CN112048092A - Thermal-oxidative-aging-resistant nylon 6 composite material and preparation method thereof - Google Patents
Thermal-oxidative-aging-resistant nylon 6 composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a thermal-oxidative-aging-resistant nylon 6 composite material and a preparation method thereof, wherein the composite material comprises a nylon substrate, wherein a silicon dioxide layer, a modified carbon nanotube layer and a hard film layer are sequentially arranged on the surface of the nylon substrate; the modified carbon nanotube layer is mainly prepared from dopamine and carbon nanotubes; the nylon matrix comprises the following raw materials: 60-70 parts of nylon 6 resin, 15-20 parts of ABS resin, 5-8 parts of compatilizer, 0.05-0.1 part of carbon black and 1-1.2 parts of antioxidant. The application discloses a nylon 6 composite material with thermal-oxidative aging resistance and a preparation method thereof, ABS doping modification greatly improves the shock resistance of products, and the prepared nylon 6 composite material has excellent mechanical property and thermal-oxidative aging resistance, can be applied to multiple fields, and is high in practicability.
Description
Technical Field
The invention relates to the technical field of nylon materials, in particular to a nylon 6 composite material with thermal-oxidative aging resistance and a preparation method thereof.
Background
Polyamide is commonly known as Nylon (Nylon), called Polyamide (PA for short), has a density of 1.15g/cm3, and is a general name of thermoplastic resins containing repeated amide groups- [ NHCO ] -in the molecular main chain, and comprises aliphatic PA, aliphatic-aromatic PA and aromatic PA. The material has excellent mechanical property, heat resistance, abrasion resistance, chemical resistance and self-lubricating property, is widely applied at present, but the toughness of the material cannot meet the requirements of people.
The ABS resin is an acrylonitrile-butadiene-styrene copolymer which is a thermoplastic high polymer material with high strength, good toughness and easy processing and forming, and the mechanical property of the nylon material can be effectively improved by blending the ABS resin and the nylon.
At present, nylon and ABS resin blended materials are available in the market, although the nylon and ABS resin blended materials have higher mechanical strength, the impact strength still cannot meet the requirements of people, the thermal-oxidative aging resistance is poor, and the application range is narrow, so that the application discloses a thermal-oxidative aging resistant nylon 6 composite material and a preparation method thereof to solve the problem.
Disclosure of Invention
The invention aims to provide a nylon 6 composite material with thermal-oxidative-aging resistance and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the composite material comprises a nylon substrate, wherein a silicon dioxide layer, a modified carbon nanotube layer and a hard film layer are sequentially arranged on the surface of the nylon substrate.
According to an optimized scheme, the modified carbon nanotube layer is mainly prepared from dopamine and carbon nanotubes.
According to an optimized scheme, the hard film layer is a nitride hard film layer, and specifically is any one of aluminum-titanium-nitrogen, aluminum-chromium-nitrogen and aluminum-titanium-silicon-nitrogen.
In an optimized scheme, the silicon dioxide layer is mainly prepared from silicon dioxide with hindered phenol groups grafted on the surface.
According to an optimized scheme, the nylon matrix comprises the following raw materials in parts by weight: 60-70 parts of nylon 6 resin, 15-20 parts of ABS resin, 5-8 parts of compatilizer, 0.05-0.1 part of carbon black and 1-1.2 parts of antioxidant.
In an optimized scheme, the antioxidant is any one or mixture of thioether antioxidant and inorganic phosphate antioxidant.
The preparation method of the nylon 6 composite material with the thermal-oxidative aging resistance comprises the following steps:
1) preparing a nylon matrix:
2) taking a nylon matrix, polishing the nylon matrix in the same direction by a metallographic specimen pre-grinding machine, cleaning the nylon matrix after polishing, soaking the nylon matrix in a sodium hydroxide solution, and cleaning and drying the nylon matrix for later use;
3) stirring isopropanol, ammonia water and deionized water in a constant-temperature water bath, adding the nylon substrate treated in the step 2), dropwise adding tetraethoxysilane, continuously stirring for reaction during dropwise adding, adding a silane coupling agent, continuously reacting, taking out the nylon substrate after reaction, sequentially washing with deionized water and absolute ethyl alcohol, and drying;
4) taking 3, 5-propionic acid and trichloromethane, adding thionyl chloride in a constant-temperature water bath at 50-55 ℃, continuously stirring for reaction, removing trichloromethane and unreacted thionyl chloride, cleaning and drying to obtain a material A; dissolving a material A in toluene, carrying out ultrasonic treatment, putting the nylon matrix treated in the step 3), adding triethylamine, reacting at constant temperature under the protection of nitrogen, taking out the nylon matrix after reaction, and cleaning and drying;
5) taking a carbon nano tube and deionized water, stirring, performing ultrasonic oscillation, adding a Tris-HCl buffer solution, adjusting the pH value with dilute hydrochloric acid, adding dopamine, stirring for 6-8 hours at 25-28 ℃, performing suction filtration, cleaning and drying to obtain a modified carbon nano tube;
6) preparing a dopamine buffer solution from Tris-HCl buffer solution and dopamine, adding the modified carbon nano tube, carrying out ultrasonic oscillation, adding the nylon substrate treated in the step 4), reacting at 25-30 ℃, washing with deionized water, drying, and carrying out magnetron sputtering on the surface to deposit a nitride hard film layer to obtain the nylon 6 composite material.
The optimized scheme comprises the following steps:
1) preparing a nylon matrix: uniformly mixing nylon 6 resin, ABS resin, a compatilizer, carbon black and an antioxidant, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out processing molding to obtain a nylon matrix; in the step 1), raw materials (nylon 6 resin, ABS resin, compatilizer, carbon black and antioxidant) of each component are weighed according to a proportion, the raw materials are blended and extruded to prepare a nylon matrix, the ABS resin is added during preparation of the nylon matrix to toughen the nylon 6 resin so as to improve the mechanical property of the nylon matrix, and meanwhile, the thermal stability and the thermal-oxidative aging resistance of the prepared nylon matrix are improved; during preparation, an antioxidant is also added, wherein the antioxidant comprises but not limited to thioether antioxidant and inorganic phosphate antioxidant, and the thioether antioxidant and the inorganic phosphate antioxidant are synergistic with each other to improve the heat-oxygen aging resistance of the product; in the scheme, a processing aid is added, including but not limited to ethylene bis stearamide, the dispersibility of the components can be further improved by adding the components, and the prepared nylon matrix has excellent mechanical property and thermal-oxidative-aging resistance;
2) taking a nylon matrix, polishing the nylon matrix in the same direction by a metallographic specimen pre-grinding machine, cleaning the nylon matrix after polishing, soaking the nylon matrix in a sodium hydroxide solution for 5-10min, and cleaning and drying the nylon matrix for later use; in the step 2), a metallographic specimen pre-grinding machine is adopted to grind the metallographic specimen, and then the metallographic specimen is placed in a sodium hydroxide solution to be coarsened, so that the surface of a nylon matrix is rough, and the adhesive force of a subsequent silicon dioxide layer is improved;
3) taking isopropanol, ammonia water and deionized water, stirring for 10-20min in a constant-temperature water bath, adding the nylon substrate treated in the step 2), dropwise adding ethyl orthosilicate, continuously stirring and reacting for 0.5-0.8h during dropwise adding, then adding a silane coupling agent, continuously reacting for 0.5-1h, taking out the nylon substrate after reaction, sequentially washing with deionized water and absolute ethyl alcohol, and drying; in the step 3), isopropanol, ammonia water and tetraethoxysilane are used as raw materials, a sol-gel method is adopted to prepare the silicon dioxide microspheres, the silicon dioxide microspheres are adsorbed on the surface of a nylon substrate to form a film, and then the surface of the nylon substrate is subjected to surface grafting modification by a silane coupling agent, so that subsequent hindered phenol group grafting is facilitated;
4) taking 3, 5-propionic acid and trichloromethane, adding thionyl chloride in a constant-temperature water bath at 50-55 ℃, continuously stirring for reacting for 5-5.5h, removing trichloromethane and unreacted thionyl chloride, cleaning and drying to obtain a material A; dissolving the material A in toluene, carrying out ultrasonic treatment for 20-30min, adding the nylon matrix treated in the step 3), adding triethylamine, reacting at the constant temperature of 50-60 ℃ for 18-20h under the protection of nitrogen, taking out the nylon matrix after reaction, and cleaning and drying; in the step 4), 3, 5-propionic acid, trichloromethane and thionyl chloride are used as raw materials to react to prepare beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, and the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is grafted to the surface of a silicon dioxide microsphere, so that a silicon dioxide layer is formed on the surface of a nylon substrate; at present, the technology also discloses that organic molecules with antioxidant capacity are grafted on the surface of nano silicon dioxide through a silane coupling agent, but the organic molecules are generally added in the preparation process of a nylon matrix and are mixed with nylon 6 resin for melt extrusion molding, but the organic molecules are modified by the application and are arranged on the surface of the nylon matrix to form a silicon dioxide layer, so that the aim of avoiding the condition that the silicon dioxide grafted with the organic molecules with antioxidant capacity is not uniformly dispersed in the nylon matrix is achieved, and the processing difficulty and the cost are improved; on the other hand, the nylon film is arranged on the surface of a nylon substrate to form a film layer, so that a certain physical isolation effect on oxygen can be achieved in a high-temperature environment, and the thermal-oxidative aging resistance of the product is further improved; the silicon dioxide layer can also be used as a transition layer between the carbon nano tube and the nylon matrix to ensure the product performance;
5) taking a carbon nano tube and deionized water, stirring for 10-15min, ultrasonically oscillating for 20-30min, adding Tris-HCl buffer solution, adjusting the pH to 8-9 with dilute hydrochloric acid, adding dopamine, stirring for 6-8h at 25-28 ℃, carrying out suction filtration, cleaning and drying to obtain a modified carbon nano tube;
6) preparing a dopamine buffer solution from Tris-HCl buffer solution and dopamine, adding the modified carbon nano tube, carrying out ultrasonic oscillation for 20-30min, adding the nylon substrate treated in the step 4), reacting for 20-24h at 25-30 ℃, washing with deionized water, drying, and carrying out magnetron sputtering on the surface to deposit a nitride hard film layer to obtain the nylon 6 composite material. Modifying the carbon nano tube in the step 5) to prepare the carbon nano tube coated with the polydopamine, and placing the carbon nano tube and the nylon substrate treated in the step 4) into a dopamine buffer solution together to form a modified carbon nano tube layer on the surface of the nylon substrate.
The carbon nano tube can be used as a basic unit for forming a macroscopic material with high porosity, light weight and good compression performance, has excellent shock resistance and buffer performance, and the mechanical property and shock resistance of a product can be effectively improved by arranging the modified carbon nano tube layer; the dopamine is used for modifying the carbon nano tube, and the main purpose is to improve the dispersion performance of the carbon nano tube, and meanwhile, the surface of the carbon nano tube is coated with the polydopamine, so that the impact resistance of the modified carbon nano tube layer can be further improved, and meanwhile, the dopamine can be effectively adsorbed on the surface of a polydopamine layer formed on the surface of a silicon dioxide layer, and the polydopamine is excellent in adhesive force and uniform in dispersion; after the modified carbon nanotube layer is prepared, the nitride hard film layer is prepared on the surface of the modified carbon nanotube layer, when the composite material is subjected to frontal impact, the physical acting force between the carbon nanotubes is poor, the impact load cannot be transversely transferred among the tubes, and the stress concentration phenomenon easily occurs, so that the impact area structure is broken, and the material outside the area cannot be effectively utilized.
Meanwhile, the thermal oxidation aging resistance of the product can be improved through the steps of modifying the carbon nanotube layer, coating poly dopamine, depositing a hard film and the like, a certain physical isolation effect on oxygen is achieved in a high-temperature environment, and the thermal oxidation aging resistance of the product is further improved.
In an optimized scheme, in the step 3), the silane coupling agent is KH-550.
The optimized proposal is that when the nitride hard film layer is deposited in the step 6), the temperature is 60-70 DEG C
Compared with the prior art, the invention has the following beneficial effects:
the application discloses a nylon 6 composite material with thermal-oxidative aging resistance and a preparation method thereof, ABS doping modification greatly improves the shock resistance of products, and the prepared nylon 6 composite material has excellent mechanical property and thermal-oxidative aging resistance, can be applied to multiple fields, and is high in practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a nylon 6 composite material with thermal-oxidative aging resistance comprises the following steps:
the method comprises the following steps: preparing a nylon matrix: uniformly mixing nylon 6 resin, ABS resin, a compatilizer, carbon black and an antioxidant, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out processing molding to obtain a nylon matrix;
step two: taking a nylon matrix, polishing the nylon matrix in the same direction by a metallographic specimen pre-grinding machine, cleaning the nylon matrix after polishing, soaking the nylon matrix in a sodium hydroxide solution for 5min, and cleaning and drying the nylon matrix for later use;
step three: stirring isopropanol, ammonia water and deionized water in a constant-temperature water bath for 10min, adding the nylon substrate treated in the step two, dropwise adding tetraethoxysilane, continuously stirring and reacting for 0.5h during dropwise adding, then adding a silane coupling agent, continuously reacting for 0.5h, taking out the nylon substrate after reaction, sequentially cleaning with deionized water and absolute ethyl alcohol, and drying; the silane coupling agent is KH-550.
Step four: taking 3, 5-propionic acid and trichloromethane, adding thionyl chloride in a constant-temperature water bath at 50 ℃, continuously stirring for reacting for 5 hours, removing trichloromethane and unreacted thionyl chloride, cleaning and drying to obtain a material A; dissolving the material A in toluene, performing ultrasonic treatment for 20min, adding the nylon matrix treated in the third step, adding triethylamine, reacting at the constant temperature of 50 ℃ for 18h under the protection of nitrogen, taking out the nylon matrix after reaction, and cleaning and drying;
step five: taking a carbon nano tube and deionized water, stirring for 10min, ultrasonically oscillating for 20min, adding a Tris-HCl buffer solution, adjusting the pH value to 8 with dilute hydrochloric acid, adding dopamine, stirring for 6h at 25 ℃, performing suction filtration and cleaning, and drying to obtain a modified carbon nano tube;
step six: preparing a dopamine buffer solution from Tris-HCl buffer solution and dopamine, adding the modified carbon nano tube, carrying out ultrasonic oscillation for 20min, adding the nylon substrate treated in the fourth step, reacting for 20h at 25 ℃, washing with deionized water, drying, and carrying out magnetron sputtering on the surface to deposit a nitride hard film layer to obtain the nylon 6 composite material; when the nitride hard film layer is deposited, the temperature is controlled at 60 ℃.
In this embodiment, the nylon substrate comprises the following raw materials: 60 parts of nylon 6 resin, 15 parts of ABS resin, 5 parts of compatilizer, 0.05 part of carbon black and 1 part of antioxidant. The hard film layer is a nitride hard film layer, in particular an aluminum titanium nitrogen film layer; the antioxidant is thioether antioxidant.
Example 2:
a preparation method of a nylon 6 composite material with thermal-oxidative aging resistance comprises the following steps:
the method comprises the following steps: preparing a nylon matrix: uniformly mixing nylon 6 resin, ABS resin, a compatilizer, carbon black and an antioxidant, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out processing molding to obtain a nylon matrix;
step two: taking a nylon matrix, polishing the nylon matrix in the same direction by adopting a metallographic specimen pre-grinding machine, cleaning the nylon matrix after polishing, soaking the nylon matrix in a sodium hydroxide solution for 8min, and cleaning and drying the nylon matrix for later use;
step three: stirring isopropanol, ammonia water and deionized water in a constant-temperature water bath for 15min, adding the nylon substrate treated in the step two, dropwise adding tetraethoxysilane, continuously stirring and reacting for 0.7h during dropwise adding, then adding a silane coupling agent, continuously reacting for 0.8h, taking out the nylon substrate after reaction, sequentially cleaning with deionized water and absolute ethyl alcohol, and drying; the silane coupling agent is KH-550.
Step four: taking 3, 5-propionic acid and trichloromethane, adding thionyl chloride in a constant-temperature water bath at 52 ℃, continuously stirring for reacting for 5.2 hours, removing trichloromethane and unreacted thionyl chloride, and cleaning and drying to obtain a material A; dissolving the material A in toluene, performing ultrasonic treatment for 25min, adding the nylon matrix treated in the third step, adding triethylamine, reacting at the constant temperature of 55 ℃ for 19h under the protection of nitrogen, taking out the nylon matrix after reaction, and cleaning and drying;
step five: taking a carbon nano tube and deionized water, stirring for 12min, carrying out ultrasonic oscillation for 25min, adding a Tris-HCl buffer solution, adjusting the pH value to 8.5 by using dilute hydrochloric acid, adding dopamine, stirring for 7h at the temperature of 27 ℃, carrying out suction filtration, cleaning and drying to obtain a modified carbon nano tube;
step six: preparing a dopamine buffer solution from Tris-HCl buffer solution and dopamine, adding the modified carbon nano tube, carrying out ultrasonic oscillation for 25min, adding the nylon substrate treated in the fourth step, reacting for 22h at 28 ℃, washing with deionized water, drying, and carrying out magnetron sputtering on the surface to deposit a nitride hard film layer to obtain the nylon 6 composite material; when the nitride hard film layer is deposited, the temperature is controlled to be 65 ℃.
In this embodiment, the nylon substrate comprises the following raw materials: by weight, 65 parts of nylon 6 resin, 18 parts of ABS resin, 7 parts of compatilizer, 0.08 part of carbon black and 1.1 part of antioxidant. The hard film layer is a nitride hard film layer, in particular to aluminum chromium nitrogen; the antioxidant is inorganic phosphate antioxidant.
Example 3:
a preparation method of a nylon 6 composite material with thermal-oxidative aging resistance comprises the following steps:
the method comprises the following steps: preparing a nylon matrix: uniformly mixing nylon 6 resin, ABS resin, a compatilizer, carbon black and an antioxidant, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out processing molding to obtain a nylon matrix;
step two: taking a nylon matrix, polishing the nylon matrix in the same direction by a metallographic specimen pre-grinding machine, cleaning the nylon matrix after polishing, soaking the nylon matrix in a sodium hydroxide solution for 10min, and cleaning and drying the nylon matrix for later use;
step three: stirring isopropanol, ammonia water and deionized water in a constant-temperature water bath for 20min, adding the nylon substrate treated in the step two, dropwise adding tetraethoxysilane, continuously stirring and reacting for 0.8h during dropwise adding, then adding a silane coupling agent, continuously reacting for 1h, taking out the nylon substrate after reaction, sequentially cleaning with deionized water and absolute ethyl alcohol, and drying; the silane coupling agent is KH-550.
Step four: taking 3, 5-propionic acid and trichloromethane, adding thionyl chloride in a constant-temperature water bath at 55 ℃, continuously stirring for reacting for 5.5 hours, removing trichloromethane and unreacted thionyl chloride, and cleaning and drying to obtain a material A; dissolving the material A in toluene, performing ultrasonic treatment for 30min, adding the nylon matrix treated in the third step, adding triethylamine, reacting at the constant temperature of 60 ℃ for 20h under the protection of nitrogen, taking out the nylon matrix after reaction, and cleaning and drying;
step five: taking a carbon nano tube and deionized water, stirring for 15min, ultrasonically oscillating for 30min, adding Tris-HCl buffer solution, adjusting the pH value to 9 with dilute hydrochloric acid, adding dopamine, stirring for 8h at 28 ℃, performing suction filtration and cleaning, and drying to obtain a modified carbon nano tube;
step six: preparing a dopamine buffer solution from Tris-HCl buffer solution and dopamine, adding the modified carbon nano tube, carrying out ultrasonic oscillation for 30min, adding the nylon substrate treated in the fourth step, reacting for 24h at 30 ℃, washing with deionized water, drying, and carrying out magnetron sputtering on the surface to deposit a nitride hard film layer to obtain the nylon 6 composite material; when the nitride hard film layer is deposited, the temperature is controlled at 70 ℃.
In this embodiment, the nylon substrate comprises the following raw materials: by weight, 70 parts of nylon 6 resin, 20 parts of ABS resin, 8 parts of compatilizer, 0.1 part of carbon black and 1.2 parts of antioxidant. The hard film layer is a nitride hard film layer, in particular to aluminum titanium silicon nitrogen; the antioxidant is a mixture of thioether antioxidant and inorganic phosphate antioxidant.
Examples 1-3 were prepared according to the protocol disclosed in the present application, and the performance of the nylon 6 composite material prepared therefrom was tested, with the following specific test data:
| item | Detection method | Example 1 | Example 2 | Example 3 |
| Tensile Strength (MPa) | ISO 527 (speed 10 mm/min) | 79 | 81 | 82 |
| Flexural Strength (MPa) | ISO 178 (speed 10 mm/min) | 128 | 134 | 136 |
| Notched impact Strength (KJ/m)2） | ISO 180 | 18.1 | 18.7 | 18.9 |
| Tensile strength retention (%) after 136 ℃' 168h hot air aging | / | 94.5 | 95.1 | 95.1 |
| Notched impact strength retention (%) | / | 93.7 | 94.2 | 94.3 |
Comparative example 1:
a preparation method of a nylon 6 composite material with thermal-oxidative aging resistance comprises the following steps:
the method comprises the following steps: preparing a nylon matrix: uniformly mixing nylon 6 resin, ABS resin, a compatilizer, carbon black and an antioxidant, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out processing molding to obtain a nylon matrix;
step two: taking a nylon matrix, polishing the nylon matrix in the same direction by adopting a metallographic specimen pre-grinding machine, cleaning the nylon matrix after polishing, soaking the nylon matrix in a sodium hydroxide solution for 8min, and cleaning and drying the nylon matrix for later use;
step three: stirring isopropanol, ammonia water and deionized water in a constant-temperature water bath for 15min, adding the nylon substrate treated in the step two, dropwise adding tetraethoxysilane, continuously stirring and reacting for 0.7h during dropwise adding, then adding a silane coupling agent, continuously reacting for 0.8h, taking out the nylon substrate after reaction, sequentially cleaning with deionized water and absolute ethyl alcohol, and drying; the silane coupling agent is KH-550.
Step four: taking 3, 5-propionic acid and trichloromethane, adding thionyl chloride in a constant-temperature water bath at 52 ℃, continuously stirring for reacting for 5.2 hours, removing trichloromethane and unreacted thionyl chloride, and cleaning and drying to obtain a material A; dissolving the material A in toluene, performing ultrasonic treatment for 25min, adding the nylon matrix treated in the third step, adding triethylamine, reacting at the constant temperature of 55 ℃ for 19h under the protection of nitrogen, taking out the nylon matrix after reaction, and cleaning and drying;
step five: taking a carbon nano tube and deionized water, stirring for 12min, carrying out ultrasonic oscillation for 25min, adding a Tris-HCl buffer solution, adjusting the pH value to 8.5 by using dilute hydrochloric acid, adding dopamine, stirring for 7h at the temperature of 27 ℃, carrying out suction filtration, cleaning and drying to obtain a modified carbon nano tube;
step six: and (3) preparing a dopamine buffer solution from Tris-HCl buffer solution and dopamine, adding the modified carbon nano tube, carrying out ultrasonic oscillation for 25min, adding the nylon substrate treated in the fourth step, reacting for 22h at 28 ℃, and washing with deionized water to obtain the nylon 6 composite material.
In this embodiment, the nylon substrate comprises the following raw materials: by weight, 65 parts of nylon 6 resin, 18 parts of ABS resin, 7 parts of compatilizer, 0.08 part of carbon black and 1.1 part of antioxidant. The antioxidant is inorganic phosphate antioxidant.
Comparative example 2:
a preparation method of a nylon 6 composite material with thermal-oxidative aging resistance comprises the following steps:
the method comprises the following steps: preparing a nylon matrix: uniformly mixing nylon 6 resin, ABS resin, a compatilizer, carbon black and an antioxidant, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out processing molding to obtain a nylon matrix;
step two: taking a nylon matrix, polishing the nylon matrix in the same direction by adopting a metallographic specimen pre-grinding machine, cleaning the nylon matrix after polishing, soaking the nylon matrix in a sodium hydroxide solution for 8min, and cleaning and drying the nylon matrix for later use;
step three: stirring isopropanol, ammonia water and deionized water in a constant-temperature water bath for 15min, adding the nylon substrate treated in the step two, dropwise adding tetraethoxysilane, continuously stirring and reacting for 0.7h during dropwise adding, then adding a silane coupling agent, continuously reacting for 0.8h, taking out the nylon substrate after reaction, sequentially cleaning with deionized water and absolute ethyl alcohol, and drying; the silane coupling agent is KH-550.
Step four: taking 3, 5-propionic acid and trichloromethane, adding thionyl chloride in a constant-temperature water bath at 52 ℃, continuously stirring for reacting for 5.2 hours, removing trichloromethane and unreacted thionyl chloride, and cleaning and drying to obtain a material A; dissolving the material A in toluene, performing ultrasonic treatment for 25min, adding the nylon matrix treated in the third step, adding triethylamine, reacting at the constant temperature of 55 ℃ for 19h under the protection of nitrogen, taking out the nylon matrix after reaction, and cleaning and drying;
step five: and (3) preparing a dopamine buffer solution from Tris-HCl buffer solution and dopamine, then adding the carbon nano tube, carrying out ultrasonic oscillation for 25min, then adding the nylon substrate treated in the fourth step, reacting for 22h at 28 ℃, and washing with deionized water to obtain the nylon 6 composite material.
In this embodiment, the nylon substrate comprises the following raw materials: by weight, 65 parts of nylon 6 resin, 18 parts of ABS resin, 7 parts of compatilizer, 0.08 part of carbon black and 1.1 part of antioxidant. The antioxidant is inorganic phosphate antioxidant.
Comparative example 3:
a preparation method of a nylon 6 composite material with thermal-oxidative aging resistance comprises the following steps:
the method comprises the following steps: preparing a nylon matrix: uniformly mixing nylon 6 resin, ABS resin, a compatilizer, carbon black and an antioxidant, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out processing molding to obtain a nylon matrix;
step two: taking a nylon matrix, polishing the nylon matrix in the same direction by adopting a metallographic specimen pre-grinding machine, cleaning the nylon matrix after polishing, soaking the nylon matrix in a sodium hydroxide solution for 8min, and cleaning and drying the nylon matrix for later use;
step three: stirring isopropanol, ammonia water and deionized water in a constant-temperature water bath for 15min, adding the nylon substrate treated in the step two, dropwise adding tetraethoxysilane, continuously stirring and reacting for 0.7h during dropwise adding, then adding a silane coupling agent, continuously reacting for 0.8h, taking out the nylon substrate after reaction, sequentially cleaning with deionized water and absolute ethyl alcohol, and drying; the silane coupling agent is KH-550.
Step four: taking 3, 5-propionic acid and trichloromethane, adding thionyl chloride in a constant-temperature water bath at 52 ℃, continuously stirring for reacting for 5.2 hours, removing trichloromethane and unreacted thionyl chloride, and cleaning and drying to obtain a material A; and (3) dissolving the material A in toluene, carrying out ultrasonic treatment for 25min, adding the nylon matrix treated in the third step, adding triethylamine, reacting at the constant temperature of 55 ℃ for 19h under the protection of nitrogen, taking out the nylon matrix after reaction, and cleaning and drying to obtain the nylon 6 composite material.
In this embodiment, the nylon substrate comprises the following raw materials: by weight, 65 parts of nylon 6 resin, 18 parts of ABS resin, 7 parts of compatilizer, 0.08 part of carbon black and 1.1 part of antioxidant. The antioxidant is inorganic phosphate antioxidant.
Comparative example 4:
a preparation method of a nylon 6 composite material with thermal-oxidative aging resistance comprises the following steps:
the method comprises the following steps: preparing a nylon matrix: and (2) uniformly mixing nylon 6 resin, ABS resin, a compatilizer, carbon black and an antioxidant, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out processing molding to obtain the nylon 6 composite material.
In this embodiment, the nylon substrate comprises the following raw materials: by weight, 65 parts of nylon 6 resin, 18 parts of ABS resin, 7 parts of compatilizer, 0.08 part of carbon black and 1.1 part of antioxidant. The antioxidant is inorganic phosphate antioxidant.
| Item | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Tensile Strength (MPa) | 81 | 73 | 69 | 58 | 46 |
| Flexural Strength (MPa) | 134 | 120 | 115 | 101 | 90 |
| Notched impact Strength (KJ/m)2） | 18.7 | 15.4 | 13.6 | 11.0 | 9.7 |
| Tensile strength retention (%) after 136 ℃' 168h hot air aging | 95.1 | 87.3 | 81.4 | 71.2 | 63.4 |
| Notched impact strength retention (%) | 94.2 | 84.6 | 80.2 | 70.4 | 62.7 |
From the above, taking example 2 as an experimental group, the present application sets 4 group pair proportions, specifically, examples 1 to 4, wherein:
comparative example 1 was modified based on example 2, in comparative example 1, no nitride hard film layer was deposited, and other process parameters and component contents were consistent with example 2.
Comparative example 2 is improved on the basis of comparative example 1, in comparative example 2, the deposition of the nitride hard film layer is not carried out, the carbon nanotube layer is prepared by only adopting the common carbon nanotube, and other step parameters and component contents are consistent with those of example 2.
Comparative example 3 was improved based on comparative example 2, in comparative example 3, the deposition of the nitride hard film layer was not performed, the modified carbon nanotube layer was not prepared, and other process parameters and component contents were consistent with those of example 2.
Comparative example 4 was improved on the basis of comparative example 3, in comparative example 4, the deposition of the nitride hard film layer, the preparation of the modified carbon nanotube layer, and the preparation of the silicon dioxide layer were not performed, and other process parameters and component contents were the same as those of example 2.
The data show that the ABS doping modification greatly improves the impact resistance of the product, and the prepared nylon 6 composite material has excellent mechanical property and thermal-oxidative-aging resistance, can be applied to multiple fields, and has high practicability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A nylon 6 composite material with thermal-oxidative aging resistance is characterized in that: the composite material comprises a nylon substrate, wherein a silicon dioxide layer, a modified carbon nanotube layer and a hard film layer are sequentially arranged on the surface of the nylon substrate.
2. The thermo-oxidative aging resistant nylon 6 composite material of claim 1, wherein: the modified carbon nanotube layer is mainly prepared from dopamine and carbon nanotubes.
3. The thermo-oxidative aging resistant nylon 6 composite material of claim 1, wherein: the hard film layer is a nitride hard film layer, and specifically is any one of aluminum-titanium-nitrogen, aluminum-chromium-nitrogen and aluminum-titanium-silicon-nitrogen.
4. The thermo-oxidative aging resistant nylon 6 composite material of claim 1, wherein: the silicon dioxide layer is mainly prepared from silicon dioxide with a surface grafted with hindered phenol groups.
5. The thermo-oxidative aging resistant nylon 6 composite material of claim 1, wherein: the nylon matrix comprises the following raw materials: 60-70 parts of nylon 6 resin, 15-20 parts of ABS resin, 5-8 parts of compatilizer, 0.05-0.1 part of carbon black and 1-1.2 parts of antioxidant.
6. The thermo-oxidative aging resistant nylon 6 composite material of claim 5, wherein: the antioxidant is any one or mixture of thioether antioxidant and inorganic phosphate antioxidant.
7. A preparation method of a nylon 6 composite material with thermal-oxidative aging resistance is characterized by comprising the following steps: the method comprises the following steps:
1) preparing a nylon matrix:
2) taking a nylon matrix, polishing the nylon matrix in the same direction by a metallographic specimen pre-grinding machine, cleaning the nylon matrix after polishing, soaking the nylon matrix in a sodium hydroxide solution, and cleaning and drying the nylon matrix for later use;
3) stirring isopropanol, ammonia water and deionized water in a constant-temperature water bath, adding the nylon substrate treated in the step 2), dropwise adding tetraethoxysilane, continuously stirring for reaction during dropwise adding, adding a silane coupling agent, continuously reacting, taking out the nylon substrate after reaction, sequentially washing with deionized water and absolute ethyl alcohol, and drying;
4) taking 3, 5-propionic acid and trichloromethane, adding thionyl chloride in a constant-temperature water bath at 50-55 ℃, continuously stirring for reaction, removing trichloromethane and unreacted thionyl chloride, cleaning and drying to obtain a material A; dissolving a material A in toluene, carrying out ultrasonic treatment, putting the nylon matrix treated in the step 3), adding triethylamine, reacting at constant temperature under the protection of nitrogen, taking out the nylon matrix after reaction, and cleaning and drying;
5) taking a carbon nano tube and deionized water, stirring, performing ultrasonic oscillation, adding a Tris-HCl buffer solution, adjusting the pH value with dilute hydrochloric acid, adding dopamine, stirring for 6-8 hours at 25-28 ℃, performing suction filtration, cleaning and drying to obtain a modified carbon nano tube;
6) preparing a dopamine buffer solution from Tris-HCl buffer solution and dopamine, adding the modified carbon nano tube, carrying out ultrasonic oscillation, adding the nylon substrate treated in the step 4), reacting at 25-30 ℃, washing with deionized water, drying, and carrying out magnetron sputtering on the surface to deposit a nitride hard film layer to obtain the nylon 6 composite material.
8. The method for preparing nylon 6 composite material with thermal-oxidative aging resistance according to claim 7, which is characterized in that: the method comprises the following steps:
1) preparing a nylon matrix: uniformly mixing nylon 6 resin, ABS resin, a compatilizer, carbon black and an antioxidant, putting the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out processing molding to obtain a nylon matrix;
2) taking a nylon matrix, polishing the nylon matrix in the same direction by a metallographic specimen pre-grinding machine, cleaning the nylon matrix after polishing, soaking the nylon matrix in a sodium hydroxide solution for 5-10min, and cleaning and drying the nylon matrix for later use;
3) taking isopropanol, ammonia water and deionized water, stirring for 10-20min in a constant-temperature water bath, adding the nylon substrate treated in the step 2), dropwise adding ethyl orthosilicate, continuously stirring and reacting for 0.5-0.8h during dropwise adding, then adding a silane coupling agent, continuously reacting for 0.5-1h, taking out the nylon substrate after reaction, sequentially washing with deionized water and absolute ethyl alcohol, and drying;
4) taking 3, 5-propionic acid and trichloromethane, adding thionyl chloride in a constant-temperature water bath at 50-55 ℃, continuously stirring for reacting for 5-5.5h, removing trichloromethane and unreacted thionyl chloride, cleaning and drying to obtain a material A; dissolving the material A in toluene, carrying out ultrasonic treatment for 20-30min, adding the nylon matrix treated in the step 3), adding triethylamine, reacting at the constant temperature of 50-60 ℃ for 18-20h under the protection of nitrogen, taking out the nylon matrix after reaction, and cleaning and drying;
5) taking a carbon nano tube and deionized water, stirring for 10-15min, ultrasonically oscillating for 20-30min, adding Tris-HCl buffer solution, adjusting the pH to 8-9 with dilute hydrochloric acid, adding dopamine, stirring for 6-8h at 25-28 ℃, carrying out suction filtration, cleaning and drying to obtain a modified carbon nano tube;
6) preparing a dopamine buffer solution from Tris-HCl buffer solution and dopamine, adding the modified carbon nano tube, carrying out ultrasonic oscillation for 20-30min, adding the nylon substrate treated in the step 4), reacting for 20-24h at 25-30 ℃, washing with deionized water, drying, and carrying out magnetron sputtering on the surface to deposit a nitride hard film layer to obtain the nylon 6 composite material.
9. The method for preparing nylon 6 composite material with thermal-oxidative aging resistance according to claim 8, which is characterized in that: in the step 3), the silane coupling agent is KH-550.
10. The method for preparing nylon 6 composite material with thermal-oxidative aging resistance according to claim 8, which is characterized in that: and 6) depositing the nitride hard film layer at the temperature of 60-70 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114957861A (en) * | 2022-08-02 | 2022-08-30 | 山东寿光鲁清石化有限公司 | Polypropylene material and preparation method thereof |
| CN115572478A (en) * | 2022-10-28 | 2023-01-06 | 宁波坚锋新材料有限公司 | High-performance flame-retardant PA6 based on fishing net wire reclaimed materials and preparation method thereof |
| CN117467401A (en) * | 2023-12-04 | 2024-01-30 | 佛山市顺德区创世纪实业有限公司 | Anti-aging silicone sealant and preparation method thereof |
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2020
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114957861A (en) * | 2022-08-02 | 2022-08-30 | 山东寿光鲁清石化有限公司 | Polypropylene material and preparation method thereof |
| CN114957861B (en) * | 2022-08-02 | 2022-10-11 | 山东寿光鲁清石化有限公司 | Polypropylene material and preparation method thereof |
| CN115572478A (en) * | 2022-10-28 | 2023-01-06 | 宁波坚锋新材料有限公司 | High-performance flame-retardant PA6 based on fishing net wire reclaimed materials and preparation method thereof |
| CN115572478B (en) * | 2022-10-28 | 2024-02-13 | 宁波坚锋新材料有限公司 | High-performance flame-retardant PA6 based on fishing net filament reclaimed material and preparation method thereof |
| CN117467401A (en) * | 2023-12-04 | 2024-01-30 | 佛山市顺德区创世纪实业有限公司 | Anti-aging silicone sealant and preparation method thereof |
| CN117467401B (en) * | 2023-12-04 | 2024-05-24 | 佛山市顺德区创世纪实业有限公司 | Anti-aging silicone sealant and preparation method thereof |
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