Anti-aging impact-resistant automobile nylon composite corrugated pipe and preparation method thereof

Abstract

The invention discloses an anti-aging impact-resistant automobile nylon composite corrugated pipe and a preparation method thereof, and relates to the technical field of pipes, the anti-aging impact-resistant automobile nylon composite corrugated pipe comprises the following components by weight: 40-80 parts of modified polypropylene, 5-40 parts of nylon, 5-20 parts of an anti-aging master batch, 5-15 parts of a flame retardant, 0.5-3 parts of carbon black and other auxiliary agents, modified polypropylene, nylon, anti-aging master batch, carbon black and other auxiliaries are mixed and extruded and granulated through a double-screw extruder, then a single-screw extruder, a corrugated pipe forming mold and a vacuum setting device are used for matched forming, annealing treatment is performed after cooling setting, and the finished nylon composite corrugated pipe is obtained. By designing the anti-aging master batch, the function of high environmental adaptability of the nylon composite corrugated pipe is realized, the problems of aging, toughness weakening and brittleness increase of the nylon composite corrugated pipe caused by an external environment are solved, the UV resistance and thermal stability of the nylon composite corrugated pipe are improved, and the use scene of the nylon composite corrugated pipe is widened.

Description

Technical Field

[0001] The invention relates to the technical field of pipes, in particular to an anti-aging and impact-resistant automotive nylon composite corrugated pipe and a preparation method thereof. Background Art

[0002] With its unique corrugated design, automotive nylon composite corrugated tube provides good flexibility and twisting ability, enabling it to adapt to complex automotive wiring requirements. The choice of nylon material gives automotive nylon composite corrugated tube a variety of features. Nylon has high toughness and impact resistance, good product stability, and can maintain stable performance under different temperature environments. In the automotive industry, nylon composite corrugated tubes are widely used in wire harness protection, fuel systems, cooling systems, and exhaust systems. They can effectively protect wire harnesses from wear and damage, prevent fuel leakage and evaporation, and withstand the influence of high temperature and corrosive environments. In addition, nylon composite corrugated tubes also have good electrical insulation and flame retardant properties, providing favorable protection for the safety of automotive electrical equipment.

[0003] Although nylon bellows are corrosion-resistant, impact-resistant, high-strength and easy to bend, the nylon material itself is easy to absorb moisture and easily deform or melt at high temperatures. These characteristics limit its scope of use. Nylon bellows exposed to the external environment for a long time will be affected by factors such as ultraviolet rays, humidity and temperature, which will lead to material aging, reduced toughness and increased brittleness.

[0004] Patent document CN113088029B discloses a high impact resistant double-wall corrugated pipe and a preparation method thereof. The above patent realizes that the polypropylene double-wall corrugated pipe has high ring stiffness, is strong below the impact external pressure and has good impact resistance.

[0005] In summary, the above patent uses 60-80 parts of modified polypropylene, 25-35 parts of nylon 12, 5-10 parts of interface improver, 8-12 parts of impact modifier, 4-6 parts of nano-silicon dioxide, 3-5 parts of nano-barium sulfate, 0.8-1.6 parts of ethylene bis stearic acid amide, 1.5-3.5 parts of antioxidant 1010 and 1-3 parts of silane coupling agent A-171, mixes the raw materials by weight, and dries them at 80°C for 1-3 hours, and conveys the dried materials to the extruder for extruding the inner and outer walls of the double-wall corrugated pipe respectively for plasticization and extrusion, and the plasticized extruded materials are molded into a double-wall corrugated pipe under vacuum and cooled to form, so as to prepare a double-wall corrugated pipe with high ring stiffness, low external pressure and good impact resistance, but there is room for optimization in the environmental adaptability of the nylon composite corrugated pipe;

[0006] To this end, the present application proposes an anti-aging and impact-resistant automotive nylon composite corrugated pipe with strong environmental adaptability and a preparation method thereof. Summary of the invention

[0007] The purpose of the present invention is to provide an anti-aging and impact-resistant automotive nylon composite bellows and a preparation method thereof, so as to solve the technical problem of poor environmental adaptability of the nylon composite bellows proposed in the above background technology.

[0008] To achieve the above object, the present invention provides the following technical solution: an anti-aging and impact-resistant automotive nylon composite corrugated pipe, comprising the following components by weight: modified polypropylene: 40 to 80 parts;

[0009] Nylon: 5 to 40 parts;

[0010] Anti-aging masterbatch: 5 to 20 parts;

[0011] Flame retardant: 5 to 15 parts;

[0012] Compatibilizer: 5 to 20 parts;

[0013] Toughening agent: 2 to 30 parts;

[0014] Carbon black: 0.5 to 3 parts;

[0015] Impact modifier: 1 to 4 parts;

[0016] Silane coupling agent: 0.1 to 0.5 parts;

[0017] The preparation method of the anti-aging masterbatch is as follows: prepare 50 to 70 parts of nylon, 20 to 35 parts of mica flakes, 3 to 10 parts of anti-aging agent, 1 to 5 parts of zinc stearate, 0.2 to 12 parts of silane coupling agent and 0.5 to 1 part of antioxidant, dry the mica flakes at 120° C. for 4 hours, put the treated materials into a high-speed mixer, mix them for 10 to 15 minutes at a speed of 800 to 1000 rpm and a temperature of 60 to 80° C., and mix the mixture. The combined material is put into a twin-screw extruder and extruded at a screw speed of 300rpm-400rpm and a pressure of -0.08MP, wherein the segmented temperature of the twin-screw extruder is controlled to 220°C for zone one, 235°C for zone two, 245°C for zone three, 250°C for zone four and 255°C for the die head. The extrudate is cooled in a water tank at a water temperature of 25°C-30°C and then cut into particles with a particle size of 2mm-3mm. The particles are dried in an environment of 80°C for 6h to obtain anti-aging masterbatch.

[0018] Preferably, the nylon is nylon 6 and nylon 66, and the weight ratio of nylon 6 to nylon 66 is 1:2.

[0019] Preferably, the flame retardant is ferric hydroxide and red phosphorus, and the weight ratio of ferric hydroxide to red phosphorus is 7:3.

[0020] Preferably, the compatibilizer is maleic anhydride grafted polypropylene.

[0021] Preferably, the toughening agent is maleic anhydride grafted POE.

[0022] Preferably, the impact modifier is methyl methacrylate-butadiene-styrene copolymer.

[0023] Preferably, the antioxidant is 2,2,6,6-tetramethyl-4-piperidinol.

[0024] Preferably, the antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0025] Preferably, the preparation method is:

[0026] S1: Dry the nylon at 120℃ for 4h and the modified polypropylene at 80℃ for 2h;

[0027] S2: Mix carbon black and silane coupling agent and process in a high-speed mixer at a speed of 1000 rpm for 10 min;

[0028] S3: Add modified polypropylene, nylon and compatibilizer into a high-speed mixer at a mixing temperature of 60°C and a mixing time of 5 minutes;

[0029] S4: adding anti-aging masterbatch, flame retardant, toughening agent, impact modifier and treated carbon black / silane mixture in sequence and mixing for 10 minutes;

[0030] S5: putting the mixture into a twin-screw extruder for extrusion, the zone temperatures of the twin-screw extruder are 170°C for zone 1, 185°C for zone 2, 190°C for zone 3, 185°C for zone 4 and 180°C for die head, cooling and pelletizing after extrusion, and drying the pellets in an environment of 80°C for 3h;

[0031] S6: Put the pellets into a single screw extruder, the single screw base and temperature zones are divided into zone 1 180°C, zone 2 200°C, zone 3 210°C and mold 220°C, use a bellows molding mold with a vacuum shaping device to shape, and after shaping, cool and shape in sections in an environment with a water temperature of 20°C to 30°C;

[0032] S7: annealing the shaped corrugated pipe in an oven at 80° C. for 2 h to obtain a finished nylon composite corrugated pipe.

[0033] Preferably, the preparation method of the modified polyethylene is:

[0034] S1: preparing polypropylene particles, perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, Ziegler-Natta catalyst and maleic anhydride grafted polypropylene;

[0035] S2: Mixing polypropylene particles with maleic anhydride grafted polypropylene, adding the mixture into the main feed port of a twin-screw extruder, and injecting perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and Ziegler-Natta catalyst into the reaction zone of the twin-screw extruder through the feed port, wherein the temperature of the feeding zone is 160° C. to 180° C., the temperature of the melting zone is 190° C. to 210° C., and the temperature of the reaction zone is 200° C. to 220° C.;

[0036] S3: Cooling, pelletizing, washing and drying the extruded strips to obtain modified polypropylene.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] 1. The present invention realizes the function of strong environmental adaptability of nylon composite corrugated pipe by designing anti-aging masterbatch, solves the problems of aging, weakened toughness and increased brittleness of nylon composite corrugated pipe caused by external environment, improves the UV resistance and thermal stability of nylon composite corrugated pipe, prolongs the service life of nylon composite corrugated pipe, and broadens the application scenarios of nylon composite corrugated pipe;

[0039] 2. The present invention achieves the function of reducing the moisture absorption capacity of the nylon composite corrugated pipe by designing modified polypropylene, solves the problems of volume expansion, performance degradation and chemical resistance reduction caused by water absorption of the nylon composite corrugated pipe, can maintain the dimensional stability of the nylon composite corrugated pipe, improves the durability and reliability of the nylon composite corrugated pipe, and reduces the accumulation of internal stress during the extrusion process;

[0040] 3. The present invention achieves the function of improving dispersibility while avoiding phase separation by designing a flame retardant system with iron hydroxide and red phosphorus, solves the problem of agglomeration occurring during the preparation of the nylon composite corrugated pipe, can improve the smoke suppression and thermal stability of the nylon composite corrugated pipe, reduces the moisture absorption capacity of the nylon composite corrugated pipe, and prolongs the service life of the nylon composite corrugated pipe;

[0041] 4. The present invention achieves the function of improving the wear resistance of the nylon composite corrugated pipe by designing carbon black, solves the problems of the nylon composite corrugated pipe being not durable, not wear-resistant and easy to age, can meet specific color requirements, reduces the expansion coefficient of the nylon composite corrugated pipe, and improves the mechanical strength, thermal stability and wear resistance of the nylon composite corrugated pipe. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 It is a schematic diagram of the composition of the present invention;

[0043] Figure 2 It is a schematic diagram of the preparation process of the nylon composite corrugated pipe of the present invention;

[0044] Figure 3 This is a schematic diagram of the preparation process of the anti-aging masterbatch of the present invention;

[0045] Figure 4 It is a schematic diagram of the preparation process of modified polypropylene of the present invention. DETAILED DESCRIPTION

[0046] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0047] Example 1: Please refer to Figure 1 , Figure 2 , Figure 3 and Figure 4 , an anti-aging and impact-resistant automotive nylon composite corrugated pipe, comprising the following components in parts by weight: modified polypropylene: 60 parts;

[0048] Nylon: 25 parts;

[0049] Anti-aging masterbatch: 15 parts;

[0050] Flame retardant: 10 parts;

[0051] Compatibilizer: 10 parts;

[0052] Toughener: 15 parts;

[0053] Carbon black: 2 parts;

[0054] Impact modifier: 2 parts;

[0055] Silane coupling agent: 0.3 parts;

[0056] The preparation method of the anti-aging masterbatch is as follows: prepare 50 parts of nylon, 20 mica sheets, 5 parts of anti-aging agent, 3 parts of zinc stearate, 6 parts of silane coupling agent and 0.7 parts of antioxidant, dry the mica sheets at 120° C. for 4 hours, put the treated materials into a high-speed mixer, mix them for 15 minutes at a speed of 800 rpm and a temperature of 80° C., put the mixed materials into a twin-screw extruder, extrude them at a screw speed of 400 rpm and a pressure of -0.08 MP, wherein the segmented temperature of the twin-screw extruder is controlled to 220° C. for zone 1, 235° C. for zone 2, 245° C. for zone 3, 250° C. for zone 4 and 255° C. for the die, cool the extrudate in a water tank at a water temperature of 25° C., cut it into particles with a particle size of 2 mm, and dry the particles in an environment of 80° C. for 6 hours to obtain the anti-aging masterbatch;

[0057] The nylon is nylon 6 and nylon 66, and the weight ratio of nylon 6 to nylon 66 is 1:2;

[0058] The flame retardant is ferric hydroxide and red phosphorus, and the weight ratio of ferric hydroxide to red phosphorus is 7:3;

[0059] The compatibilizer is maleic anhydride grafted polypropylene;

[0060] The toughening agent is maleic anhydride grafted POE;

[0061] The impact modifier is methyl methacrylate-butadiene-styrene copolymer;

[0062] The anti-aging agent is 2,2,6,6-tetramethyl-4-piperidinol;

[0063] The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate;

[0064] Further, polypropylene particles, perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, Ziegler-Natta catalyst and maleic anhydride grafted polypropylene are prepared, and after the raw materials are dried, the polypropylene particles are mixed with the maleic anhydride grafted polypropylene, and added to the main feed port of the twin-screw extruder, and perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and Ziegler-Natta catalyst are injected into the reaction zone of the twin-screw extruder through the feed port, wherein the feeding zone temperature is 160° C. to 180° C., and the melting zone temperature is 190℃~210℃, the temperature of the reaction zone is 200℃~220℃, the extruded strip is cooled, pelletized, washed and dried to obtain modified polypropylene, 50 parts of nylon, 20 mica flakes, 5 parts of anti-aging agent, 3 parts of zinc stearate, 6 parts of silane coupling agent and 0.7 parts of antioxidant are prepared, the mica flakes are dried at 120℃ for 4h, the treated materials are put into a high-speed mixer, mixed for 15min at a speed of 800rpm and a temperature of 80℃, the mixed materials are put into a twin-screw extruder, and extruded at a screw speed of 400rpm and a pressure of -0.08MP, wherein the segmented temperature of the twin-screw extruder is controlled to 220 in one zone ℃, zone 235℃, zone 3 245℃, zone 4 250℃ and die head 255℃, cool the extrudate in a water tank at 25℃ and cut into particles with a particle size of 2mm, dry the particles at 80℃ for 6h to obtain anti-aging masterbatch, dry nylon at 120℃ for 4h, and modified polypropylene at 80℃ for 2h, mix carbon black with silane coupling agent, and treat in a high-speed mixer at a speed of 1000rpm for 10min, add modified polypropylene, nylon and compatibilizer into the high-speed mixer, the mixing temperature is 60℃, the mixing time is 5min, and anti-aging masterbatch, flame retardant, toughening agent, impact modifier and treated carbon black are added in sequence / silane mixture, mix for 10 minutes, put the mixture into a twin-screw extruder for extrusion, the zone temperature of the twin-screw extruder is 170°C for zone one, 185°C for zone two, 190°C for zone three, 185°C for zone four and 180°C for the head, cool and pelletize after extrusion, dry the pellets in an environment of 80°C for 3 hours, put the pellets into a single-screw extruder, the single-screw base and temperature zones are 180°C for zone one, 200°C for zone two, 210°C for zone three and 220°C for the mold, use a bellows molding mold with a vacuum molding device to mold, after molding, cool and shape in sections in an environment of 20°C to 30°C water temperature, anneal the molded bellows in an oven at 80°C for 2 hours, and obtain a finished nylon composite bellows.

[0065] Example 2: Please refer to Figure 1 , Figure 2 and Figure 4, an anti-aging and impact-resistant automotive nylon composite corrugated pipe, comprising the following components in parts by weight: modified polypropylene: 60 parts;

[0066] Nylon: 25 parts;

[0067] Anti-aging masterbatch: 15 parts;

[0068] Flame retardant: 10 parts;

[0069] Compatibilizer: 10 parts;

[0070] Toughener: 15 parts;

[0071] Carbon black: 2 parts;

[0072] Impact modifier: 2 parts;

[0073] Silane coupling agent: 0.3 parts;

[0074] The preparation method of the anti-aging masterbatch is as follows: prepare 50 parts of nylon, 20 mica sheets, 5 parts of anti-aging agent, 3 parts of zinc stearate, 6 parts of silane coupling agent and 0.7 parts of antioxidant, dry the mica sheets at 120° C. for 4 hours, put the treated materials into a high-speed mixer, mix them for 15 minutes at a speed of 800 rpm and a temperature of 80° C., put the mixed materials into a twin-screw extruder, extrude them at a screw speed of 400 rpm and a pressure of -0.08 MP, wherein the segmented temperature of the twin-screw extruder is controlled to 220° C. for zone 1, 235° C. for zone 2, 245° C. for zone 3, 250° C. for zone 4 and 255° C. for the die, cool the extrudate in a water tank at a water temperature of 25° C., cut it into particles with a particle size of 2 mm, and dry the particles in an environment of 80° C. for 6 hours to obtain the anti-aging masterbatch;

[0075] Further, polypropylene particles, perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, Ziegler-Natta catalyst and maleic anhydride grafted polypropylene are prepared, and after the raw materials are dried, the polypropylene particles are mixed with the maleic anhydride grafted polypropylene and added to the main feeding port of the twin-screw extruder, and perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and Ziegler-Natta catalyst are injected into the reaction zone of the twin-screw extruder through the feed port, wherein the feeding zone temperature is 160°C to 180°C, the melting zone temperature is 190°C to 210°C, and the reaction zone temperature is 200°C to 220°C. The extruded strips are cooled, pelletized, washed and dried to obtain modified polypropylene, and the nylon is dried at 120°C for 4 hours, and the modified polypropylene is dried at 80°C for 2 hours. The carbon black and silane are mixed. The coupling agent was mixed and processed in a high-speed mixer at a speed of 1000 rpm for 10 minutes. The modified polypropylene, nylon and compatibilizer were added to the high-speed mixer at a mixing temperature of 60°C for 5 minutes. The flame retardant, toughening agent, impact modifier and treated carbon black / silane mixture were added in sequence and mixed for 10 minutes. The mixture was put into a twin-screw extruder for extrusion. The zone temperatures of the twin-screw extruder were 170°C for zone one, 185°C for zone two, 190°C for zone three and 190°C for zone four. 185℃ and die head 180℃, cool and pelletize after extrusion, dry the pellets in an 80℃ environment for 3h, put the pellets into a single screw extruder, the single screw foundation and temperature zones are divided into zone 180℃, zone 200℃, zone 3 210℃ and mold 220℃, use a bellows forming mold with a vacuum shaping device to form, after forming, cool and shape in sections in an environment with a water temperature of 20℃~30℃, anneal the shaped bellows in an 80℃ oven for 2h to obtain a finished nylon composite bellows.

[0076] Example 3: Please refer to Figure 1 , Figure 2 and Figure 3 , an anti-aging and impact-resistant automotive nylon composite corrugated pipe, comprising the following components in parts by weight: modified polypropylene: 60 parts;

[0077] Nylon: 25 parts;

[0078] Anti-aging masterbatch: 15 parts;

[0079] Flame retardant: 10 parts;

[0080] Compatibilizer: 10 parts;

[0081] Toughener: 15 parts;

[0082] Carbon black: 2 parts;

[0083] Impact modifier: 2 parts;

[0084] Silane coupling agent: 0.3 parts;

[0085] The preparation method of the anti-aging masterbatch is as follows: prepare 50 parts of nylon, 20 mica sheets, 5 parts of anti-aging agent, 3 parts of zinc stearate, 6 parts of silane coupling agent and 0.7 parts of antioxidant, dry the mica sheets at 120° C. for 4 hours, put the treated materials into a high-speed mixer, mix them for 15 minutes at a speed of 800 rpm and a temperature of 80° C., put the mixed materials into a twin-screw extruder, extrude them at a screw speed of 400 rpm and a pressure of -0.08 MP, wherein the segmented temperature of the twin-screw extruder is controlled to 220° C. for zone 1, 235° C. for zone 2, 245° C. for zone 3, 250° C. for zone 4 and 255° C. for the die, cool the extrudate in a water tank at a water temperature of 25° C., cut it into particles with a particle size of 2 mm, and dry the particles in an environment of 80° C. for 6 hours to obtain the anti-aging masterbatch;

[0086] Further, 50 parts of nylon, 20 mica flakes, 5 parts of anti-aging agent, 3 parts of zinc stearate, 6 parts of silane coupling agent and 0.7 parts of antioxidant were prepared, the mica flakes were dried at 120°C for 4 hours, the treated materials were put into a high-speed mixer, mixed at a speed of 800 rpm and a temperature of 80°C for 15 minutes, the mixed materials were put into a twin-screw extruder, and the screw speed was 400 rpm and the pressure was -0.08 MPa. The extrusion was carried out, wherein the segmented temperatures of the twin-screw extruder were controlled to be 220°C in the first zone, 235°C in the second zone, 245°C in the third zone, 250°C in the fourth zone and 255°C in the die head. The extrudate was cooled in a water tank at a water temperature of 25°C and then cut into particles with a particle size of 2 mm. The particles were dried at 80°C for 6 hours to obtain anti-aging masterbatch. Nylon was dried at 120°C for 4 hours. Carbon black was mixed with a silane coupling agent and the mixture was heated at a high speed of 1000 rpm. The mixture was treated in a mixer for 10 minutes, nylon and compatibilizer were added to a high-speed mixer, the mixing temperature was 60°C, the mixing time was 5 minutes, anti-aging masterbatch, flame retardant, toughening agent, impact modifier and treated carbon black / silane mixture were added in sequence, mixed for 10 minutes, and the mixture was put into a twin-screw extruder for extrusion. The zone temperatures of the twin-screw extruder were 170°C for zone 1, 185°C for zone 2, 190°C for zone 3, 185°C for zone 4 and 180°C for the head. ℃, cooled and pelletized after extrusion, the pellets were dried in an environment of 80 ℃ for 3 hours, and put into a single-screw extruder. The single-screw foundation and temperature zones were divided into zone one 180 ℃, zone two 200 ℃, zone three 210 ℃ and mold 220 ℃. The bellows forming mold was used in conjunction with a vacuum shaping device for shaping. After shaping, the bellows was cooled and shaped in sections in an environment of 20 ℃ ~ 30 ℃ with water temperature. The shaped bellows was annealed in an oven at 80 ℃ for 2 hours to obtain a finished nylon composite bellows.

[0087] Example 4: Please refer to Figure 1 , Figure 2 , Figure 3 and Figure 4 , an anti-aging and impact-resistant automotive nylon composite corrugated pipe, comprising the following components in parts by weight: modified polypropylene: 60 parts;

[0088] Nylon: 25 parts;

[0089] Anti-aging masterbatch: 15 parts;

[0090] Flame retardant: 10 parts;

[0091] Compatibilizer: 10 parts;

[0092] Toughener: 15 parts;

[0093] Carbon black: 2 parts;

[0094] Impact modifier: 2 parts;

[0095] Silane coupling agent: 0.3 parts;

[0096] The preparation method of the anti-aging masterbatch is as follows: prepare 50 parts of nylon, 20 mica sheets, 5 parts of anti-aging agent, 3 parts of zinc stearate, 6 parts of silane coupling agent and 0.7 parts of antioxidant, dry the mica sheets at 120° C. for 4 hours, put the treated materials into a high-speed mixer, mix them for 15 minutes at a speed of 800 rpm and a temperature of 80° C., put the mixed materials into a twin-screw extruder, extrude them at a screw speed of 400 rpm and a pressure of -0.08 MP, wherein the segmented temperature of the twin-screw extruder is controlled to 220° C. for zone 1, 235° C. for zone 2, 245° C. for zone 3, 250° C. for zone 4 and 255° C. for the die, cool the extrudate in a water tank at a water temperature of 25° C., cut it into particles with a particle size of 2 mm, and dry the particles in an environment of 80° C. for 6 hours to obtain the anti-aging masterbatch;

[0097] Further, polypropylene particles, perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, Ziegler-Natta catalyst and maleic anhydride grafted polypropylene are prepared, and after the raw materials are dried, the polypropylene particles are mixed with the maleic anhydride grafted polypropylene, and added to the main feed port of the twin-screw extruder, and perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and Ziegler-Natta catalyst are injected into the reaction zone of the twin-screw extruder through the feed port, wherein the feeding zone temperature is 160° C. to 180° C., and the melting zone temperature is 120° C. to 180° C. The temperature of the reaction zone is 190°C to 210°C, the temperature of the reaction zone is 200°C to 220°C, the extruded strip is cooled, pelletized, washed and dried to obtain modified polypropylene, 50 parts of nylon, 20 mica sheets, 5 parts of anti-aging agent, 3 parts of zinc stearate, 6 parts of silane coupling agent and 0.7 parts of antioxidant are prepared, the mica sheets are dried at 120°C for 4 hours, the treated materials are placed in a high-speed mixer, mixed at a speed of 800rpm and a temperature of 80°C for 15 minutes, the mixed materials are placed in a twin-screw extruder, and extruded at a screw speed of 400rpm and a pressure of -0.08MP, wherein the segmented temperature of the twin-screw extruder is controlled as one zone 2 The temperature of the first zone is 20℃, the second zone is 235℃, the third zone is 245℃, the fourth zone is 250℃ and the head is 255℃. The extrudate is cooled in a water tank with a water temperature of 25℃ and then cut into particles with a particle size of 2mm. The particles are dried in an environment of 80℃ for 6h to obtain an anti-aging masterbatch. The nylon is dried in an environment of 120℃ for 4h, and the modified polypropylene is dried in an environment of 80℃ for 2h. The carbon black is mixed with the silane coupling agent and treated in a high-speed mixer with a speed of 1000rpm for 10min. The modified polypropylene, nylon and compatibilizer are added to the high-speed mixer. The mixing temperature is 60℃ and the mixing time is 5min. The anti-aging masterbatch, toughening agent, impact modifier and treated carbon black / The silane mixture is mixed for 10 minutes, and the mixture is put into a twin-screw extruder for extrusion. The zone temperatures of the twin-screw extruder are 170°C for zone 1, 185°C for zone 2, 190°C for zone 3, 185°C for zone 4 and 180°C for the die head. After extrusion, the pellets are cooled and pelletized. The pellets are dried in an environment of 80°C for 3 hours. The pellets are put into a single-screw extruder. The single-screw base and temperature zones are 180°C for zone 1, 200°C for zone 2, 210°C for zone 3 and 220°C for the mold. The bellows molding mold is used in combination with a vacuum shaping device for molding. After molding, the bellows is cooled and shaped in an environment of 20°C to 30°C in water temperature. The shaped bellows is annealed in an oven at 80°C for 2 hours to obtain a finished nylon composite bellows.

[0098] Example 5: Please refer to Figure 1 , Figure 2 , Figure 3 and Figure 4, an anti-aging and impact-resistant automotive nylon composite corrugated pipe, comprising the following components in parts by weight: modified polypropylene: 60 parts;

[0099] Nylon: 25 parts;

[0100] Anti-aging masterbatch: 15 parts;

[0101] Flame retardant: 10 parts;

[0102] Compatibilizer: 10 parts;

[0103] Toughener: 15 parts;

[0104] Carbon black: 2 parts;

[0105] Impact modifier: 2 parts;

[0106] Silane coupling agent: 0.3 parts;

[0107] The preparation method of the anti-aging masterbatch is as follows: prepare 50 parts of nylon, 20 mica sheets, 5 parts of anti-aging agent, 3 parts of zinc stearate, 6 parts of silane coupling agent and 0.7 parts of antioxidant, dry the mica sheets at 120° C. for 4 hours, put the treated materials into a high-speed mixer, mix them for 15 minutes at a speed of 800 rpm and a temperature of 80° C., put the mixed materials into a twin-screw extruder, extrude them at a screw speed of 400 rpm and a pressure of -0.08 MP, wherein the segmented temperature of the twin-screw extruder is controlled to 220° C. for zone 1, 235° C. for zone 2, 245° C. for zone 3, 250° C. for zone 4 and 255° C. for the die, cool the extrudate in a water tank at a water temperature of 25° C., cut it into particles with a particle size of 2 mm, and dry the particles in an environment of 80° C. for 6 hours to obtain the anti-aging masterbatch;

[0108] Further, polypropylene particles, perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, Ziegler-Natta catalyst and maleic anhydride grafted polypropylene were prepared, and the polypropylene particles and maleic anhydride grafted polypropylene were mixed after the raw materials were dried, and added to the main feed port of the twin-screw extruder, and perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and Ziegler-Natta catalyst were injected into the reaction zone of the twin-screw extruder through the feed port, wherein the feeding zone temperature was 160°C ~180℃, the temperature of the melting zone is 190℃~210℃, the temperature of the reaction zone is 200℃~220℃, the extruded strip is cooled, pelletized, washed and dried to obtain modified polypropylene, 50 parts of nylon, 20 mica sheets, 5 parts of anti-aging agent, 3 parts of zinc stearate, 6 parts of silane coupling agent and 0.7 parts of antioxidant are prepared, the mica sheets are dried at 120℃ for 4h, the treated materials are placed in a high-speed mixer, mixed at a speed of 800rpm and a temperature of 80℃ for 15min, the mixed materials are placed in a twin-screw extruder, and the screw speed is 400rpm and the pressure is -0.08MP. The extruder was extruded, wherein the segmented temperatures of the twin-screw extruder were controlled to be 220°C in zone 1, 235°C in zone 2, 245°C in zone 3, 250°C in zone 4 and 255°C in the die head. The extrudate was cooled in a water tank at 25°C and then cut into particles with a particle size of 2 mm. The particles were dried at 80°C for 6 hours to obtain anti-aging masterbatch. Nylon was dried at 120°C for 4 hours, and modified polypropylene was dried at 80°C for 2 hours. The modified polypropylene, nylon and compatibilizer were added into a high-speed mixer. The mixing temperature was 60°C and the mixing time was 5 minutes. The anti-aging masterbatch, flame retardant, toughening agent and impact modifier were added in sequence and mixed for 10 minutes. n, the mixture is put into a twin-screw extruder for extrusion, the zone temperatures of the twin-screw extruder are 170°C for zone one, 185°C for zone two, 190°C for zone three, 185°C for zone four and 180°C for the die head. After extrusion, the mixture is cooled and pelletized. The pellets are dried in an environment of 80°C for 3 hours, and the pellets are put into a single-screw extruder. The single-screw base and temperature zones are 180°C for zone one, 200°C for zone two, 210°C for zone three and 220°C for the mold. The mixture is formed using a bellows forming mold in combination with a vacuum shaping device. After forming, the mixture is cooled and shaped in sections in an environment of 20°C to 30°C in water temperature. The shaped bellows is annealed in an oven at 80°C for 2 hours to obtain a finished nylon composite bellows.

[0109] Example 6: Please refer to Figure 1 , Figure 2 , Figure 3 and Figure 4 , an anti-aging and impact-resistant automotive nylon composite corrugated pipe, comprising the following components in parts by weight: modified polypropylene: 60 parts;

[0110] Nylon: 25 parts;

[0111] Anti-aging masterbatch: 15 parts;

[0112] Flame retardant: 10 parts;

[0113] Compatibilizer: 10 parts;

[0114] Toughener: 15 parts;

[0115] Carbon black: 2 parts;

[0116] Impact modifier: 2 parts;

[0117] Silane coupling agent: 0.3 parts;

[0118] The preparation method of the anti-aging masterbatch is as follows: prepare 50 parts of nylon, 20 mica sheets, 5 parts of anti-aging agent, 3 parts of zinc stearate, 6 parts of silane coupling agent and 0.7 parts of antioxidant, dry the mica sheets at 120° C. for 4 hours, put the treated materials into a high-speed mixer, mix them for 15 minutes at a speed of 800 rpm and a temperature of 80° C., put the mixed materials into a twin-screw extruder, extrude them at a screw speed of 400 rpm and a pressure of -0.08 MP, wherein the segmented temperature of the twin-screw extruder is controlled to 220° C. for zone 1, 235° C. for zone 2, 245° C. for zone 3, 250° C. for zone 4 and 255° C. for the die, cool the extrudate in a water tank at a water temperature of 25° C., cut it into particles with a particle size of 2 mm, and dry the particles in an environment of 80° C. for 6 hours to obtain the anti-aging masterbatch;

[0119] Further, polypropylene particles, perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, Ziegler-Natta catalyst and maleic anhydride grafted polypropylene are prepared, and after the raw materials are dried, the polypropylene particles are mixed with the maleic anhydride grafted polypropylene, and added to the main feeding port of the twin-screw extruder, and perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and Ziegler-Natta catalyst are injected into the reaction zone of the twin-screw extruder through the feed port, wherein the feeding zone temperature is 160°C to 180°C, the melting zone temperature is 190°C to 210°C, and the reaction is carried out. The temperature of the reaction zone is 200℃~220℃, the extruded strip is cooled, pelletized, washed and dried to obtain modified polypropylene, 50 parts of nylon, 20 mica flakes, 5 parts of anti-aging agent, 3 parts of zinc stearate, 6 parts of silane coupling agent and 0.7 parts of antioxidant are prepared, the mica flakes are dried at 120℃ for 4h, the treated materials are put into a high-speed mixer, mixed for 15min at a speed of 800rpm and a temperature of 80℃, the mixed materials are put into a twin-screw extruder, and extruded at a screw speed of 400rpm and a pressure of -0.08MP, wherein the segmented temperature of the twin-screw extruder is controlled to 220℃ in zone 1, 235℃ in zone 2, 245℃ in zone 3 and 250℃ in zone 4. and the die head 255℃, the extrudate is cooled in a water tank with a water temperature of 25℃ and then cut into particles with a particle size of 2mm, the particles are dried in an environment of 80℃ for 6h to obtain an anti-aging masterbatch, the nylon is dried in an environment of 120℃ for 4h, the modified polypropylene is dried in an environment of 80℃ for 2h, the carbon black is mixed with the silane coupling agent, and treated in a high-speed mixer with a speed of 1000rpm for 10min, the modified polypropylene, nylon and compatibilizer are added to the high-speed mixer, the mixing temperature is 60℃, the mixing time is 5min, the anti-aging masterbatch, flame retardant, toughening agent, impact modifier and the treated carbon black / silane mixture are added in turn, and mixed for 10min, wherein the flame retardant is selected from aluminum hydroxide and magnesium hydroxide. The flame retardant system is prepared, the weight ratio of aluminum hydroxide to magnesium hydroxide is 1:2, the mixture is put into a twin-screw extruder for extrusion, the zone temperatures of the twin-screw extruder are 170°C for zone one, 185°C for zone two, 190°C for zone three, 185°C for zone four and 180°C for the die head, and the pellets are cooled and pelletized after extrusion. The pellets are dried in an environment of 80°C for 3 hours, and the pellets are put into a single-screw extruder. The single-screw base and temperature zones are 180°C for zone one, 200°C for zone two, 210°C for zone three and 220°C for the mold. The bellows molding mold is used in combination with a vacuum molding device for molding. After molding, it is cooled and molded in an environment of 20°C to 30°C in water temperature, and the molded bellows is annealed in an oven at 80°C for 2 hours to obtain a finished nylon composite bellows.

[0120] Performance Testing

[0121] Test 1: 20 samples of nylon composite corrugated pipes prepared in Examples 1-6 were selected, and the samples were selected to have the same size and shape. The samples were tested using a tensile testing machine. The test results are shown in the following table:

[0122]

[0123]

[0124] Test 2: 20 samples of nylon composite corrugated pipes prepared in Examples 1-6 were selected, and the samples were selected to have the same size and shape. The samples were tested using a Shore D hardness tester. The test results are shown in the following table:

[0125]

[0126] Test 3: 20 samples of nylon composite corrugated pipes prepared in Examples 1-6 were selected, and the samples were selected to have the same size and shape. The samples were notched using a notch sample making machine, and the samples were tested using an impact testing machine. The test results are shown in the following table:

[0127]

[0128] Test 4: 20 samples of nylon composite corrugated pipes prepared in Examples 1-6 were selected, and the samples were selected with the same size and shape. The samples were tested using a QUV ultraviolet aging test chamber. The test cycle was 500 hours. The test results are shown in the following table:

[0129]

[0130] Working principle: prepare 50 to 70 parts of nylon, 20 to 35 parts of mica flakes, 3 to 10 parts of anti-aging agent, 1 to 5 parts of zinc stearate, 0.2 to 12 parts of silane coupling agent and 0.5 to 1 part of antioxidant, dry the mica flakes at 120°C for 4 hours, put the treated materials into a high-speed mixer, mix them at a speed of 800 rpm to 1000 rpm and a temperature of 60°C to 80°C for 10 to 15 minutes, and mix the mixed materials. The material is put into a twin-screw extruder, and extruded at a screw speed of 300 rpm to 400 rpm and a pressure of -0.08 MP, wherein the segmented temperature of the twin-screw extruder is controlled to be 220° C. in the first zone, 235° C. in the second zone, 245° C. in the third zone, 250° C. in the fourth zone and 255° C. in the die head, and the extrudate is cooled in a water tank at a water temperature of 25° C. to 30° C. and then cut into particles with a particle size of 2 mm to 3 mm, and the particles are dried in an environment of 80° C. for 6 hours to obtain an anti-aging masterbatch;

[0131] Prepare polypropylene particles, perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, Ziegler-Natta catalyst and maleic anhydride grafted polypropylene, mix the polypropylene particles with the maleic anhydride grafted polypropylene after drying the raw materials, add them into the main feeding port of a twin-screw extruder, inject perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and Ziegler-Natta catalyst into the reaction zone of the twin-screw extruder through the feed port, wherein the feeding zone temperature is 160° C. to 180° C., the melting zone temperature is 190° C. to 210° C., and the reaction zone temperature is 200° C. to 220° C., and cool, pelletize, wash and dry the extruded strips to obtain modified polypropylene;

[0132] Prepare 5 to 40 parts of nylon, 5 to 20 parts of anti-aging masterbatch, 5 to 15 parts of flame retardant, 5 to 20 parts of compatibilizer, 2 to 30 parts of toughening agent, 0.5 to 3 parts of carbon black, 1 to 4 parts of impact modifier and 0.1 to 0.5 parts of silane coupling agent, dry the nylon in a 120°C environment for 4 hours, dry the modified polypropylene in an 80°C environment for 2 hours, mix the carbon black and the silane coupling agent, and process them in a high-speed mixer with a rotation speed of 1000 rpm for 10 minutes;

[0133] Add modified polypropylene, nylon and compatibilizer into a high-speed mixer at a mixing temperature of 60°C for 5 minutes. Add anti-aging masterbatch, flame retardant, toughening agent, impact modifier and treated carbon black / silane mixture in turn and mix for 10 minutes. Put the mixture into a twin-screw extruder for extrusion. The zone temperatures of the twin-screw extruder are 170°C for zone one, 185°C for zone two, 190°C for zone three, 185°C for zone four and 180°C for the die head. Cool and pelletize after extrusion. Dry the pellets in an environment of 80°C for 3 hours. Put the pellets into a single-screw extruder. The single-screw foundation and temperature zones are 180°C for zone one, 200°C for zone two, 210°C for zone three and 220°C for the mold. Use a bellows molding mold in combination with a vacuum shaping device to shape the product. After shaping, cool and shape the product in sections in an environment of 20°C to 30°C. Anneal the shaped bellows in an oven at 80°C for 2 hours to obtain a finished nylon composite bellows.

[0134] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

Claims

1. An anti-aging and impact-resistant automotive nylon composite bellows, characterized by: The invention comprises the following components by weight: modified polypropylene: 40 to 80 parts; Nylon: 5 to 40 parts; Anti-aging masterbatch: 5 to 20 parts; Flame retardant: 5 to 15 parts; Compatibilizer: 5 to 20 parts; Toughening agent: 2 to 30 parts; Carbon black: 0.5 to 3 parts; Impact modifier: 1 to 4 parts; Silane coupling agent: 0.1 to 0.5 parts; The preparation method of the anti-aging masterbatch is as follows: prepare 50 to 70 parts of nylon, 20 to 35 parts of mica flakes, 3 to 10 parts of anti-aging agent, 1 to 5 parts of zinc stearate, 0.2 to 12 parts of silane coupling agent and 0.5 to 1 part of antioxidant, dry the mica flakes at 120° C. for 4 hours, put the treated materials into a high-speed mixer, mix them for 10 to 15 minutes at a speed of 800 to 1000 rpm and a temperature of 60 to 80° C., and mix the mixture. The combined material is put into a twin-screw extruder and extruded at a screw speed of 300rpm-400rpm and a pressure of -0.08MP, wherein the segmented temperature of the twin-screw extruder is controlled to 220°C for zone one, 235°C for zone two, 245°C for zone three, 250°C for zone four and 255°C for the die head. The extrudate is cooled in a water tank at a water temperature of 25°C-30°C and then cut into particles with a particle size of 2mm-3mm. The particles are dried in an environment of 80°C for 6h to obtain anti-aging masterbatch.

2. The anti-aging and impact-resistant automotive nylon composite bellows according to claim 1, characterized in that: The nylon is nylon 6 and nylon 66, and the weight ratio of nylon 6 to nylon 66 is 1:

2.

3. The anti-aging and impact-resistant automotive nylon composite corrugated pipe according to claim 1, characterized in that: The flame retardant is ferric hydroxide and red phosphorus, and the weight ratio of ferric hydroxide to red phosphorus is 7:

3.

4. The anti-aging and impact-resistant automotive nylon composite bellows according to claim 1, characterized in that: The compatibilizer is maleic anhydride grafted polypropylene.

5. The anti-aging and impact-resistant automotive nylon composite bellows according to claim 1, characterized in that: The toughening agent is maleic anhydride grafted POE.

6. The anti-aging and impact-resistant automotive nylon composite bellows according to claim 1, characterized in that: The impact modifier is methyl methacrylate-butadiene-styrene copolymer.

7. The anti-aging and impact-resistant automotive nylon composite bellows according to claim 1, characterized in that: The anti-aging agent is 2,2,6,6-tetramethyl-4-piperidinol.

8. The anti-aging and impact-resistant automotive nylon composite bellows according to claim 1, characterized in that: The antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

9. A method for preparing an anti-aging and impact-resistant automotive nylon composite corrugated pipe, applicable to an anti-aging and impact-resistant automotive nylon composite corrugated pipe according to any one of claims 1 to 8, characterized in that: The preparation method is: S1: Dry the nylon at 120℃ for 4h and the modified polypropylene at 80℃ for 2h; S2: Mix carbon black and silane coupling agent and process in a high-speed mixer at a speed of 1000 rpm for 10 min; S3: Add modified polypropylene, nylon and compatibilizer into a high-speed mixer at a mixing temperature of 60°C and a mixing time of 5 minutes; S4: adding anti-aging masterbatch, flame retardant, toughening agent, impact modifier and treated carbon black / silane mixture in sequence and mixing for 10 minutes; S5: putting the mixture into a twin-screw extruder for extrusion, the zone temperatures of the twin-screw extruder are 170°C for zone 1, 185°C for zone 2, 190°C for zone 3, 185°C for zone 4 and 180°C for die head, cooling and pelletizing after extrusion, and drying the pellets in an environment of 80°C for 3h; S6: Put the pellets into a single screw extruder, the single screw base and temperature zones are divided into zone 1 180°C, zone 2 200°C, zone 3 210°C and mold 220°C, use a bellows molding mold with a vacuum shaping device to shape, and after shaping, cool and shape in sections in an environment with a water temperature of 20°C to 30°C; S7: annealing the shaped corrugated pipe in an oven at 80° C. for 2 h to obtain a finished nylon composite corrugated pipe.

10. The method for preparing an anti-aging and impact-resistant automotive nylon composite corrugated pipe according to claim 9, characterized in that: The preparation method of the modified polyethylene is: S1: preparing polypropylene particles, perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, Ziegler-Natta catalyst and maleic anhydride grafted polypropylene; S2: Mixing polypropylene granules with maleic anhydride grafted polypropylene, adding the mixture into the main feed port of a twin-screw extruder, and injecting perfluorooctyl vinyl ether, dodecafluoroheptyl methacrylate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and Ziegler-Natta catalyst into the reaction zone of the twin-screw extruder through the feed port, wherein the temperature of the feeding zone is 160° C. to 180° C., the temperature of the melting zone is 190° C. to 210° C., and the temperature of the reaction zone is 200° C. to 220° C.; S3: Cooling, pelletizing, washing and drying the extruded strips to obtain modified polypropylene.

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