reaction mass ratio of the magnesium-aluminum hydrotalcite material and γ-aminopropyltriethoxysilane is 1:(0.03-0.04); when preparing the intermediate product, the reaction mass ratio of the modified hydrotalcite material, 4-hydroxybenzaldehyde, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:0.02:(0.04-0.05); when preparing the hydrotalcite flame retardant material, the reaction mass ratio of the intermediate product and cyanuric chloride is 1:(0.20-0.25).

[0021] More optimally, in step three, the contents of the components of the mixture are: in parts by mass, 100-120 parts of polyamide resin, 5-10 parts of flame retardant fiber, 10-15 parts of hydrotalcite flame retardant material, 5-10 parts of toughening agent, 8-15 parts of plasticizer, 0.5-0.7 parts of antioxidant, and 1.2-1.8 parts of heat stabilizer; wherein the toughening agent is a silicone rubber toughening agent, the plasticizer is dioctyl adipate, the antioxidant is a phosphite antioxidant, and the heat stabilizer is cuprous iodide.

[0022] More optimally, in step three, the extrusion granulation parameters are: temperature of 250-280°C, rotation speed of 400 rpm / min; injection molding parameters: temperature of 250-350°C.

[0023] Beneficial effects of the present invention:

[0024] The present invention is characterized by the following steps: in step 1, eugenol, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and sodium hydride are added to obtain a sodium alcohol nucleophilic solution. In this step, eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide undergo a hydrosilylation reaction to obtain a modified phosphaphenanthrene. Sodium hydride is then added to the modified phosphaphenanthrene to undergo an acid-base neutralization reaction, resulting in a sodium alcohol nucleophilic solution. Hexachlorocyclotriphosphazene, aminosulfonic acid, and calcium sulfate dihydrate are then added to obtain a linear polyphosphazene. This linear polyphosphazene is a highly functional elastomer and therefore exhibits excellent flexibility. Furthermore, because it contains multiple flame-retardant elements, such as nitrogen and phosphorus, it exhibits excellent synergistic flame-retardant properties. The sodium alcohol nucleophilic solution is then slowly added dropwise to the linear polyphosphazene solution, resulting in a flame retardant that exhibits both flame retardancy and flexibility. Therefore, polyamide 6 and flame retardant are fully mixed, melt extruded, pelletized and melt spun to obtain flame retardant fibers with good flame retardant properties and flexibility.

[0025] The present invention is characterized by the following steps: in step 2, a flame-retardant hydrotalcite material is prepared by adding a magnesium-aluminum hydrotalcite material, γ-aminopropyltriethoxysilane, 4-hydroxybenzaldehyde, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and cyanuric chloride. In this step, the magnesium-aluminum hydrotalcite material, which has a large number of surface hydroxyl groups, is modified using γ-aminopropyltriethoxysilane to introduce functional amino groups into the modified hydrotalcite material. 4-hydroxybenzaldehyde is then added to the modified hydrotalcite material to undergo a Schiff base reaction, forming a C=N bond. 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is then added to undergo a nucleophilic addition reaction, yielding an intermediate with various flame-retardant structures. Cyanuric chloride is then added to the magnesium-aluminum hydrotalcite material, or to the hydroxyl groups introduced by 4-hydroxybenzaldehyde, to undergo a substitution reaction, ultimately yielding the flame-retardant hydrotalcite material.

[0026] The present invention is characterized in that, in step three, the polyamide resin, flame retardant fiber, and hydrotalcite flame retardant material are pre-mixed, and then a toughening agent, a plasticizer, an antioxidant, and a heat stabilizer are added and mixed evenly to obtain a mixture; the mixture is sequentially subjected to extrusion granulation and injection molding to obtain a finished product. Pre-mixing the polyamide resin, flame retardant fiber, and hydrotalcite flame retardant material can effectively improve the dispersibility and mechanical properties of the flame retardant material. Specifically, the linear flame retardant fiber has a larger aspect ratio, while the layered hydrotalcite flame retardant material has a larger lamellar structure. During the mixing process, the fibers can be interspersed and entangled between the hydrotalcite lamellar layers, forming a physically entangled structure. This structure can prevent the agglomeration and stacking of the hydrotalcite lamellar layers, while also limiting the excessive orientation of the fibers, allowing the two to be better dispersed in the material. Moreover, the flame retardant fiber and the polyamide resin are both polyamide structures, so substances with the same structure can be dispersed with each other. Furthermore, when the material is subjected to external impact forces, the fibers bear the majority of the tensile stress, while the hydrotalcite flakes deflect cracks, dissipating more energy and thus improving the material's impact resistance. Furthermore, flame-retardant fibers and hydrotalcite flame-retardant materials exhibit a synergistic effect in flame retardancy. Flame-retardant fibers typically form an insulating layer on the material's surface, preventing the transfer of heat and oxygen. Hydrotalcite, on the other hand, decomposes upon heating, absorbing heat and releasing inert gases such as water and carbon dioxide, which dilute the concentration of combustible gases. The resulting metal oxide layer also acts as a barrier. The two work together to more effectively suppress combustion and enhance flame retardancy.

[0027] In summary, the finished product prepared by the present invention has good flame retardancy and impact resistance, and therefore has broad application prospects in the field of polymer material technology. DETAILED DESCRIPTION

[0028] The following will provide a clear and complete description of the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0029] Source of raw materials:

[0030] Polyamide 6, provided by Shanghai Huifei Chemical Co., Ltd., model NYLATRON GSMPA6; magnesium aluminum hydrotalcite material, provided by Hefei Anyuhe New Materials Technology Co., Ltd., model D213; polyamide resin, provided by Dongguan Yingxiang Plastic Raw Materials Co., Ltd., model TA124; silicone rubber toughening agent, provided by Dongguan Xingyuan Chemical Co., Ltd., model S-2001; phosphite antioxidant, provided by Anhui Jingzhicai New Materials Co., Ltd., model 168.

[0031] Example 1: Step 1: S1: Eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are uniformly mixed, and then azobisisobutyronitrile is added, and the mixture is stirred and reacted at 90° C. for 15 hours. After the reaction is completed, it is purified by rotary evaporation to obtain a modified phosphaphenanthrene; the modified phosphaphenanthrene is dissolved in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; sodium hydride is dissolved in tetrahydrofuran to obtain a sodium hydride solution; under a nitrogen environment, the modified phosphaphenanthrene solution is added to the sodium hydride solution, and the mixture is refluxed at 70° C. for 14 hours. After the reaction is completed, it is filtered to obtain a sodium alcohol nucleophilic solution; when preparing the modified phosphaphenanthrene solution, the reaction molar ratio of eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1.2; when preparing the sodium alcohol nucleophilic solution, the reaction molar ratio of modified phosphaphenanthrene and sodium hydride is 1:1.4;

[0032] S2: Under a nitrogen atmosphere, hexachlorocyclotriphosphazene is dissolved in 1,2,4-trichlorobenzene, and aminosulfonic acid and calcium sulfate dihydrate are added, and the mixture is reacted at 220°C for 5 hours. After the reaction, the mixture is cooled, precipitated, filtered, and washed to obtain a linear polyphosphazene. The linear polyphosphazene is dissolved in tetrahydrofuran to obtain a linear polyphosphazene solution. When preparing the linear polyphosphazene, the reaction mass ratio of hexachlorocyclotriphosphazene, aminosulfonic acid, and calcium sulfate dihydrate is 37:0.4:0.04.

[0033] S3: slowly adding the sodium alcohol nucleophilic solution dropwise to the linear polyphosphazene solution, reflux reacting at 70°C for 14 hours, and after the reaction is completed, precipitating, dissolving, and vacuum drying to obtain a flame retardant; fully mixing polyamide 6 and the flame retardant, and then melt extruding, pelletizing, and melt spinning to obtain a flame retardant fiber; when preparing the flame retardant, the reaction mass ratio of the solute of the sodium alcohol nucleophilic solution to the linear polyphosphazene is 1.1:4; the addition amount of the flame retardant is 8wt% of the polyamide 6; melt extrusion parameters: temperature of 240°C, screw speed of 70rpm / min; melt spinning parameters: temperature of 270°C, winding speed of 650m / min;

[0034] Step 2: Add magnesium aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to a mixed solvent, fully disperse them, adjust the pH to 9.2, stir and react at 70°C for 4 hours, and filter, wash, dry and grind to obtain a modified hydrotalcite material after the reaction is completed; dissolve 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in ethanol to obtain a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution; add the modified hydrotalcite material and 4-hydroxybenzaldehyde to ethanol, stir and react at 75°C for 5 hours, and then dropwise add 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide solution, continue to react for 8 hours, cool, filter, wash, and vacuum dry after the reaction to obtain an intermediate product; the mixed solvent consists of ethylene glycol and deionized water in a volume ratio of 1.1:10; when preparing the modified hydrotalcite material, the reaction mass ratio of the magnesium aluminum hydrotalcite material and γ-aminopropyltriethoxysilane is 1:0.035; when preparing the intermediate product, the reaction mass ratio of the modified hydrotalcite material, 4-hydroxybenzaldehyde, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:0.02:0.045;

[0035] Under a nitrogen environment, the intermediate product is dissolved in tetrahydrofuran, and triethylamine is added and stirred thoroughly to obtain a reaction solution; cyanuric chloride is dissolved in tetrahydrofuran to obtain a cyanuric chloride solution; the reaction solution is allowed to stand at 3°C ​​for 8 minutes, and the cyanuric chloride solution is added dropwise. After the addition is completed, the reaction is refluxed at 65°C for 12 hours. After the reaction is completed, the reaction is filtered, rotary evaporated, dissolved, washed, dried, and filtered to obtain a hydrotalcite flame retardant material; when preparing the hydrotalcite flame retardant material, the reaction mass ratio of the intermediate product to the cyanuric chloride is 1:0.23;

[0036] Step 3: Pre-mix 120 parts of polyamide resin, 10 parts of flame retardant fiber, and 15 parts of hydrotalcite flame retardant material, fully disperse them for 30 minutes, then add 10 parts of silicone rubber toughening agent, 15 parts of dioctyl adipate, 0.7 parts of phosphite antioxidant, and 1.8 parts of cuprous iodide and mix them evenly to obtain a mixture; the mixture is sequentially extruded granulated and injection molded to obtain a finished product; extrusion granulation parameters: temperature is 280°C, speed is 400rpm / min; injection molding parameters: temperature is 350°C.

[0037] Example 2: Step 1: S1: Eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are uniformly mixed, and then azobisisobutyronitrile is added, and the mixture is stirred and reacted at 87° C. for 14 hours. After the reaction is completed, it is purified by rotary evaporation to obtain a modified phosphaphenanthrene; the modified phosphaphenanthrene is dissolved in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; sodium hydride is dissolved in tetrahydrofuran to obtain a sodium hydride solution; under a nitrogen environment, the modified phosphaphenanthrene solution is added to the sodium hydride solution, and the mixture is refluxed at 67° C. for 13 hours. After the reaction is completed, it is filtered to obtain a sodium alcohol nucleophilic solution; when preparing the modified phosphaphenanthrene solution, the reaction molar ratio of eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1.2; when preparing the sodium alcohol nucleophilic solution, the reaction molar ratio of modified phosphaphenanthrene and sodium hydride is 1:1.4;

[0038] S2: Under a nitrogen atmosphere, hexachlorocyclotriphosphazene was dissolved in 1,2,4-trichlorobenzene, and aminosulfonic acid and calcium sulfate dihydrate were added, and the mixture was reacted at 210°C for 4.5 hours. After the reaction, the mixture was cooled, precipitated, filtered, and washed to obtain a linear polyphosphazene. The linear polyphosphazene was dissolved in tetrahydrofuran to obtain a linear polyphosphazene solution. When preparing the linear polyphosphazene, the reaction mass ratio of hexachlorocyclotriphosphazene, aminosulfonic acid, and calcium sulfate dihydrate was 37:0.4:0.04.

[0039] S3: slowly adding the sodium alcohol nucleophilic solution dropwise to the linear polyphosphazene solution, reflux reacting at 67°C for 13 hours, and after the reaction is completed, precipitating, dissolving, and vacuum drying to obtain a flame retardant; fully mixing polyamide 6 and the flame retardant, and then melt extruding, pelletizing, and melt spinning to obtain a flame retardant fiber; when preparing the flame retardant, the reaction mass ratio of the solute of the sodium alcohol nucleophilic solution to the linear polyphosphazene is 1.1:4; the addition amount of the flame retardant is 8wt% of the polyamide 6; melt extrusion parameters: temperature of 220°C, screw speed of 60rpm / min; melt spinning parameters: temperature of 260°C, winding speed of 600m / min;

[0040] Step 2: Add magnesium aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to a mixed solvent, fully disperse them, adjust the pH to 9.1, stir and react at 67°C for 3.5h, and filter, wash, dry and grind to obtain a modified hydrotalcite material after the reaction is completed; dissolve 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in ethanol to obtain a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution; add the modified hydrotalcite material and 4-hydroxybenzaldehyde to ethanol, stir and react at 73°C for 4.5h, and then add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide dropwise. The invention discloses a method for preparing a modified hydrotalcite material, wherein the reaction mass ratio of the magnesium aluminum hydrotalcite material and γ-aminopropyltriethoxysilane is 1:0.035; and the reaction mass ratio of the modified hydrotalcite material, 4-hydroxybenzaldehyde and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:0.02:0.045.

[0041] Under a nitrogen environment, the intermediate product is dissolved in tetrahydrofuran, and triethylamine is added and stirred thoroughly to obtain a reaction solution; cyanuric chloride is dissolved in tetrahydrofuran to obtain a cyanuric chloride solution; the reaction solution is allowed to stand at 2°C for 6 minutes, and the cyanuric chloride solution is added dropwise. After the addition is completed, the reaction solution is refluxed at 62°C for 10 hours. After the reaction is completed, the solution is filtered, rotary evaporated, dissolved, washed, dried, and filtered to obtain a hydrotalcite flame retardant material; when preparing the hydrotalcite flame retardant material, the reaction mass ratio of the intermediate product to the cyanuric chloride is 1:0.23;

[0042] Step 3: Pre-mix 120 parts of polyamide resin, 10 parts of flame retardant fiber, and 15 parts of hydrotalcite flame retardant material, fully disperse them for 25 minutes, then add 10 parts of silicone rubber toughening agent, 15 parts of dioctyl adipate, 0.7 parts of phosphite antioxidant, and 1.8 parts of cuprous iodide and mix them evenly to obtain a mixture; the mixture is sequentially extruded granulated and injection molded to obtain a finished product; extrusion granulation parameters: temperature is 270°C, speed is 400rpm / min; injection molding parameters: temperature is 300°C.

[0043] Example 3: Step 1: S1: Eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are uniformly mixed, and then azobisisobutyronitrile is added, and the mixture is stirred and reacted at 85° C. for 13 hours. After the reaction is completed, it is purified by rotary evaporation to obtain a modified phosphaphenanthrene; the modified phosphaphenanthrene is dissolved in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; sodium hydride is dissolved in tetrahydrofuran to obtain a sodium hydride solution; under a nitrogen environment, the modified phosphaphenanthrene solution is added to the sodium hydride solution, and the mixture is refluxed at 65° C. for 12 hours. After the reaction is completed, it is filtered to obtain a sodium alcohol nucleophilic solution; when preparing the modified phosphaphenanthrene solution, the reaction molar ratio of eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1.2; when preparing the sodium alcohol nucleophilic solution, the reaction molar ratio of modified phosphaphenanthrene and sodium hydride is 1:1.4;

[0044] S2: Under a nitrogen atmosphere, hexachlorocyclotriphosphazene is dissolved in 1,2,4-trichlorobenzene, and aminosulfonic acid and calcium sulfate dihydrate are added, and the mixture is reacted at 200°C for 4 hours. After the reaction is completed, the mixture is cooled, precipitated, filtered, and washed to obtain a linear polyphosphazene. The linear polyphosphazene is dissolved in tetrahydrofuran to obtain a linear polyphosphazene solution. When preparing the linear polyphosphazene, the reaction mass ratio of hexachlorocyclotriphosphazene, aminosulfonic acid, and calcium sulfate dihydrate is 37:0.4:0.04.

[0045] S3: slowly adding the sodium alcohol nucleophilic solution dropwise to the linear polyphosphazene solution, reflux reacting at 65°C for 12 hours, and after the reaction is completed, precipitating, dissolving, and vacuum drying to obtain a flame retardant; fully mixing polyamide 6 and the flame retardant, and then melt extruding, pelletizing, and melt spinning to obtain a flame retardant fiber; when preparing the flame retardant, the reaction mass ratio of the solute of the sodium alcohol nucleophilic solution to the linear polyphosphazene is 1.1:4; the addition amount of the flame retardant is 8wt% of the polyamide 6; melt extrusion parameters: temperature of 210°C, screw speed of 50rpm / min; melt spinning parameters: temperature of 250°C, winding speed of 550m / min;

[0046] Step 2: Add magnesium aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to a mixed solvent, fully disperse them, adjust the pH to 9.0, stir and react at 65°C for 3 hours, and filter, wash, dry and grind to obtain a modified hydrotalcite material; dissolve 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in ethanol to obtain a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution; add the modified hydrotalcite material and 4-hydroxybenzaldehyde to ethanol, stir and react at 70°C for 4 hours, and then dropwise add 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide solution, continue to react for 5 hours, cool, filter, wash, and vacuum dry after the reaction to obtain an intermediate product; the mixed solvent consists of ethylene glycol and deionized water in a volume ratio of 1.1:10; when preparing the modified hydrotalcite material, the reaction mass ratio of the magnesium aluminum hydrotalcite material and γ-aminopropyltriethoxysilane is 1:0.035; when preparing the intermediate product, the reaction mass ratio of the modified hydrotalcite material, 4-hydroxybenzaldehyde, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:0.02:0.045;

[0047] Under a nitrogen environment, the intermediate product is dissolved in tetrahydrofuran, and triethylamine is added and stirred thoroughly to obtain a reaction liquid; cyanuric chloride is dissolved in tetrahydrofuran to obtain a cyanuric chloride solution; the reaction liquid is allowed to stand at 0°C for 5 minutes, and the cyanuric chloride solution is added dropwise. After the addition is completed, the reaction is refluxed at 60°C for 8 hours. After the reaction is completed, the reaction is filtered, rotary evaporated, dissolved, washed, dried, and filtered to obtain a hydrotalcite flame retardant material; when preparing the hydrotalcite flame retardant material, the reaction mass ratio of the intermediate product to the cyanuric chloride is 1:0.23;

[0048] Step 3: Pre-mix 120 parts of polyamide resin, 10 parts of flame retardant fiber, and 15 parts of hydrotalcite flame retardant material, fully disperse them for 20 minutes, then add 10 parts of silicone rubber toughening agent, 15 parts of dioctyl adipate, 0.7 parts of phosphite antioxidant, and 1.8 parts of cuprous iodide and mix them evenly to obtain a mixture; the mixture is sequentially extruded granulated and injection molded to obtain a finished product; extrusion granulation parameters: temperature is 250°C, speed is 400rpm / min; injection molding parameters: temperature is 250°C.

[0049] Comparative Example 1: The flame retardant fiber is removed, and the rest is the same as Example 1, and the specific steps are as follows: Step 1: Add magnesium aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to a mixed solvent, fully disperse them evenly, adjust the pH to 9.2, and stir and react at 70°C for 4 hours. After the reaction, filter, wash, dry, and grind to obtain a modified hydrotalcite material; dissolve 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in ethanol to obtain a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution; add the modified hydrotalcite material and 4-hydroxybenzaldehyde to ethanol, stir and react at 75°C. The reaction mixture was stirred for 5 hours, and then a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution was added dropwise, and the reaction was continued for 8 hours. After the reaction, the mixture was cooled, filtered, washed, and vacuum-dried to obtain an intermediate product. The mixed solvent consisted of ethylene glycol and deionized water in a volume ratio of 1.1:10. When preparing the modified hydrotalcite material, the reaction mass ratio of the magnesium-aluminum hydrotalcite material and γ-aminopropyltriethoxysilane was 1:0.035. When preparing the intermediate product, the reaction mass ratio of the modified hydrotalcite material, 4-hydroxybenzaldehyde, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was 1:0.02:0.045.

[0050] Under a nitrogen environment, the intermediate product is dissolved in tetrahydrofuran, and triethylamine is added and stirred thoroughly to obtain a reaction solution; cyanuric chloride is dissolved in tetrahydrofuran to obtain a cyanuric chloride solution; the reaction solution is allowed to stand at 3°C ​​for 8 minutes, and the cyanuric chloride solution is added dropwise. After the addition is completed, the reaction is refluxed at 65°C for 12 hours. After the reaction is completed, the reaction is filtered, rotary evaporated, dissolved, washed, dried, and filtered to obtain a hydrotalcite flame retardant material; when preparing the hydrotalcite flame retardant material, the reaction mass ratio of the intermediate product to the cyanuric chloride is 1:0.23;

[0051] Step 2: Pre-mix 120 parts of polyamide resin and 15 parts of hydrotalcite flame retardant material, fully disperse them for 30 minutes, then add 10 parts of silicone rubber toughening agent, 15 parts of dioctyl adipate, 0.7 parts of phosphite antioxidant, and 1.8 parts of cuprous iodide and mix them evenly to obtain a mixture; the mixture is sequentially subjected to extrusion granulation and injection molding to obtain a finished product; extrusion granulation parameters: temperature is 280°C, speed is 400 rpm / min; injection molding parameters: temperature is 350°C.

[0052] Comparative Example 2: The hydrotalcite flame retardant material is removed, and the rest is the same as Example 1, and the specific steps are as follows: Step 1: S1: Eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are mixed evenly, and then azobisisobutyronitrile is added, and the mixture is stirred at 90°C for 15 hours. After the reaction is completed, it is purified by rotary evaporation to obtain modified phosphaphenanthrene; the modified phosphaphenanthrene is dissolved in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; sodium hydride is dissolved in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; to obtain a sodium hydride solution; under a nitrogen environment, the modified phosphaphenanthrene solution was added to the sodium hydride solution, and the mixture was refluxed at 70°C for 14 hours. After the reaction was completed, the mixture was filtered to obtain a sodium alcohol nucleophilic solution; when preparing the modified phosphaphenanthrene solution, the reaction molar ratio of eugenol to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was 1:1.2; when preparing the sodium alcohol nucleophilic solution, the reaction molar ratio of the modified phosphaphenanthrene to sodium hydride was 1:1.4;

[0053] S2: Under a nitrogen atmosphere, hexachlorocyclotriphosphazene is dissolved in 1,2,4-trichlorobenzene, and aminosulfonic acid and calcium sulfate dihydrate are added, and the mixture is reacted at 220°C for 5 hours. After the reaction, the mixture is cooled, precipitated, filtered, and washed to obtain a linear polyphosphazene. The linear polyphosphazene is dissolved in tetrahydrofuran to obtain a linear polyphosphazene solution. When preparing the linear polyphosphazene, the reaction mass ratio of hexachlorocyclotriphosphazene, aminosulfonic acid, and calcium sulfate dihydrate is 37:0.4:0.04.

[0054] S3: slowly adding the sodium alcohol nucleophilic solution dropwise to the linear polyphosphazene solution, reflux reacting at 70°C for 14 hours, and after the reaction is completed, precipitating, dissolving, and vacuum drying to obtain a flame retardant; fully mixing polyamide 6 and the flame retardant, and then melt extruding, pelletizing, and melt spinning to obtain a flame retardant fiber; when preparing the flame retardant, the reaction mass ratio of the solute of the sodium alcohol nucleophilic solution to the linear polyphosphazene is 1.1:4; the addition amount of the flame retardant is 8wt% of the polyamide 6; melt extrusion parameters: temperature of 240°C, screw speed of 70rpm / min; melt spinning parameters: temperature of 270°C, winding speed of 650m / min;

[0055] Step 2: Pre-mix 120 parts of polyamide resin and 10 parts of flame retardant fiber, fully disperse them for 30 minutes, then add 10 parts of silicone rubber toughening agent, 15 parts of dioctyl adipate, 0.7 parts of phosphite antioxidant, and 1.8 parts of cuprous iodide and mix them evenly to obtain a mixture; the mixture is sequentially subjected to extrusion granulation and injection molding to obtain a finished product; extrusion granulation parameters: temperature is 280°C, speed is 400 rpm / min; injection molding parameters: temperature is 350°C.

[0056] Comparative Example 3: The flame retardant fiber and the hydrotalcite flame retardant material were removed, and the rest were the same as in Example 1, and the specific steps were as follows: Step 1: 120 parts of polyamide resin, 10 parts of silicone rubber toughening agent, 15 parts of dioctyl adipate, 0.7 parts of phosphite antioxidant, and 1.8 parts of cuprous iodide were mixed uniformly to obtain a mixture; the mixture was sequentially subjected to extrusion granulation and injection molding to obtain a finished product; extrusion granulation parameters: temperature: 280°C, speed: 400 rpm / min; injection molding parameters: temperature: 350°C.

[0057] Detection test:

[0058] Flame retardant performance test: Referring to GB / T 2406.2-2009 "Determination of combustion behavior of plastics by oxygen index method Part 2: Room temperature test", the finished product prepared by the present invention was used as a sample with a sample size of 90×10×4 mm, and the oxygen index value was recorded.

[0059] Impact resistance test: Referring to GB / T 1843-2020 “Determination of Izod Impact Strength of Plastics”, the finished product prepared in the present invention was used as a sample with a sample size of 80×10×4 mm, and the impact strength was recorded.

[0060] Mechanical properties test: Referring to GB / T 1040.2-2006 "Determination of tensile properties of plastics - Part 2: Test conditions for molded and extruded plastics", the finished product prepared in this invention was used as a specimen with a specimen size of 170 × 20 × 4 mm, and the tensile strength was recorded. The results are shown in the following table:

[0061] Oxygen index / % <![CDATA[Impact strength / (KJ / m 2 )]]> <![CDATA[Tensile strength / MPa > Example 1 31 22.4 67 Example 2 31 21.8 66 Example 3 30 21.2 65 Comparative Example 1 27 18.3 57 Comparative Example 2 24 19.5 61 Comparative Example 3 21 17.1 53

[0062] Conclusion: The dosage of Examples 1 to 3 remains unchanged, and only some reaction parameters are modified. From the experimental data, it can be seen that there is no significant fluctuation in the performance of the samples.

[0063] Comparative Example 1: The flame retardant fiber is removed, and the rest is the same as Example 1. From the experimental data, it can be seen that compared with Example 1, the oxygen index is reduced by 27%, and the impact strength is reduced by 18.3KJ / m 2 The tensile strength is reduced to 57MPa. The reason is analyzed as follows: the flame retardant fiber contains a variety of flame retardant elements and functional elastomer linear polyphosphazene, so it has good flame retardancy and flexibility. Therefore, after adding it to the sample in fiber form, it can effectively improve the oxygen index, impact strength and tensile strength of the sample. Therefore, removing the flame retardant fiber will reduce the performance.

[0064] Comparative Example 2: The hydrotalcite flame retardant material was removed, and the rest was the same as Example 1. From the experimental data, it can be seen that compared with Example 1, the oxygen index was reduced by 24%, and the impact strength was reduced by 19.5KJ / m 2, the tensile strength is reduced to 61MPa. The reasons are analyzed as follows: hydrotalcite flame retardant material contains a variety of flame retardant structures, so the oxygen index is reduced after removing it; in addition, due to the layered structure characteristics of hydrotalcite flame retardant material, it can effectively improve the impact strength and tensile strength of the sample, so removing the hydrotalcite flame retardant material will reduce the performance.

[0065] Comparative Example 3: The flame retardant fiber and hydrotalcite flame retardant material were removed, and the rest was the same as Example 1. From the experimental data, it can be seen that compared with Example 1, the oxygen index was reduced by 21%, and the impact strength was reduced by 17.1KJ / m 2 , the tensile strength is reduced to 53MPa. The reason is analyzed as follows: According to Comparative Examples 1 and 2, the addition of flame retardant fibers and hydrotalcite flame retardant materials can effectively improve the oxygen index, impact strength and tensile strength of the sample. Therefore, the performance will be significantly reduced after removing the two materials.

[0066] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "include," "comprise," or any other variations thereof are intended to encompass non-exclusive inclusion, such that a process, method, article, or apparatus comprising a series of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0067] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing an impact-resistant flame-retardant polyamide cable tie, characterized in that: The following steps are involved: Step 1: fully mixing polyamide 6 and flame retardant, and then melt-extruding, pelletizing, and melt-spinning to obtain flame-retardant fiber; Step 2: adding magnesium aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to a mixed solvent, fully dispersing them evenly, adjusting the pH to 9.0-9.2, stirring and reacting at 65-70° C. for 3-4 hours, and filtering, washing, drying, and grinding after the reaction to obtain a modified hydrotalcite material; adding the modified hydrotalcite material and 4-hydroxybenzaldehyde to ethanol, stirring and reacting at 70-75° C. for 4-5 hours, and then adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution dropwise, continuing the reaction for 5-8 hours, and cooling, filtering, washing, and vacuum drying after the reaction to obtain an intermediate product; Under a nitrogen environment, the intermediate product is dissolved in tetrahydrofuran, and triethylamine is added and stirred thoroughly to obtain a reaction solution; cyanuric chloride is dissolved in tetrahydrofuran to obtain a cyanuric chloride solution; the reaction solution is allowed to stand at 0-3°C for 5-8 minutes, and the cyanuric chloride solution is added dropwise. After the addition is completed, the reaction solution is refluxed at 60-65°C for 8-12 hours. After the reaction is completed, the solution is filtered, rotary evaporated, dissolved, washed, dried, and filtered to obtain a hydrotalcite flame retardant material; Step 3: pre-mixing the polyamide resin, flame retardant fiber, and hydrotalcite flame retardant material, fully dispersing them for 20-30 minutes, then adding a toughening agent, a plasticizer, an antioxidant, and a heat stabilizer and mixing them evenly to obtain a mixture; extruding the mixture into pellets and injection molding them in sequence to obtain a finished product; the contents of the components of the mixture are as follows: by mass: 100-120 parts of polyamide resin, 5-10 parts of flame retardant fiber, 10-15 parts of hydrotalcite flame retardant material, 5-10 parts of toughening agent, 8-15 parts of plasticizer, 0.5-0.7 parts of antioxidant, and 1.2-1.8 parts of heat stabilizer; wherein the toughening agent is a silicone rubber toughening agent, the plasticizer is dioctyl adipate, the antioxidant is a phosphite antioxidant, and the heat stabilizer is cuprous iodide; The preparation process of flame retardant is: S1: Eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are mixed evenly, and then azobisisobutyronitrile is added. The mixture is stirred at 85-90°C for 13-15 hours. After the reaction is completed, the mixture is purified by rotary evaporation to obtain modified phosphaphenanthrene; Dissolving the modified phosphaphenanthrene in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; dissolving sodium hydride in tetrahydrofuran to obtain a sodium hydride solution; adding the modified phosphaphenanthrene solution to the sodium hydride solution under a nitrogen atmosphere, reflux reacting at 65-70° C. for 12-14 hours, and filtering after the reaction to obtain a sodium alcohol nucleophilic solution; S2: Under a nitrogen atmosphere, dissolving hexachlorocyclotriphosphazene in 1,2,4-trichlorobenzene, adding sulfamic acid and calcium sulfate dihydrate, and reacting at 200-220° C. for 4-5 hours. After the reaction is completed, cooling, precipitating, filtering, and washing to obtain a linear polyphosphazene; dissolving the linear polyphosphazene in tetrahydrofuran to obtain a linear polyphosphazene solution; S3: slowly dropwise adding the sodium alcohol nucleophilic solution into the linear polyphosphazene solution, and reflux reacting at 65-70° C. for 12-14 hours. After the reaction is completed, the flame retardant is obtained by precipitation, dissolution, and vacuum drying.

2. The method for preparing an impact-resistant flame-retardant polyamide cable tie according to claim 1, characterized in that: In step 1, the melt extrusion parameters are: temperature of 210-240° C., screw speed of 50-70 rpm; the melt spinning parameters are: temperature of 250-270° C., winding speed of 550-650 m / min.

3. The method for preparing an impact-resistant flame-retardant polyamide cable tie according to claim 1, characterized in that: In step 1, the amount of flame retardant added is 7-9 wt % of polyamide 6.

4. The method for preparing an impact-resistant flame-retardant polyamide cable tie according to claim 1, wherein: When preparing the modified phosphaphenanthrene solution, the reaction molar ratio of eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:(1.1-1.3); when preparing the sodium alcohol nucleophilic solution, the reaction molar ratio of the modified phosphaphenanthrene and sodium hydride is 1:(1.3-1.5); when preparing the linear polyphosphazene, the reaction mass ratio of hexachlorocyclotriphosphazene, aminosulfonic acid, and calcium sulfate dihydrate is (35-40):0.4:0.04; when preparing the flame retardant, the reaction mass ratio of the solute of the sodium alcohol nucleophilic solution and the linear polyphosphazene is (1.0-1.2):

4.

5. The method for preparing an impact-resistant flame-retardant polyamide cable tie according to claim 1, characterized in that: In step 2, the mixed solvent consists of ethylene glycol and deionized water in a volume ratio of (1.0-1.2):10; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dissolved in ethanol to obtain a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution.

6. The method for preparing an impact-resistant flame-retardant polyamide cable tie according to claim 1, characterized in that: In step 2, when preparing the modified hydrotalcite material, the reaction mass ratio of the magnesium-aluminum hydrotalcite material and γ-aminopropyltriethoxysilane is 1:(0.03-0.04); when preparing the intermediate product, the reaction mass ratio of the modified hydrotalcite material, 4-hydroxybenzaldehyde, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:0.02:(0.04-0.05); when preparing the hydrotalcite flame retardant material, the reaction mass ratio of the intermediate product and cyanuric chloride is 1:(0.20-0.25).

7. The method for preparing an impact-resistant flame-retardant polyamide cable tie according to claim 1, characterized in that: In step 3, the extrusion granulation parameters are: temperature of 250-280°C, rotation speed of 400 rpm; injection molding parameters: temperature of 250-350°C.