High-temperature-resistant corrosion-resistant nylon 66 material for cable tie and preparation method of high-temperature-resistant corrosion-resistant nylon 66 material

Abstract

The invention relates to the technical field of synthesis of high polymer materials, in particular to a high-temperature-resistant and corrosion-resistant nylon 66 material for a ribbon and a preparation method of the high-temperature-resistant and corrosion-resistant nylon 66 material. The invention provides a high-temperature-resistant and corrosion-resistant nylon 66 material for a ribbon. The high-temperature-resistant and corrosion-resistant nylon 66 material comprises the following raw materials in parts by weight: 70-85 parts of nylon 66 resin; 10 to 20 parts of polyolefin elastomer; 2-5 parts of modified nano silicon dioxide, 0.5-1 part of an antioxidant and 0.5-1 part of a lubricant. The polyolefin elastomer (POE) and the modified nano silicon dioxide are added into the nylon 66 resin according to a specific proportion, so that the high-temperature resistance of the nylon 66 material is improved, the permeation of a corrosive medium is effectively hindered, and the corrosion resistance of the nylon 66 material is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material synthesis, and in particular to a high-temperature-resistant and corrosion-resistant nylon 66 material for cable ties and a preparation method thereof. Background Art

[0002] Since its introduction, nylon cable ties have found widespread application in numerous fields, including electronics, construction, logistics, and aerospace, thanks to their fast tying, excellent insulation, self-locking, and ease of use. Nylon 66, with its high mechanical strength, good fiber elasticity, and excellent overall performance, has become a common material for nylon cable ties.

[0003] However, with the continuous development and progress of various industries, the performance requirements for nylon cable ties are becoming increasingly stringent. In some special application scenarios, existing nylon 66 cable ties have exposed many shortcomings. For example, in the field of electronic equipment manufacturing, as electronic equipment develops towards miniaturization and high performance, the problem of heat dissipation within the equipment has become increasingly prominent. This requires that nylon cable ties used for bundling wires and cables must have superior high-temperature resistance to ensure that the cable ties will not soften, deform, or even break during long-term use in high-temperature environments, thereby ensuring the safe and stable operation of the equipment. However, the mechanical properties of traditional nylon 66 cable ties will significantly degrade when approaching or exceeding the upper limit of their normal operating temperature (generally around 80°C). In fields such as chemical engineering and marine engineering, nylon cable ties are exposed to prolonged exposure to various chemical media, as well as corrosive environments such as high humidity and salt spray. The corrosion resistance of existing nylon 66 materials no longer meets the requirements of these harsh environments, making them susceptible to corrosion and aging, significantly shortening the service life of the cable ties and increasing equipment maintenance costs and safety risks. For example, on offshore oil drilling platforms, the nylon cable ties used to secure cables and pipelines often lose their securing properties quickly due to corrosion from seawater, oil and gas, and various chemicals. To improve the performance of nylon 66, attempts have been made to add various additives. Although some results have been achieved to a certain extent, the synergistic improvement in high temperature resistance and corrosion resistance has never been achieved to the ideal state. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a high-temperature resistant and corrosion-resistant nylon 66 material for cable ties and a preparation method. The present invention adds a specific proportion of polyolefin elastomer (POE) and modified nano-silica to nylon 66 resin, which not only improves the high-temperature resistance of the nylon 66 material, but also effectively hinders the penetration of corrosive media, thereby improving the corrosion resistance of the nylon 66 material.

[0005] To this end, the present invention provides the following technical solutions: In a first aspect, the present invention provides, in an optional embodiment, a high-temperature resistant and corrosion-resistant nylon 66 material for cable ties, comprising the following raw materials in parts by weight: 70-85 parts of nylon 66 resin; 10-20 parts of polyolefin elastomer; 2-5 parts of modified nano-silica, 0.5-1 part of antioxidant and 0.5-1 part of lubricant.

[0006] In the present invention, the elastomeric network of POE fills the gaps in the nylon 66 matrix, reduces the freedom of movement of the molecular chain, and increases the thermal deformation temperature. The amino groups of NH2-SiO2 form hydrogen bonds with the amide groups of nylon 66, enhancing the interfacial bonding force. At the same time, the silane coating fills the interfacial gaps between POE and the matrix. The two work together to form an "elastomer-rigid particle interpenetrating network", which keeps the material structurally stable at 200°C, while preventing the penetration of insulating oil molecules, thereby improving the corrosion resistance of the nylon 66 material.

[0007] Preferably, the antioxidant is selected from one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris[2,4-di-tert-butylphenyl]phosphite or dilauryl thiodipropionate; and / or the lubricant is selected from one or more of zinc stearate, calcium stearate or magnesium stearate.

[0008] Furthermore, the nylon 66 material includes the following raw materials in parts by weight: 72-80 parts of nylon 66 resin; 13-18 parts of polyolefin elastomer; 2.5-4 parts of modified nano-silica, 0.5-1 part of antioxidant and 0.5-1 part of lubricant.

[0009] Furthermore, the nylon 66 material includes the following raw materials in parts by weight: 76 parts of nylon 66 resin; 15 parts of polyolefin elastomer; 3.2 parts of modified nano-silica, 0.9 parts of antioxidant and 0.7 parts of lubricant.

[0010] In a second aspect, the present invention provides, in an optional embodiment, a method for preparing the above-mentioned high-temperature resistant and corrosion-resistant nylon 66 material for cable ties, comprising the following steps: S1: adding nano-silica to anhydrous ethanol for ultrasonic dispersion, then adding γ-aminopropyltriethoxysilane for magnetic stirring and refluxing, and finally washing and drying to obtain modified nano-silica; S2: vacuum-drying the nylon 66 resin and setting it aside; preheating the polyolefin elastomer, modified nano-silica, antioxidant, and lubricant and setting it aside; S3: The raw materials of step S2 are blended and extruded, and then cooled to room temperature and pelletized to obtain the nylon 66 material.

[0011] Preferably, in step S1, the mass volume ratio of the nano-silica and anhydrous ethanol is 1 g:350-750 mL; and / or the ultrasonic dispersion time is 20-40 minutes; and / or the mass ratio of the nano-silica and γ-aminopropyltriethoxysilane is 5:1-2; and / or the temperature of the magnetic stirring reflux is 70-90°C and the time is 3.5-4.5 hours; and / or the drying temperature is 50-70°C and the time is 10-14 hours.

[0012] Preferably, in step S2, the vacuum drying temperature is 110-130°C, and the time is 6-10 hours; and / or the temperature after preheating is 75-85°C.

[0013] Preferably, in step S3, the blending extrusion adopts a twin-screw extruder, the feeding section temperature is 220°C, the compression section temperature is 240°C, the melting section temperature is 250°C, the head temperature is 245°C, the screw speed is 200-250rpm, and the material residence time in the barrel is 5-8 minutes.

[0014] In a third aspect, the present invention provides a method for preparing a nylon 66 cable tie in an optional embodiment, comprising the following steps: The cable tie is preheated at 75-85°C for 3-5 hours with a high temperature resistant and corrosion resistant nylon 66 material. The injection molding machine is preheated according to the material temperature of 270-280°C, the mold temperature of 60-70°C, and the injection pressure of 50-70Pa. The preheated nylon 66 material is injected into the mold at a screw speed of 280-320rpm. The pressure is first maintained at 40-50Pa for 4-6 seconds, and then a dynamic pressure holding treatment is performed. Finally, the mold is cooled to room temperature, the mold is opened and the part is taken out to obtain the nylon 66 cable tie; The dynamic pressure maintaining treatment is performed by increasing the pressure from 40-50 Pa to 60 Pa, and then reducing the pressure from 60 Pa to 40-50 Pa, with a cycle every 2 seconds and a number of cycles of 3-5 times.

[0015] In this invention, dynamic pressure forces the nylon 66 molecular chains to align within the network formed by POE and NH2-SiO2, reducing internal voids and microcracks and creating a denser crystalline structure. This structure blocks the penetration of insulating oil molecules while increasing crystallinity and raising the heat distortion temperature.

[0016] In a fourth aspect, the present invention provides a nylon 66 cable tie in an optional embodiment, which is prepared using the above-mentioned preparation method.

[0017] Compared with the prior art, the present invention has one of the following beneficial effects: 1. This invention creates a unique "elastomer-rigid particle interpenetrating network" structure by adding a specific ratio of polyolefin elastomer (POE) and modified nanosilica to nylon 66 resin. The POE elastomer network fills the gaps within the nylon 66 matrix, effectively reducing the freedom of motion of the molecular chains and thereby increasing the material's heat distortion temperature. The amino groups on the surface of the modified nanosilica form hydrogen bonds with the amide groups of the nylon 66, enhancing interfacial bonding. The silane coating also fills the interfacial gaps between the POE and the matrix, further stabilizing the material structure.

[0018] 2. On the one hand, the unique "elastomer-rigid particle interpenetrating network" structure makes the material denser, effectively hindering the penetration of corrosive media. On the other hand, the presence of modified nano-silica enhances the chemical stability of the nylon 66 material. When the cable tie is immersed in corrosive media such as the insulating paint used in motor stators, a protective passivation film forms on the material surface, preventing the corrosive media from chemically reacting with the nylon 66 matrix.

[0019] 3. The polyolefin elastomer (POE) used in this invention exhibits a unique synergistic mechanism with modified nano-silica. The non-polar segments of POE and the amino groups of the modified nano-silica combine through physical entanglement and hydrogen bonding. Together, they act on the nylon 66 matrix, achieving a synergistic improvement in high-temperature resistance and corrosion resistance. This synergistic effect is specific and does not occur with other common toughening agents (such as EVA and TPU).

[0020] 4. During the nylon 66 material preparation process, the pretreatment and co-extrusion conditions of each raw material are precisely controlled to ensure uniform dispersion of each component and fully utilize their performance advantages. In the injection molding process for nylon cable ties, not only are traditional injection molding process parameters (such as injection pressure, mold temperature, holding pressure, barrel temperature, and screw speed) optimized and adjusted, but a dynamic pressure holding treatment step is also innovatively added. This step applies periodic pressure during the holding phase, which promotes the directional alignment of the nylon 66 molecular chains within the network formed by POE and modified nano-silica. This further reduces internal voids and microcracks, resulting in a denser crystalline structure and significantly improving the cable tie's overall performance. DETAILED DESCRIPTION

[0021] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0022] In the following examples and comparative examples, nylon 66 resin was purchased from Suzhou Shipneng Plastic Co., Ltd. with the model number Zytel e51hsb nc010, polyolefin elastomer was purchased from Jiangsu Runfeng Synthetic Technology Co., Ltd. with the model number POLY, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate was purchased from Shanghai Buding Chemical with the model number antioxidant 1010, ethylene-vinyl acetate copolymer was purchased from Wuhan Jiyesheng Chemical Co., Ltd. with the model number BJ-707, and thermoplastic polyurethane elastomer was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd. with the model number 990R.

[0023] The technical solution of the present invention will be described below with reference to embodiments.

[0024] Example 1 This embodiment provides a nylon 66 material for cable ties, comprising the following raw materials: 76 kg of nylon 66 resin, 15 kg of polyolefin elastomer, 3.2 kg of modified nano-silica, 0.9 kg of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 0.7 kg of zinc stearate.

[0025] The preparation method of the nylon 66 material for the cable tie comprises the following steps: S1: 5 kg of nano-silica was added to 500 L of anhydrous ethanol and ultrasonically dispersed for 30 minutes. Then, 1 kg of γ-aminopropyltriethoxysilane was added and refluxed at 80°C with magnetic stirring for 4 hours. After reflux, the mixture was cooled to room temperature and washed with ethanol three times (filtration / centrifugation was required after each washing to retain the solid filter cake). The washed solid filter cake was vacuum dried at 60°C for 12 hours to obtain modified nano-silica; S2: After drying nylon 66 resin under vacuum at 120°C for 8 hours, the mixture is set aside. After preheating the polyolefin elastomer, modified nano-silica, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and zinc stearate to 80°C, the mixture is set aside. S3: Add the raw materials prepared in step S2 to a twin-screw extruder, control the temperature of the feeding section to 220°C, the temperature of the compression section to 240°C, the temperature of the melting section to 250°C, the head temperature to 245°C, the screw speed to 220 rpm, and the material residence time in the barrel to 6 minutes, and perform blending and extrusion. After the extrudate is cooled to room temperature by water, it is stretched and pelletized to obtain nylon 66 material for cable ties.

[0026] The prepared nylon 66 material was preheated at 80°C for 4 hours, and the injection molding machine was preheated according to a material temperature of 270°C, a mold temperature of 70°C, and an injection pressure of 60 Pa. The preheated nylon 66 material was injected into the mold by the screw at a speed of 300 rpm. The pressure was first maintained at 50 Pa for 5 seconds, then the pressure was increased from 50 Pa to 60 Pa, and then the pressure was reduced from 60 Pa to 50 Pa. The cycle was repeated every 2 seconds for 5 times. Finally, the mold was cooled to room temperature, the mold was opened and the part was taken out to obtain the nylon 66 cable tie.

[0027] Example 2 This embodiment provides a nylon 66 material for cable ties, comprising the following raw materials: 80 kg of nylon 66 resin, 10 kg of polyolefin elastomer, 5 kg of modified nano-silica, 0.5 kg of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 1 kg of zinc stearate.

[0028] The preparation method of the nylon 66 material for the cable tie comprises the following steps: S1: 5 kg of nano-silica was added to 500 L of anhydrous ethanol and ultrasonically dispersed for 30 minutes. Then, 1 kg of γ-aminopropyltriethoxysilane was added and refluxed at 80°C with magnetic stirring for 4 hours. After reflux, the mixture was cooled to room temperature and washed with ethanol three times (filtration / centrifugation was required after each washing to retain the solid filter cake). The washed solid filter cake was vacuum dried at 60°C for 12 hours to obtain modified nano-silica; S2: After drying nylon 66 resin under vacuum at 120°C for 8 hours, the mixture is set aside. After preheating the polyolefin elastomer, modified nano-silica, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and zinc stearate to 80°C, the mixture is set aside. S3: Add the raw materials prepared in step S2 to a twin-screw extruder, control the temperature of the feeding section to 220°C, the temperature of the compression section to 240°C, the temperature of the melting section to 250°C, the head temperature to 245°C, the screw speed to 220 rpm, and the material residence time in the barrel to 6 minutes, and perform blending and extrusion. After the extrudate is cooled to room temperature by water, it is stretched and pelletized to obtain nylon 66 material for cable ties.

[0029] The prepared nylon 66 material was preheated at 80°C for 4 hours, and the injection molding machine was preheated according to a material temperature of 270°C, a mold temperature of 70°C, and an injection pressure of 60 Pa. The preheated nylon 66 material was injected into the mold by the screw at a speed of 300 rpm. The pressure was first maintained at 50 Pa for 5 seconds, then the pressure was increased from 50 Pa to 60 Pa, and then the pressure was reduced from 60 Pa to 50 Pa. The cycle was repeated every 2 seconds for 5 times. Finally, the mold was cooled to room temperature, the mold was opened and the part was taken out to obtain the nylon 66 cable tie.

[0030] Example 3 This embodiment provides a nylon 66 material for cable ties, comprising the following raw materials: 70 kg of nylon 66 resin, 20 kg of polyolefin elastomer, 2 kg of modified nano-silica, 1 kg of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 0.5 kg of zinc stearate.

[0031] The preparation method of the nylon 66 material for the cable tie comprises the following steps: S1: 5 kg of nano-silica was added to 500 L of anhydrous ethanol and ultrasonically dispersed for 30 minutes. Then, 1 kg of γ-aminopropyltriethoxysilane was added and refluxed at 80°C with magnetic stirring for 4 hours. After reflux, the mixture was cooled to room temperature and washed with ethanol three times (filtration / centrifugation was required after each washing to retain the solid filter cake). The washed solid filter cake was vacuum dried at 60°C for 12 hours to obtain modified nano-silica; S2: After drying nylon 66 resin under vacuum at 120°C for 8 hours, the mixture is set aside. After preheating the polyolefin elastomer, modified nano-silica, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and zinc stearate to 80°C, the mixture is set aside. S3: Add the raw materials prepared in step S2 to a twin-screw extruder, control the temperature of the feeding section to 220°C, the temperature of the compression section to 240°C, the temperature of the melting section to 250°C, the head temperature to 245°C, the screw speed to 220 rpm, and the material residence time in the barrel to 6 minutes, and perform blending and extrusion. After the extrudate is cooled to room temperature by water, it is stretched and pelletized to obtain nylon 66 material for cable ties.

[0032] The prepared nylon 66 material was preheated at 80°C for 4 hours, and the injection molding machine was preheated according to a material temperature of 270°C, a mold temperature of 70°C, and an injection pressure of 60 Pa. The preheated nylon 66 material was injected into the mold by the screw at a speed of 300 rpm. The pressure was first maintained at 50 Pa for 5 seconds, then the pressure was increased from 50 Pa to 60 Pa, and then the pressure was reduced from 60 Pa to 50 Pa. The cycle was repeated every 2 seconds for 5 times. Finally, the mold was cooled to room temperature, the mold was opened and the part was taken out to obtain the nylon 66 cable tie.

[0033] Example 4 This embodiment provides a nylon 66 material for cable ties, comprising the following raw materials: 85 kg of nylon 66 resin, 20 kg of polyolefin elastomer, 2.5 kg of modified nano-silica, 0.9 kg of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 0.7 kg of zinc stearate.

[0034] The preparation method of the nylon 66 material for the cable tie comprises the following steps: S1: 5 kg of nano-silica was added to 500 L of anhydrous ethanol and ultrasonically dispersed for 30 minutes. Then, 1 kg of γ-aminopropyltriethoxysilane was added and refluxed at 80°C with magnetic stirring for 4 hours. After reflux, the mixture was cooled to room temperature and washed with ethanol three times (filtration / centrifugation was required after each washing to retain the solid filter cake). The washed solid filter cake was vacuum dried at 60°C for 12 hours to obtain modified nano-silica; S2: After drying nylon 66 resin under vacuum at 120°C for 8 hours, the mixture is set aside. After preheating the polyolefin elastomer, modified nano-silica, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and zinc stearate to 80°C, the mixture is set aside. S3: Add the raw materials prepared in step S2 to a twin-screw extruder, control the temperature of the feeding section to 220°C, the temperature of the compression section to 240°C, the temperature of the melting section to 250°C, the head temperature to 245°C, the screw speed to 220 rpm, and the material residence time in the barrel to 6 minutes, and perform blending and extrusion. After the extrudate is cooled to room temperature by water, it is stretched and pelletized to obtain nylon 66 material for cable ties.

[0035] The prepared nylon 66 material was preheated at 80°C for 4 hours, and the injection molding machine was preheated according to a material temperature of 270°C, a mold temperature of 70°C, and an injection pressure of 60 Pa. The preheated nylon 66 material was injected into the mold by the screw at a speed of 300 rpm. The pressure was first maintained at 50 Pa for 5 seconds, then the pressure was increased from 50 Pa to 60 Pa, and then the pressure was reduced from 60 Pa to 50 Pa. The cycle was repeated every 2 seconds for 5 times. Finally, the mold was cooled to room temperature, the mold was opened and the part was taken out to obtain the nylon 66 cable tie.

[0036] Comparative Example 1 This comparative example provides a nylon 66 material for a cable tie, comprising the following raw materials: 91 kg of nylon 66 resin, 3.2 kg of modified nano-silica, 0.9 kg of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 0.7 kg of zinc stearate.

[0037] The preparation method of the nylon 66 material for the cable tie comprises the following steps: S1: 5 kg of nano-silica was added to 500 L of anhydrous ethanol and ultrasonically dispersed for 30 minutes. Then, 1 kg of γ-aminopropyltriethoxysilane was added and refluxed at 80°C with magnetic stirring for 4 hours. After reflux, the mixture was cooled to room temperature and washed with ethanol three times (filtration / centrifugation was required after each washing to retain the solid filter cake). The washed solid filter cake was vacuum dried at 60°C for 12 hours to obtain modified nano-silica; S2: After drying nylon 66 resin under vacuum at 120°C for 8 hours, the mixture is set aside. Modified nano-silica, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and zinc stearate are preheated to 80°C and set aside. S3: Add the raw materials prepared in step S2 to a twin-screw extruder, control the temperature of the feeding section to 220°C, the temperature of the compression section to 240°C, the temperature of the melting section to 250°C, the head temperature to 245°C, the screw speed to 220 rpm, and the material residence time in the barrel to 6 minutes, and perform blending and extrusion. After the extrudate is cooled to room temperature by water, it is stretched and pelletized to obtain nylon 66 material for cable ties.

[0038] The prepared nylon 66 material was preheated at 80°C for 4 hours, and the injection molding machine was preheated according to a material temperature of 270°C, a mold temperature of 70°C, and an injection pressure of 60 Pa. The preheated nylon 66 material was injected into the mold by the screw at a speed of 300 rpm. The pressure was first maintained at 50 Pa for 5 seconds, then the pressure was increased from 50 Pa to 60 Pa, and then the pressure was reduced from 60 Pa to 50 Pa. The cycle was repeated every 2 seconds for 5 times. Finally, the mold was cooled to room temperature, the mold was opened and the part was taken out to obtain the nylon 66 cable tie.

[0039] Comparative Example 2 This comparative example provides a nylon 66 material for a cable tie, comprising the following raw materials: 79.2 kg of nylon 66 resin, 15 kg of polyolefin elastomer, 0.9 kg of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 0.7 kg of zinc stearate.

[0040] The preparation method of the nylon 66 material for the cable tie comprises the following steps: S1: After drying nylon 66 resin under vacuum at 120°C for 8 hours, set aside. Preheat polyolefin elastomer, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and zinc stearate to 80°C and set aside. S2: Add the raw materials prepared in step S2 to a twin-screw extruder, control the feeding section temperature to 220°C, the compression section temperature to 240°C, the melting section temperature to 250°C, the die head temperature to 245°C, the screw speed to 220 rpm, and the material residence time in the barrel to 6 minutes, and perform blending and extrusion. After the extrudate is cooled to room temperature by water, it is stretched and pelletized to obtain nylon 66 material for cable ties.

[0041] The prepared nylon 66 material was preheated at 80°C for 4 hours, and the injection molding machine was preheated according to a material temperature of 270°C, a mold temperature of 70°C, and an injection pressure of 60 Pa. The preheated nylon 66 material was injected into the mold by the screw at a speed of 300 rpm. The pressure was first maintained at 50 Pa for 5 seconds, then the pressure was increased from 50 Pa to 60 Pa, and then the pressure was reduced from 60 Pa to 50 Pa. The cycle was repeated every 2 seconds for 5 times. Finally, the mold was cooled to room temperature, the mold was opened and the part was taken out to obtain the nylon 66 cable tie.

[0042] Comparative Example 3 This comparative example provides a nylon 66 material for a cable tie, comprising the following raw materials: 76 kg of nylon 66 resin, 15 kg of polyolefin elastomer, 3.2 kg of nano-silica, 0.9 kg of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 0.7 kg of zinc stearate.

[0043] The preparation method of the nylon 66 material for the cable tie comprises the following steps: S1: After drying nylon 66 resin under vacuum at 120°C for 8 hours, set aside. Preheat polyolefin elastomer, nano-silica, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and zinc stearate to 80°C and set aside. S2: Add the raw materials prepared in step S2 to a twin-screw extruder, control the feeding section temperature to 220°C, the compression section temperature to 240°C, the melting section temperature to 250°C, the die head temperature to 245°C, the screw speed to 220 rpm, and the material residence time in the barrel to 6 minutes, and perform blending and extrusion. After the extrudate is cooled to room temperature by water, it is stretched and pelletized to obtain nylon 66 material for cable ties.

[0044] The prepared nylon 66 material was preheated at 80°C for 4 hours, and the injection molding machine was preheated according to a material temperature of 270°C, a mold temperature of 70°C, and an injection pressure of 60 Pa. The preheated nylon 66 material was injected into the mold by the screw at a speed of 300 rpm. The pressure was first maintained at 50 Pa for 5 seconds, then the pressure was increased from 50 Pa to 60 Pa, and then the pressure was reduced from 60 Pa to 50 Pa. The cycle was repeated every 2 seconds for 5 times. Finally, the mold was cooled to room temperature, the mold was opened and the part was taken out to obtain the nylon 66 cable tie.

[0045] Comparative Example 4 This comparative example provides a nylon 66 material for a cable tie, comprising the following raw materials: 76 kg of nylon 66 resin, 15 kg of ethylene-vinyl acetate copolymer, 3.2 kg of modified nano-silica, 0.9 kg of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 0.7 kg of zinc stearate.

[0046] The preparation method of the nylon 66 material for the cable tie comprises the following steps: S1: 5 kg of nano-silica was added to 500 L of anhydrous ethanol and ultrasonically dispersed for 30 minutes. Then, 1 kg of γ-aminopropyltriethoxysilane was added and refluxed at 80°C with magnetic stirring for 4 hours. After reflux, the mixture was cooled to room temperature and washed with ethanol three times (filtration / centrifugation was required after each washing to retain the solid filter cake). The washed solid filter cake was vacuum dried at 60°C for 12 hours to obtain modified nano-silica; S2: After drying nylon 66 resin under vacuum at 120°C for 8 hours, set aside. Ethylene-vinyl acetate copolymer, modified nano-silica, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and zinc stearate were preheated to 80°C and set aside. S3: Add the raw materials prepared in step S2 to a twin-screw extruder, control the temperature of the feeding section to 220°C, the temperature of the compression section to 240°C, the temperature of the melting section to 250°C, the head temperature to 245°C, the screw speed to 220 rpm, and the material residence time in the barrel to 6 minutes, and perform blending and extrusion. After the extrudate is cooled to room temperature by water, it is stretched and pelletized to obtain nylon 66 material for cable ties.

[0047] The prepared nylon 66 material was preheated at 80°C for 4 hours, and the injection molding machine was preheated according to a material temperature of 270°C, a mold temperature of 70°C, and an injection pressure of 60 Pa. The preheated nylon 66 material was injected into the mold by the screw at a speed of 300 rpm. The pressure was first maintained at 50 Pa for 5 seconds, then the pressure was increased from 50 Pa to 60 Pa, and then the pressure was reduced from 60 Pa to 50 Pa. The cycle was repeated every 2 seconds for 5 times. Finally, the mold was cooled to room temperature, the mold was opened and the part was taken out to obtain the nylon 66 cable tie.

[0048] Comparative Example 5 This comparative example provides a nylon 66 material for a cable tie, comprising the following raw materials: 76 kg of nylon 66 resin, 15 kg of thermoplastic polyurethane elastomer, 3.2 kg of modified nano-silica, 0.9 kg of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 0.7 kg of zinc stearate.

[0049] The preparation method of the nylon 66 material for the cable tie comprises the following steps: S1: 5 kg of nano-silica was added to 500 L of anhydrous ethanol and ultrasonically dispersed for 30 minutes. Then, 1 kg of γ-aminopropyltriethoxysilane was added and refluxed at 80°C with magnetic stirring for 4 hours. After reflux, the mixture was cooled to room temperature and washed with ethanol three times (filtration / centrifugation was required after each washing to retain the solid filter cake). The washed solid filter cake was vacuum dried at 60°C for 12 hours to obtain modified nano-silica; S2: After drying nylon 66 resin under vacuum at 120°C for 8 hours, set aside. Preheat thermoplastic polyurethane elastomer, modified nano-silica, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and zinc stearate to 80°C and set aside. S3: Add the raw materials prepared in step S2 to a twin-screw extruder, control the temperature of the feeding section to 220°C, the temperature of the compression section to 240°C, the temperature of the melting section to 250°C, the head temperature to 245°C, the screw speed to 220 rpm, and the material residence time in the barrel to 6 minutes, and perform blending and extrusion. After the extrudate is cooled to room temperature by water, it is stretched and pelletized to obtain nylon 66 material for cable ties.

[0050] The prepared nylon 66 material was preheated at 80°C for 4 hours, and the injection molding machine was preheated according to a material temperature of 270°C, a mold temperature of 70°C, and an injection pressure of 60 Pa. The preheated nylon 66 material was injected into the mold by the screw at a speed of 300 rpm. The pressure was first maintained at 50 Pa for 5 seconds, then the pressure was increased from 50 Pa to 60 Pa, and then the pressure was reduced from 60 Pa to 50 Pa. The cycle was repeated every 2 seconds for 5 times. Finally, the mold was cooled to room temperature, the mold was opened and the part was taken out to obtain the nylon 66 cable tie.

[0051] Comparative Example 6 This comparative example provides a nylon 66 material for a cable tie, comprising the following raw materials: 76 kg of nylon 66 resin, 15 kg of polyolefin elastomer, 3.2 kg of modified nano-silica, 0.9 kg of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and 0.7 kg of zinc stearate.

[0052] The preparation method of the nylon 66 material for the cable tie comprises the following steps: S1: 5 kg of nano-silica was added to 500 L of anhydrous ethanol and ultrasonically dispersed for 30 minutes. Then, 1 kg of γ-aminopropyltriethoxysilane was added and refluxed at 80°C with magnetic stirring for 4 hours. After reflux, the mixture was cooled to room temperature and washed with ethanol three times (filtration / centrifugation was required after each washing to retain the solid filter cake). The washed solid filter cake was vacuum dried at 60°C for 12 hours to obtain modified nano-silica; S2: After drying nylon 66 resin under vacuum at 120°C for 8 hours, the mixture is set aside. After preheating the polyolefin elastomer, modified nano-silica, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and zinc stearate to 80°C, the mixture is set aside. S3: Add the raw materials prepared in step S2 to a twin-screw extruder, control the temperature of the feeding section to 220°C, the temperature of the compression section to 240°C, the temperature of the melting section to 250°C, the head temperature to 245°C, the screw speed to 220 rpm, and the material residence time in the barrel to 6 minutes, and perform blending and extrusion. After the extrudate is cooled to room temperature by water, it is stretched and pelletized to obtain nylon 66 material for cable ties.

[0053] The prepared nylon 66 material was preheated at 80°C for 4 hours, and the injection molding machine was preheated according to a material temperature of 270°C, a mold temperature of 70°C, and an injection pressure of 60 Pa. The preheated nylon 66 material was injected into the mold at a screw speed of 300 rpm, and the pressure was maintained at 50 Pa for 15 seconds. Finally, the mold was cooled to room temperature, the mold was opened, and the part was taken out to obtain the nylon 66 cable tie.

[0054] Experimental example The performance tests were performed on the nylon 66 cable ties prepared in Examples 1-4 and Comparative Examples 1-6: Heat Deflection Temperature (HDT) test: According to ASTM D648, load 1.82 MPa, heating rate 2 ° C / min, record the temperature when the sample is bent and deformed by 0.25 mm.

[0055] High-temperature tensile strength retention rate: Place the cable tie in a 200°C constant temperature oven for 1000 hours. After taking it out, test the tensile strength according to ASTM D638 and calculate the retention rate (retention rate = tensile strength after treatment / initial tensile strength × 100%). Insulating oil immersion test: Soak the cable tie in H-grade insulating oil (model: 1032 alkyd insulating varnish) at 150°C for 48 hours. After taking it out, bake it at 200°C for 2 hours to observe whether it breaks or cracks.

[0056] The performance test results are shown in Table 1: Table 1 Test results of nylon 66 materials prepared in Examples 1-4 and Comparative Examples 1-6 As can be seen from Table 1, compared with Example 1, the HDT of Comparative Example 1 decreased by 27°C, the high-temperature tensile retention rate decreased by 29.05%, and the insulating oil immersion resulted in brittle fracture. Compared with Example 1, the HDT of Comparative Example 2 decreased by 22°C, the tensile retention rate after immersion decreased by 22.37%, and local cracking occurred. Compared with Example 1, the HDT of Comparative Example 3 decreased by 17°C, the tensile retention rate after immersion decreased by 17.8%, and embrittlement occurred. Compared with Example 1, the HDT of Comparative Example 4 decreased by 24°C, the tensile retention rate after immersion decreased by 25.3%, and fracture occurred. Compared with Example 1, the HDT of Comparative Example 5 decreased by 20°C, the tensile retention rate after immersion decreased by 21.13%, and cracking occurred. Compared with Example 1, the HDT of Comparative Example 5 decreased by 12°C, the high-temperature tensile retention rate decreased by 12.19%, and occasional fracture occurred after immersion. It can be seen that the present invention, by adding a specific proportion of polyolefin elastomer (POE) and modified nano-silica to nylon 66 resin, not only improves the high temperature resistance of nylon 66 material, but also effectively hinders the penetration of corrosive media, thereby improving the corrosion resistance of nylon 66 material.

[0057] Although the principles of the present invention have been described in detail above in conjunction with the preferred embodiments of the present invention, those skilled in the art should understand that the above embodiments are merely illustrative of the present invention and are not intended to limit the scope of the present invention. The details in the embodiments do not constitute a limitation on the scope of the present invention. Without departing from the spirit and scope of the present invention, any obvious changes such as equivalent transformations and simple substitutions based on the technical solution of the present invention fall within the scope of protection of the present invention.

Claims

1. A high temperature resistant and corrosion resistant nylon 66 material for cable ties, characterized in that: The invention comprises the following raw materials in parts by weight: 70-85 parts of nylon 66 resin; 10-20 parts of polyolefin elastomer; 2-5 parts of modified nano silicon dioxide; 0.5-1 part of antioxidant; and 0.5-1 part of lubricant.

2. The high temperature resistant and corrosion resistant nylon 66 material for cable ties according to claim 1, characterized in that: The antioxidant is selected from one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris[2,4-di-tert-butylphenyl]phosphite or dilauryl thiodipropionate; and / or, The lubricant is selected from one or more of zinc stearate, calcium stearate or magnesium stearate.

3. The high temperature resistant and corrosion resistant nylon 66 material for cable ties according to claim 1, characterized in that: The nylon 66 material comprises the following raw materials in parts by weight: 72-80 parts of nylon 66 resin; 13-18 parts of polyolefin elastomer; 2.5-4 parts of modified nano-silicon dioxide; 0.5-1 part of antioxidant; and 0.5-1 part of lubricant.

4. The high temperature resistant and corrosion resistant nylon 66 material for cable ties according to claim 1, characterized in that: The nylon 66 material comprises the following raw materials in parts by weight: 76 parts of nylon 66 resin; 15 parts of polyolefin elastomer; 3.2 parts of modified nano-silicon dioxide; 0.9 parts of antioxidant; and 0.7 parts of lubricant.

5. A method for preparing the high temperature resistant and corrosion resistant nylon 66 material for cable ties according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1: adding nano-silica to anhydrous ethanol for ultrasonic dispersion, then adding γ-aminopropyltriethoxysilane for magnetic stirring and refluxing, and finally washing and drying to obtain modified nano-silica; S2: vacuum-drying the nylon 66 resin and setting it aside; preheating the polyolefin elastomer, modified nano-silica, antioxidant, and lubricant and setting it aside; S3: The raw materials of step S2 are blended and extruded, and then cooled to room temperature and pelletized to obtain the nylon 66 material.

6. The method for preparing the high temperature resistant and corrosion resistant nylon 66 material for cable ties according to claim 5, characterized in that: In step S1, the mass volume ratio of the nano-silica and anhydrous ethanol is 1g:350-750mL; and / or, The ultrasonic dispersion time is 20-40 minutes; and / or, The mass ratio of the nano-silica to γ-aminopropyltriethoxysilane is 5:1-2; and / or, The magnetic stirring reflux temperature is 70-90° C. and the time is 3.5-4.5 hours; and / or, The drying temperature is 50-70° C. and the drying time is 10-14 hours.

7. The method for preparing the high temperature resistant and corrosion resistant nylon 66 material for cable ties according to claim 5, characterized in that: In step S2, the vacuum drying temperature is 110-130° C. and the time is 6-10 hours; and / or, The temperature after preheating is 75-85°C.

8. The method for preparing the high temperature resistant and corrosion resistant nylon 66 material for cable ties according to claim 5, characterized in that: In step S3, the blending extrusion adopts a twin-screw extruder with a feeding section temperature of 220°C, a compression section temperature of 240°C, a melting section temperature of 250°C, a die head temperature of 245°C, a screw speed of 200-250rpm, and a material residence time in the barrel of 5-8 minutes.

9. A method for preparing a nylon 66 cable tie, characterized in that: The following steps are involved: The high-temperature resistant and corrosion-resistant nylon 66 material for the cable tie according to any one of claims 1 to 4 is preheated at 75-85° C. for 3-5 hours, and the injection molding machine is preheated according to the material temperature of 270-280° C., the mold temperature of 60-70° C., and the injection pressure of 50-70 Pa. The preheated nylon 66 material is injected into the mold at a screw speed of 280-320 rpm, and the pressure is first maintained at 40-50 Pa for 4-6 seconds, and then a dynamic pressure holding treatment is performed. Finally, the mold is cooled to room temperature, the mold is opened and the part is taken out to obtain the nylon 66 cable tie; The dynamic pressure maintaining treatment is performed by increasing the pressure from 40-50 Pa to 60 Pa, and then reducing the pressure from 60 Pa to 40-50 Pa, with a cycle every 2 seconds and a number of cycles of 3-5 times.

10. A nylon 66 cable tie, characterized in that: The preparation method according to claim 9 is used for preparation.

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