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

Abstract

The invention relates to the technical field of high polymer materials, in particular to an impact-resistant flame-retardant polyamide cable tie and a preparation method thereof. The preparation method comprises the following steps: fully and uniformly mixing polyamide 6 and a flame retardant, and carrying out melt extrusion, pelletizing and melt spinning to obtain the flame-retardant fiber. The preparation method comprises the following steps: adding a magnesium-aluminum hydrotalcite material, gamma-aminopropyltriethoxysilane, 4-hydroxybenzaldehyde, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and cyanuric chloride to prepare a hydrotalcite flame-retardant material, and further adding the magnesium-aluminum hydrotalcite material, gamma-aminopropyltriethoxysilane, 4-hydroxybenzaldehyde, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and cyanuric chloride to prepare the hydrotalcite flame-retardant material. The preparation method comprises the following steps: pre-mixing polyamide resin, flame-retardant fibers and a hydrotalcite flame-retardant material, adding a flexibilizer, a plasticizer, an antioxidant and a heat stabilizer, and uniformly mixing to obtain a mixture; and sequentially carrying out extrusion granulation and injection molding on the mixed material to obtain a finished product. The finished product prepared by the invention has good flame retardant property and impact resistance, thereby having wide application prospects in the technical field of high polymer materials.

Description

Technical Field

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

[0002] In many fields of modern industry and life, although polyamide cable ties seem ordinary, they play an irreplaceable and important role, demonstrating various modern values. Polyamide cable ties have good chemical corrosion resistance and heat resistance. In industries such as chemical engineering and food processing, the production environment is often relatively complex, with various chemical substances and relatively high temperatures. Polyamide cable ties can resist the erosion of a variety of chemical reagents, maintain stable performance within a certain temperature range, and will not age or be damaged quickly due to contact with chemical substances or high temperatures, thus ensuring the long-term effectiveness of binding and reducing maintenance costs. In addition, the ease of use of polyamide cable ties is also one of their important values. Polyamide cable ties are easy to operate. One only needs to pass the cable tie through the item to be tied and then tighten the lock, without the need for complex tools and techniques. This ease of use enables it to be quickly applied in various situations, improving work efficiency. Whether on the large-scale production lines in factories or in daily household repairs, polyamide cable ties can easily handle the binding tasks.

[0003] However, during transportation and use, if the impact resistance of the polyamide cable ties for bundling goods is insufficient, they are extremely prone to breakage. This will cause the items they bind to scatter, which may not only damage the items but also lead to safety accidents. On industrial production lines, operations such as the vibration of mechanical equipment and the installation and disassembly of components will also impact the cable ties. Moreover, in some specific fields, such as the field of electronic and electrical appliances, electrical equipment generates heat during operation. If a short circuit or other faults occur, it may trigger a fire. As a commonly used tool for binding wires and cables, if polyamide cable ties do not have good flame retardant performance, once they encounter fire, they will burn rapidly, thereby fueling the spread of the fire and aggravating the fire hazard.

[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 purpose of the present invention is to provide an impact-resistant and flame-retardant polyamide cable tie and a preparation method thereof to solve the problems in the prior art.

[0006] To solve the above technical problems, the present invention provides the following technical solutions:

[0007] A preparation method of an impact-resistant and flame-retardant polyamide cable tie, comprising the following steps:

[0008] Step 1: Thoroughly mix polyamide 6 and the flame retardant evenly, then conduct melt extrusion, pelletizing, and melt spinning to obtain flame-retardant fibers;

[0009] Step 2: Add the magnesium-aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to the mixed solvent, disperse them evenly, adjust the pH to 9.0 - 9.2, stir and react at 65 - 70 °C for 3 - 4 h. After the reaction, conduct suction filtration, washing, drying, and grinding to obtain the modified hydrotalcite material; Add the modified hydrotalcite material and 4-hydroxybenzaldehyde to ethanol, stir and react at 70 - 75 °C for 4 - 5 h, then dropwise add the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution and continue to react for 5 - 8 h. After the reaction, conduct cooling, filtration, washing, and vacuum drying to obtain the intermediate product;

[0010] Under a nitrogen atmosphere, dissolve the intermediate product in tetrahydrofuran, then add triethylamine and stir thoroughly to obtain the reaction solution; Dissolve cyanuric chloride in tetrahydrofuran to obtain the cyanuric chloride solution; Let the reaction solution stand at 0 - 3 °C for 5 - 8 min, then dropwise add the cyanuric chloride solution. After the addition, reflux and react at 60 - 65 °C for 8 - 12 h. After the reaction, conduct filtration, rotary evaporation, dissolution, washing, drying, and filtration to obtain the hydrotalcite flame retardant material;

[0011] Step 3: Pre-mix the polyamide resin, flame-retardant fibers, and hydrotalcite flame retardant material, disperse them thoroughly for 20 - 30 min, then add the toughening agent, plasticizer, antioxidant, and heat stabilizer and mix evenly to obtain the mixed material; Subject the mixed material to extrusion granulation and injection molding in sequence to obtain the finished product.

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

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

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

[0015] S1: Thoroughly mix eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, then add azobisisobutyronitrile and stir and react at 85 - 90 °C for 13 - 15 h. After the reaction, conduct rotary evaporation and purification to obtain the modified phosphaphenanthrene; Dissolve the modified phosphaphenanthrene in tetrahydrofuran to obtain the modified phosphaphenanthrene solution; Dissolve sodium hydride in tetrahydrofuran to obtain the sodium hydride solution; Under a nitrogen atmosphere, add the modified phosphaphenanthrene solution to the sodium hydride solution and reflux and react at 65 - 70 °C for 12 - 14 h. After the reaction, conduct filtration to obtain the sodium alcohol nucleophilic solution;

[0016] S2: Under a nitrogen atmosphere, dissolve hexachlorocyclotriphosphazene in 1,2,4-trichlorobenzene, then add sulfamic acid and calcium sulfate dihydrate, and react at 200 - 220 °C for 4 - 5 h. After the reaction is completed, cool, precipitate, filter, and wash to obtain linear polyphosphazene; dissolve the linear polyphosphazene in tetrahydrofuran to obtain a linear polyphosphazene solution;

[0017] S3: Slowly drop the sodium alcohol nucleophilic solution into the linear polyphosphazene solution, and reflux and react at 65 - 70 °C for 12 - 14 h. After the reaction is completed, precipitate, dissolve, and vacuum dry to obtain the flame retardant.

[0018] More preferably, when preparing the modified phosphaphenanthrene solution, the reaction molar ratio of eugenol to 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 to sodium hydride is 1:(1.3 - 1.5); when preparing the linear polyphosphazene, the reaction mass ratio of hexachlorocyclotriphosphazene, sulfamic 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 to the linear polyphosphazene is (1.0 - 1.2):4.

[0019] More preferably, in step two, the mixed solvent consists of ethylene glycol and deionized water, and the volume ratio is (1.0 - 1.2):10; 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.

[0020] More preferably, in step two, when preparing the modified hydrotalcite material, the reaction mass ratio of the magnesium-aluminum hydrotalcite material to 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 to cyanuric chloride is 1:(0.20 - 0.25).

[0021] More preferably, in step three, the contents of each component in the mixture are: in terms of mass parts, 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 part of antioxidant, 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] Preferably, in step three, the extrusion granulation parameters are as follows: the temperature is 250 - 280 °C, and the rotation speed is 400 rpm / min; the injection molding parameters are as follows: the temperature is 250 - 350 °C.

[0023] Advantages of the present invention:

[0024] The present invention is characterized in that in step one, by adding eugenol, 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide, and sodium hydride, a sodium alcohol nucleophilic solution is obtained. In this step, eugenol and 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide undergo a hydrosilylation reaction to obtain a modified phosphaphenanthrene; then, by adding sodium hydride and the modified phosphaphenanthrene, an acid - base neutralization reaction occurs to obtain a sodium alcohol nucleophilic solution. Then, by adding hexachlorocyclotriphosphazene, sulfamic acid, and calcium sulfate dihydrate, a linear polyphosphazene is obtained. And this linear polyphosphazene is a good functional elastomer, so it has good flexibility; in addition, since this material contains multiple flame - retardant elements such as nitrogen and phosphorus, it has excellent synergistic flame - retardant performance. Therefore, when the sodium alcohol nucleophilic solution is slowly dropped into the linear polyphosphazene solution, the resulting flame retardant has both flame retardancy and flexibility. Therefore, when polyamide 6 and the flame retardant are fully mixed evenly, and through melt extrusion, pelletizing, and melt spinning, the obtained flame - retardant fiber has good flame - retardant performance and flexibility.

[0025] The present invention is characterized in that in step two, by adding a magnesium - aluminum hydrotalcite material, γ - aminopropyltriethoxysilane, 4 - hydroxybenzaldehyde, 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide, and cyanuric chloride, a hydrotalcite - based flame - retardant material is prepared. In this step, first, γ - aminopropyltriethoxysilane is used to modify the magnesium - aluminum hydrotalcite material with a large number of hydroxyl groups on the surface to introduce a modified hydrotalcite material with functional amino groups. Then, 4 - hydroxybenzaldehyde is added and a Schiff base reaction occurs with the modified hydrotalcite material to obtain a C=N bond; then, 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide is added to undergo a nucleophilic addition reaction to obtain an intermediate with multiple flame - retardant structures. Finally, cyanuric chloride is added and a substitution reaction occurs with the hydroxyl groups in the magnesium - aluminum hydrotalcite material or the hydroxyl groups introduced by adding 4 - hydroxybenzaldehyde, and finally, a hydrotalcite - based flame - retardant material is obtained.

[0026] The characteristics of the present invention are as follows. In step three, 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 mixed material. The mixed material is successively subjected to extrusion granulation and injection molding to obtain a finished product. Among them, 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 large aspect ratio, while the layered hydrotalcite flame retardant material has a large lamellar structure. During the mixing process, the fibers can interpenetrate and wind between the lamellae of the hydrotalcite, forming a physically entangled structure. This structure can prevent the agglomeration and stacking of the hydrotalcite lamellae, and at the same time limit the excessive orientation of the fibers, enabling the two to disperse better in the material. Moreover, both the flame retardant fiber and the polyamide resin have a polyamide structure, so substances with the same structure can disperse each other. In addition, when the material is subjected to impact external force, the fibers can bear most of the tensile stress, and the hydrotalcite lamellae can deflect cracks and consume more energy, thereby improving the impact resistance of the material. Furthermore, there is also a synergistic effect between the flame retardant fiber and the hydrotalcite flame retardant material in terms of flame retardancy. The flame retardant fiber usually forms a heat insulation layer on the surface of the material to prevent the transfer of heat and oxygen. When the hydrotalcite flame retardant material is heated, it decomposes endothermically, releases inert gases such as water and carbon dioxide, dilutes the concentration of combustible gases, and at the same time the formed metal oxide layer can also play a barrier role. The two cooperate with each other to more effectively inhibit the combustion of the material and improve the flame retardancy efficiency.

[0027] In summary, the finished product prepared by the present invention has good flame retardancy and impact resistance, so it has broad application prospects in the field of polymer material technology. Detailed implementation mode

[0028] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0029] Source of raw materials:

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

[0031] Example 1: Step 1: S1: Mix eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide evenly, then add azobisisobutyronitrile, and stir and react at 90 °C for 15 h. After the reaction is completed, purify by rotary evaporation to obtain modified phosphaphenanthrene; dissolve the modified phosphaphenanthrene in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; dissolve sodium hydride in tetrahydrofuran to obtain a sodium hydride solution; in a nitrogen environment, add the modified phosphaphenanthrene solution to the sodium hydride solution, and reflux and react at 70 °C for 14 h. After the reaction is completed, filter 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 is 1:1.2; when preparing the sodium alcohol nucleophilic solution, the reaction molar ratio of modified phosphaphenanthrene to sodium hydride is 1:1.4;

[0032] S2: In a nitrogen environment, dissolve hexachlorocyclotriphosphazene in 1,2,4-trichlorobenzene, then add sulfamic acid and calcium sulfate dihydrate, and react at 220 °C for 5 h. After the reaction is completed, cool, precipitate, filter, and wash to obtain linear polyphosphazene; dissolve the linear polyphosphazene in tetrahydrofuran to obtain a linear polyphosphazene solution; when preparing the linear polyphosphazene, the reaction mass ratio of hexachlorocyclotriphosphazene, sulfamic acid, and calcium sulfate dihydrate is 37:0.4:0.04;

[0033] S3: Slowly drop the sodium alcohol nucleophilic solution into the linear polyphosphazene solution, and reflux and react at 70 °C for 14 h. After the reaction is completed, precipitate, dissolve, and vacuum dry to obtain a flame retardant; fully mix polyamide 6 and the flame retardant evenly, and then melt extrude, pelletize, and melt spin to obtain flame retardant fibers; 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 8 wt% of polyamide 6; Melt extrusion parameters: temperature is 240 °C, screw speed is 70 rpm / min; Melt spinning parameters: temperature is 270 °C, winding speed is 650 m / min;

[0034] Step 2: Add the magnesium-aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to the mixed solvent, disperse them evenly, adjust the pH to 9.2, stir and react at 70 °C for 4 h. After the reaction, filter, wash, dry, and grind to obtain the 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 for 5 h, then dropwise add the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution and continue to react for 8 h. After the reaction, cool, filter, wash, and vacuum dry to obtain the intermediate product; the mixed solvent is composed of ethylene glycol and deionized water with a volume ratio of 1.1:10; when preparing the modified hydrotalcite material, the reaction mass ratio of the magnesium-aluminum hydrotalcite material to 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 atmosphere, dissolve the intermediate product in tetrahydrofuran, then add triethylamine and stir well to obtain a reaction solution; dissolve cyanuric chloride in tetrahydrofuran to obtain a cyanuric chloride solution; let the reaction solution stand at 3 °C for 8 min, then dropwise add the cyanuric chloride solution. After the addition, reflux and react at 65 °C for 12 h. After the reaction, filter, rotary evaporate, dissolve, wash, dry, and filter to obtain the hydrotalcite flame retardant material; when preparing the hydrotalcite flame retardant material, the reaction mass ratio of the intermediate product to 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 the hydrotalcite flame retardant material, disperse them evenly for 30 min, then add 10 parts of silicone rubber toughening agent, 15 parts of dioctyl adipate, 0.7 part of phosphite antioxidant, and 1.8 parts of cuprous iodide and mix well to obtain a mixed material; perform extrusion granulation and injection molding on the mixed material in sequence to obtain the finished product; Extrusion granulation parameters: temperature is 280 °C, rotation speed is 400 rpm / min; Injection molding parameters: temperature is 350 °C.

[0037] Example 2: Step 1: S1: Mix eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide evenly, then add azobisisobutyronitrile, and stir and react at 87 °C for 14 h. After the reaction is completed, purify by rotary evaporation to obtain modified phosphaphenanthrene; dissolve the modified phosphaphenanthrene in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; dissolve sodium hydride in tetrahydrofuran to obtain a sodium hydride solution; in a nitrogen environment, add the modified phosphaphenanthrene solution to the sodium hydride solution, and reflux and react at 67 °C for 13 h. After the reaction is completed, filter 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 is 1:1.2; when preparing the sodium alcohol nucleophilic solution, the reaction molar ratio of the modified phosphaphenanthrene to sodium hydride is 1:1.4;

[0038] S2: In a nitrogen environment, dissolve hexachlorocyclotriphosphazene in 1,2,4-trichlorobenzene, then add sulfamic acid and calcium sulfate dihydrate, and react at 210 °C for 4.5 h. After the reaction is completed, cool, precipitate, filter, and wash to obtain linear polyphosphazene; dissolve the linear polyphosphazene in tetrahydrofuran to obtain a linear polyphosphazene solution; when preparing the linear polyphosphazene, the reaction mass ratio of hexachlorocyclotriphosphazene, sulfamic acid, and calcium sulfate dihydrate is 37:0.4:0.04;

[0039] S3: Slowly drop the sodium alcohol nucleophilic solution into the linear polyphosphazene solution, and reflux and react at 67 °C for 13 h. After the reaction is completed, precipitate, dissolve, and vacuum dry to obtain a flame retardant; fully mix polyamide 6 and the flame retardant evenly, and then melt extrude, pelletize, and melt spin to obtain flame retardant fibers; 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 8 wt% of polyamide 6; Melt extrusion parameters: temperature is 220 °C, screw speed is 60 rpm / min; Melt spinning parameters: temperature is 260 °C, winding speed is 600 m / min;

[0040] Step 2: Add the magnesium aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to the mixed solvent, disperse them evenly, adjust the pH to 9.1, stir and react at 67 °C for 3.5 h. After the reaction, filter, wash, dry, and grind to obtain the 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 73 °C for 4.5 h, then dropwise add the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution and continue to react for 6 h. After the reaction, cool, filter, wash, and vacuum dry to obtain the intermediate product; the mixed solvent consists of ethylene glycol and deionized water with 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;

[0041] Under a nitrogen atmosphere, dissolve the intermediate product in tetrahydrofuran, then add triethylamine and stir well to obtain a reaction solution; dissolve cyanuric chloride in tetrahydrofuran to obtain a cyanuric chloride solution; let the reaction solution stand at 2 °C for 6 min, then dropwise add the cyanuric chloride solution. After the addition, reflux and react at 62 °C for 10 h. After the reaction, filter, rotary evaporate, dissolve, wash, dry, and filter to obtain the hydrotalcite flame retardant material; when preparing the hydrotalcite flame retardant material, the reaction mass ratio of the intermediate product and 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 the hydrotalcite flame retardant material, disperse evenly for 25 min, then add 10 parts of silicone rubber toughening agent, 15 parts of dioctyl adipate, 0.7 part of phosphite antioxidant, and 1.8 parts of cuprous iodide and mix well to obtain a mixed material; perform extrusion granulation and injection molding on the mixed material in sequence to obtain the finished product; Extrusion granulation parameters: temperature is 270 °C, rotation speed is 400 rpm / min; Injection molding parameters: temperature is 300 °C.

[0043] Example 3: Step 1: S1: Mix eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide evenly, then add azobisisobutyronitrile, and stir and react at 85°C for 13 h. After the reaction is completed, purify by rotary evaporation to obtain modified phosphaphenanthrene; dissolve the modified phosphaphenanthrene in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; dissolve sodium hydride in tetrahydrofuran to obtain a sodium hydride solution; under a nitrogen atmosphere, add the modified phosphaphenanthrene solution to the sodium hydride solution, and reflux and react at 65°C for 12 h. After the reaction is completed, filter to obtain a sodium alkoxide nucleophilic solution; when preparing the modified phosphaphenanthrene solution, the reaction molar ratio of eugenol to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1.2; when preparing the sodium alkoxide nucleophilic solution, the reaction molar ratio of the modified phosphaphenanthrene to sodium hydride is 1:1.4;

[0044] S2: Under a nitrogen atmosphere, dissolve hexachlorocyclotriphosphazene in 1,2,4-trichlorobenzene, then add sulfamic acid and calcium sulfate dihydrate, and react at 200°C for 4 h. After the reaction is completed, cool, precipitate, filter, and wash to obtain linear polyphosphazene; dissolve the linear polyphosphazene in tetrahydrofuran to obtain a linear polyphosphazene solution; when preparing the linear polyphosphazene, the reaction mass ratio of hexachlorocyclotriphosphazene, sulfamic acid, and calcium sulfate dihydrate is 37:0.4:0.04;

[0045] S3: Slowly drop the sodium alkoxide nucleophilic solution into the linear polyphosphazene solution, and reflux and react at 65°C for 12 h. After the reaction is completed, precipitate, dissolve, and vacuum dry to obtain a flame retardant; fully mix polyamide 6 and the flame retardant evenly, and then carry out melt extrusion, pelletizing, and melt spinning to obtain flame retardant fibers; when preparing the flame retardant, the reaction mass ratio of the solute of the sodium alkoxide nucleophilic solution to the linear polyphosphazene is 1.1:4; the addition amount of the flame retardant is 8 wt% of polyamide 6; Melt extrusion parameters: temperature is 210°C, screw speed is 50 rpm / min; Melt spinning parameters: temperature is 250°C, winding speed is 550 m / min;

[0046] Step 2: Add the magnesium-aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to the mixed solvent, disperse them evenly, adjust the pH to 9.0, stir and react at 65 °C for 3 h. After the reaction, filter, wash, dry, and grind to obtain the 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 h, then dropwise add the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution and continue to react for 5 h. After the reaction, cool, filter, wash, and vacuum dry to obtain the intermediate product; the mixed solvent consists of ethylene glycol and deionized water with a volume ratio of 1.1:10; when preparing the modified hydrotalcite material, the reaction mass ratio of the magnesium-aluminum hydrotalcite material to 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 atmosphere, dissolve the intermediate product in tetrahydrofuran, then add triethylamine and stir well to obtain a reaction solution; dissolve cyanuric chloride in tetrahydrofuran to obtain a cyanuric chloride solution; let the reaction solution stand at 0 °C for 5 min, then dropwise add the cyanuric chloride solution. After the addition, reflux and react at 60 °C for 8 h. After the reaction, filter, rotary evaporate, dissolve, wash, dry, and filter to obtain the hydrotalcite flame retardant material; when preparing the hydrotalcite flame retardant material, the reaction mass ratio of the intermediate product to 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 the hydrotalcite flame retardant material, disperse them evenly for 20 min, then add 10 parts of silicone rubber toughening agent, 15 parts of dioctyl adipate, 0.7 part of phosphite antioxidant, and 1.8 parts of cuprous iodide and mix well to obtain a mixed material; perform extrusion granulation and injection molding on the mixed material in sequence to obtain the finished product; Extrusion granulation parameters: temperature is 250 °C, rotation speed is 400 rpm / min; Injection molding parameters: temperature is 250 °C.

[0049] Comparative Example 1: Remove the flame retardant fiber, and the rest is the same as in Example 1. The specific steps are as follows: Step 1: Add the magnesium aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to the mixed solvent, disperse evenly, adjust the pH to 9.2, stir and react at 70 °C for 4 h. After the reaction, filter, wash, dry, and grind to obtain the 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 for 5 h, then dropwise add the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution, and continue to react for 8 h. After the reaction, cool, filter, wash, vacuum dry to obtain the intermediate product; the mixed solvent is composed of ethylene glycol and deionized water, and the volume ratio is 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;

[0050] Under a nitrogen atmosphere, dissolve the intermediate product in tetrahydrofuran, then add triethylamine, stir well to obtain the reaction solution; dissolve cyanuric chloride in tetrahydrofuran to obtain a cyanuric chloride solution; let the reaction solution stand at 3 °C for 8 min, then dropwise add the cyanuric chloride solution. After the addition is completed, reflux and react at 65 °C for 12 h. After the reaction, filter, rotary evaporate, dissolve, wash, dry, and filter to obtain the hydrotalcite flame retardant material; when preparing the hydrotalcite flame retardant material, the reaction mass ratio of the intermediate product and cyanuric chloride is 1:0.23;

[0051] Step 2: Premix 120 parts of polyamide resin and 15 parts of the hydrotalcite flame retardant material, disperse evenly for 30 min, then add 10 parts of silicone rubber toughening agent, 15 parts of dioctyl adipate, 0.7 part of phosphite antioxidant, and 1.8 parts of cuprous iodide and mix evenly to obtain the mixed material; extrude and pelletize the mixed material in sequence, and then injection mold to obtain the finished product; Extrusion granulation parameters: temperature is 280 °C, rotation speed is 400 rpm / min; Injection molding parameters: temperature is 350 °C.

[0052] Comparative Example 2: Remove the hydrotalcite flame retardant material, and the rest is the same as in Example 1. The specific steps are as follows: Step 1: S1: Mix eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide evenly, then add azobisisobutyronitrile, and stir and react at 90 °C for 15 h. After the reaction is completed, it is purified by rotary evaporation to obtain modified phosphaphenanthrene; dissolve the modified phosphaphenanthrene in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; dissolve sodium hydride in tetrahydrofuran to obtain a sodium hydride solution; in a nitrogen environment, add the modified phosphaphenanthrene solution to the sodium hydride solution, and reflux and react at 70 °C for 14 h. After the reaction is completed, it is filtered to obtain a sodium alkoxide nucleophilic solution; when preparing the modified phosphaphenanthrene solution, the reaction molar ratio of eugenol to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1.2; when preparing the sodium alkoxide nucleophilic solution, the reaction molar ratio of modified phosphaphenanthrene to sodium hydride is 1:1.4;

[0053] S2: In a nitrogen environment, dissolve hexachlorocyclotriphosphazene in 1,2,4-trichlorobenzene, then add sulfamic acid and calcium sulfate dihydrate, and react at 220 °C for 5 h. After the reaction is completed, it is cooled, precipitated, filtered, and washed to obtain linear polyphosphazene; dissolve the linear polyphosphazene in tetrahydrofuran to obtain a linear polyphosphazene solution; when preparing the linear polyphosphazene, the reaction mass ratio of hexachlorocyclotriphosphazene, sulfamic acid, and calcium sulfate dihydrate is 37:0.4:0.04;

[0054] S3: Slowly drop the sodium alkoxide nucleophilic solution into the linear polyphosphazene solution, and reflux and react at 70 °C for 14 h. After the reaction is completed, it is precipitated, dissolved, and vacuum dried to obtain a flame retardant; mix the polyamide 6 and the flame retardant evenly, and then perform melt extrusion, pelletizing, and melt spinning to obtain flame retardant fibers; when preparing the flame retardant, the reaction mass ratio of the solute of the sodium alkoxide nucleophilic solution to the linear polyphosphazene is 1.1:4; the addition amount of the flame retardant is 8 wt% of the polyamide 6; Melt extrusion parameters: temperature is 240 °C, screw speed is 70 rpm / min; Melt spinning parameters: temperature is 270 °C, winding speed is 650 m / min;

[0055] Step 2: Premix 120 parts of polyamide resin and 10 parts of flame retardant fibers, disperse them fully for 30 min, then add 10 parts of silicone rubber toughening agent, 15 parts of dioctyl adipate, 0.7 part of phosphite antioxidant, and 1.8 parts of copper iodide and mix evenly to obtain a mixture; perform extrusion granulation and injection molding on the mixture in sequence 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 are removed, and the rest is the same as Example 1, and the specific steps are 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 are mixed uniformly 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, rotation speed is 400rpm / min; injection molding parameters: temperature is 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 is used as a sample with a sample size of 90×10×4 mm, and the oxygen index value is recorded.

[0059] Impact resistance test: referring to GB / T 1843-2020 "Determination of cantilever beam impact strength of plastics", the finished product prepared by the present invention is used as a sample with a sample size of 80×10×4 mm, and the impact strength is 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 by the present invention was used as a sample with a sample size of 170×20×4mm, and the tensile strength was recorded. The results are as follows:

[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 obvious 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 18.3 KJ / 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 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 to 24%, and the impact strength is reduced to 19.5 KJ / m 2, the tensile strength decreased to 61 MPa. The reasons are as follows: The hydrotalcite flame retardant material contains various flame retardant structures, so the oxygen index decreases after removing it; in addition, due to the layered structure characteristics of the hydrotalcite flame retardant material, it can effectively improve the impact strength and tensile strength of the specimen. Therefore, the performance will decrease after removing the hydrotalcite flame retardant material.

[0065] Comparative Example 3: Remove the flame retardant fiber and the hydrotalcite flame retardant material, and the rest is the same as in Example 1. It can be seen from the experimental data that compared with Example 1, the oxygen index decreased to 21%, and the impact strength decreased to 17.1 KJ / m 2 , the tensile strength decreased to 53 MPa. The reasons are as follows: According to Comparative Example 1 and Comparative Example 2, the addition of the flame retardant fiber and the hydrotalcite flame retardant material can effectively improve the oxygen index, impact strength and tensile strength of the specimen. Therefore, the performance will decrease significantly after removing the two materials.

[0066] It should be noted that in this article, relational terms such as first and second are only used 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 variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device.

[0067] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of an impact-resistant and flame-retardant polyamide cable tie, characterized in that: It includes the following steps: Step 1: Thoroughly mix polyamide 6 and a flame retardant evenly, then conduct melt extrusion, pelletizing, and melt spinning to obtain flame-retardant fibers; Step 2: Add a magnesium-aluminum hydrotalcite material and γ-aminopropyltriethoxysilane to a mixed solvent, disperse them evenly, adjust the pH to 9.0 - 9.2, stir and react at 65 - 70 °C for 3 - 4 h. After the reaction, conduct suction filtration, washing, drying, and grinding to obtain a modified hydrotalcite material; Add the modified hydrotalcite material and 4-hydroxybenzaldehyde to ethanol, stir and react at 70 - 75 °C for 4 - 5 h, then dropwise add a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide solution and continue to react for 5 - 8 h. After the reaction, conduct cooling, filtration, washing, and vacuum drying to obtain an intermediate product; Under a nitrogen atmosphere, dissolve the intermediate product in tetrahydrofuran, then add triethylamine and stir thoroughly to obtain a reaction solution; Dissolve cyanuric chloride in tetrahydrofuran to obtain a cyanuric chloride solution; Let the reaction solution stand at 0 - 3 °C for 5 - 8 min, then dropwise add the cyanuric chloride solution. After the addition, reflux and react at 60 - 65 °C for 8 - 12 h. After the reaction, conduct filtration, rotary evaporation, dissolution, washing, drying, and filtration to obtain a hydrotalcite flame retardant; Step 3: Pre-mix polyamide resin, flame-retardant fibers, and the hydrotalcite flame retardant, disperse them thoroughly for 20 - 30 min, then add a toughening agent, a plasticizer, an antioxidant, and a heat stabilizer and mix evenly to obtain a mixed material; Subject the mixed material to extrusion granulation and injection molding in sequence to obtain a finished product.

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

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

4. The preparation method of an impact-resistant and flame-retardant polyamide cable tie according to claim 3, wherein: The preparation process of the flame retardant is: S1: Thoroughly mix eugenol and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, then add azobisisobutyronitrile and stir and react at 85 - 90 °C for 13 - 15 h. After the reaction, conduct rotary evaporation and purification to obtain a modified phosphaphenanthrene; Dissolve the modified phosphaphenanthrene in tetrahydrofuran to obtain a modified phosphaphenanthrene solution; Dissolve sodium hydride in tetrahydrofuran to obtain a sodium hydride solution; Under a nitrogen atmosphere, add the modified phosphaphenanthrene solution to the sodium hydride solution and reflux and react at 65 - 70 °C for 12 - 14 h. After the reaction, conduct filtration to obtain a sodium alcohol nucleophilic solution; Dissolve the linear polyphosphazene in tetrahydrofuran to obtain a linear polyphosphazene solution; S2: Under a nitrogen atmosphere, dissolve hexachlorocyclotriphosphazene in 1,2,4-trichlorobenzene, then add amidosulfonic acid and calcium sulfate dihydrate and react at 200 - 220 °C for 4 - 5 h. After the reaction, conduct cooling, precipitation, filtration, and washing to obtain linear polyphosphazene; S3: Slowly dropwise add the sodium alcohol nucleophilic solution to the linear polyphosphazene solution and reflux and react at 65 - 70 °C for 12 - 14 h. After the reaction, conduct precipitation, dissolution, and vacuum drying to obtain the flame retardant.

5. The preparation method of an impact-resistant and flame-retardant polyamide cable tie according to claim 4, wherein: When preparing the modified phosphaphenanthrene solution, the reaction molar ratio of eugenol to 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 to sodium hydride is 1:(1.3 - 1.5); when preparing 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 to linear polyphosphazene is (1.0 - 1.2):

4.

6. The preparation method of an impact-resistant and flame-retardant polyamide cable tie according to claim 1, characterized in that: In step two, the mixed solvent consists of ethylene glycol and deionized water, and the volume ratio is (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.

7. The preparation method of an impact-resistant and flame-retardant polyamide cable tie according to claim 1, characterized in that: In step two, when preparing the modified hydrotalcite material, the reaction mass ratio of the magnesium-aluminum hydrotalcite material to 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 to cyanuric chloride is 1:(0.20 - 0.25).

8. The preparation method of an impact-resistant and flame-retardant polyamide cable tie according to claim 1, characterized in that: In step three, the content of each component in the mixed material is 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; among them, 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.

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