Preparation method and application of anti-xenon lamp exposure aging black halogen-free flame-retardant nylon

Abstract

The application provides a preparation method and application of a black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging. The preparation raw material of the black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging comprises the following components in percentage by weight: 100% of polyamide resin 30-50%, glass fiber 10-30%, halogen-free flame retardant compound 10-30%, antioxidant 1-3%, water-oxygen barrier modifier 5-15%, and black masterbatch 1-3%. The black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging prepared by the preparation method of the application can meet the long-term outdoor use requirements, has excellent xenon lamp exposure aging resistance and flame-retardant performance, and is widely applied to automobile accessories.

Description

Technical Field

[0001] This invention relates to the field of nylon materials, and in particular to a method for preparing and applying a black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging. Background Technology

[0002] With the continuous advancement of science and technology, polymer materials are being used more and more widely in various fields. Nylon, as an important engineering plastic, has excellent mechanical properties, heat resistance, wear resistance, and chemical corrosion resistance, and is widely used in electronics, automobiles, aerospace, and other fields.

[0003] Nylon materials are affected by various environmental factors during use, such as light, temperature, humidity, and oxygen, leading to a gradual decline in their performance and aging. Light exposure is one of the main factors causing nylon aging. Xenon lamps, as a light source simulating sunlight, have high intensity and high energy, which can accelerate the aging process of nylon materials. Aging of nylon materials exposed to xenon lamps mainly manifests as color changes, decreased mechanical properties, and surface cracks. Aging nylon materials not only suffer from a decline in appearance quality but also experience a significant reduction in mechanical properties and service life, thus affecting their applications in various fields.

[0004] Nylon is a flammable material that produces large amounts of smoke and toxic gases during combustion, posing a serious threat to people's lives and property. Plastic parts used in new energy vehicles need to have good flame-retardant properties to improve the safety of these vehicles. To improve the flame-retardant properties of nylon, flame retardants are commonly added. Traditional flame retardants mainly include halogenated and phosphorus-based flame retardants. While halogenated flame retardants have good flame-retardant effects, they produce large amounts of smoke and toxic gases during combustion, causing serious harm to the environment and human health. Phosphorus-based flame retardants, although relatively environmentally friendly, also have some problems, such as low flame-retardant efficiency and poor compatibility with nylon. To solve the flame-retardant problem of nylon while meeting environmental protection requirements, extensive research has been conducted on halogen-free flame-retardant reinforced nylon. Currently, halogen-free flame-retardant reinforced nylon mainly improves its flame-retardant properties by adding halogen-free combustion improvers, nanocomposite materials, and reactive flame retardants.

[0005] Current halogen-free flame-retardant reinforced nylon materials have some problems in resisting xenon lamp exposure aging, such as poor aging resistance and large color changes. Therefore, the SAE-2527 standard specifies the aging test methods and performance requirements for automotive materials under xenon lamp exposure, providing a reference for the selection and design of automotive materials and offering valuable insights for the research of halogen-free flame-retardant reinforced nylons resistant to xenon lamp exposure aging.

[0006] In view of the problems existing in the prior art, this application aims to solve the problems of poor flame retardancy of nylon materials, severe aging under xenon lamp exposure, large color changes, and decreased mechanical properties. Summary of the Invention

[0007] Purpose of the invention: The purpose of this invention is to provide a method for preparing black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging, so that the prepared black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging can solve the problems of poor flame retardancy of nylon materials, severe aging under xenon lamp exposure, large color change, and decreased mechanical properties.

[0008] The technical solution of this invention:

[0009] This invention discloses a method for preparing xenon lamp-resistant, aging-resistant, black, halogen-free, flame-retardant nylon. The method is characterized in that the raw materials for preparing the xenon lamp-resistant, aging-resistant, black, halogen-free, flame-retardant nylon, by weight percentage (100%), comprise the following components: 30-50% polyamide resin, 10-30% glass fiber, 10-30% halogen-free flame retardant compound, 1-3% antioxidant, 5-15% water-oxygen barrier modifier, and 1-3% black masterbatch.

[0010] Furthermore, the polyamide resin has a weight-average molecular weight of 18–25 kDa.

[0011] Furthermore, the halogen-free flame retardant compound is prepared by mixing nano-silica, zinc borate, magnesium hydroxide and ammonium polyphosphate; the mass ratio of nano-silica, zinc borate, magnesium hydroxide and ammonium polyphosphate is 10-20:1:2-5:8-20.

[0012] Furthermore, the water and oxygen barrier modifier is prepared by reacting ethyl oleate, bis(acetylacetonyl)diisopropyl titanate, and tea polyphenols.

[0013] The preparation of the water-oxygen barrier modifier includes the following steps:

[0014] S1: Add an appropriate amount of toluene to a reaction vessel equipped with a stirrer, thermometer, and reflux condenser, and heat it to a certain temperature;

[0015] S2: Add ethyl oleate to the reaction vessel of step S1, stir to dissolve it completely, and then slowly add bis(acetylacetonyl)diisopropyl titanate dropwise while stirring during the dropwise addition. After the dropwise addition is complete, react at a certain temperature for a period of time.

[0016] S3: After the reaction is complete, add tea polyphenols slowly in batches to the reaction vessel of step S2, and raise the temperature to react for a period of time.

[0017] S4: After the reaction is complete, the reaction product is cooled to room temperature, then filtered, distilled and purified to obtain the water and oxygen barrier modifier.

[0018] Furthermore, the mass ratio of ethyl oleate, bis(acetylacetonyl)diisopropyl titanate, and tea polyphenols is 5-10:0.5-2:1.

[0019] This application provides a method for preparing a black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging, characterized by comprising the following steps:

[0020] Step 1: Add polyamide resin, halogen-free flame retardant compound, antioxidant, water and oxygen barrier modifier and black masterbatch to a high-speed mixer for premixing. The speed of the high-speed mixer is 500-1000 rpm and the mixing time is 5-10 minutes.

[0021] Step 2: Immerse the glass fiber in a 1-3% (w / w) silane coupling agent solution for 10-30 minutes. After immersion, remove the glass fiber, air dry, and set aside.

[0022] Step 3: Add the premixed material from Step 1 and the soaked glass fiber from Step 2 into a twin-screw extruder for extrusion granulation. The extrusion temperature is 200-260℃ and the screw speed is 100-300 rpm.

[0023] Step 4: After extruding the material, cool and vacuum dry to obtain black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging.

[0024] Furthermore, the heating temperature in step S1 is 80-100℃; the stirring speed in step S2 is 100-300 rpm, the reaction temperature is 80-100℃, and the reaction time is 2-4 hours; the reaction temperature in step S3 is 100-120℃, and the reaction time is 4-6 hours.

[0025] Furthermore, the antioxidant is one or more of antioxidant 1098, antioxidant 1010, antioxidant 1216, and antioxidant 1330.

[0026] This application also provides a method for preparing xenon lamp exposure-resistant black halogen-free flame-retardant nylon, and the application of the prepared xenon lamp exposure-resistant black halogen-free flame-retardant nylon in automotive plastic parts or automotive engine peripheral parts.

[0027] Ethyl oleate, bis(acetylacetonyl)diisopropyl titanate, and tea polyphenols, after reaction, form a water and oxygen barrier modifier. Through their individual effects and synergistic interactions, they achieve excellent water and oxygen barrier and anti-aging effects in nylon materials. The functions of ethyl oleate include: providing hydrophobic properties; as a fatty acid ester, ethyl oleate is hydrophobic. In nylon materials, it can form a hydrophobic layer on the surface and inside the material, preventing water penetration and absorption. Water is a major factor leading to material aging; reducing water ingress can improve the material's water resistance and stability, thereby indirectly improving its anti-aging performance. It also acts as an auxiliary dispersant, helping other components to disperse better in the nylon matrix. For example, it can make halogen-free flame retardant compounding agents and antioxidants more uniformly dispersed in nylon, ensuring the uniformity of material properties. Simultaneously, for added glass fibers, ethyl oleate can also play a certain lubricating and dispersing role, reducing agglomeration between glass fibers and improving the material's mechanical properties. The functions of bis(acetylacetonyl)diisopropyl titanate: Enhancing interfacial bonding: Bis(acetylacetonyl)diisopropyl titanate is a titanate coupling agent that reacts with active groups on the nylon molecular chain to form chemical bonds or strong physical adsorption between nylon and other additives (such as glass fiber, halogen-free flame retardants, etc.), thereby enhancing interfacial bonding. Good interfacial bonding can effectively transfer stress, improve the mechanical properties of the material, and reduce internal defects and porosity, reducing water and oxygen permeation channels and acting as a water and oxygen barrier. Improving processing performance: This titanate coupling agent can also improve the processing performance of nylon materials. It can reduce the melt viscosity of the material, making it easier to flow and form during processing, reducing energy consumption and equipment wear. At the same time, good processing performance also helps maintain material uniformity during processing, improving product quality and performance stability. The functions of tea polyphenols: Antioxidant effect: Tea polyphenols are natural antioxidants with strong antioxidant capabilities. In nylon materials, tea polyphenols can scavenge free radicals, preventing them from attacking the nylon molecular chains and thus slowing down the oxidative aging process. Free radicals are a major factor contributing to material aging; by scavenging free radicals, tea polyphenols can effectively improve the anti-aging properties of the material. Synergistic effect: Tea polyphenols and antioxidants exhibit a synergistic effect. Antioxidants mainly inhibit oxidation reactions in materials, while the addition of tea polyphenols can further enhance the effect of antioxidants, improving the material's antioxidant performance. Simultaneously, there may also be interactions between tea polyphenols and ethyl oleate and bis(acetylacetonyl)diisopropyl titanate, jointly improving the material's water and oxygen barrier properties and anti-aging performance. Beneficial effects:

[0028] This invention provides a method for preparing black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging. The method solves the problems of severe aging, significant color change, decreased mechanical properties, and surface cracking of automotive nylon parts under long-term outdoor xenon lamp exposure. Detailed Implementation

[0029] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0030] Polyamide resin (PA66, weight average molecular weight of 20kDa) was purchased from Shanghai Fuchen Plastic Raw Materials Co., Ltd.; ammonium polyphosphate was purchased from Wuhan Jiyesheng Chemical Co., Ltd.; and glass fiber was purchased from Jushi Group Co., Ltd.

[0031] Unless otherwise specified, all chemical reagents used in this invention are commercially available analytical grade reagents.

[0032] Preparation of halogen-free flame retardant compound:

[0033] S1: Add 20 kg of nano silica to 20 L of ethanol, and use an ultrasonic dispersion device to perform ultrasonic treatment for 30 minutes at an ultrasonic power of 200 W to obtain a nano silica dispersion.

[0034] S2: Add the weighed 1kg zinc borate, 2kg magnesium hydroxide and 8kg ammonium polyphosphate into a high-speed mixer, set the speed of the high-speed mixer to 800 rpm and mix for 15 minutes;

[0035] S3: Slowly add the nano-silica dispersion prepared in step S1 to the high-speed mixer in step S2 and continue mixing for 20 minutes; S4: Take out the halogen-free flame retardant compound prepared in step S3 from the high-speed mixer, dry it, and sieve it through a 100-mesh sieve to obtain the halogen-free flame retardant compound.

[0036] Preparation of water and oxygen barrier modifier A:

[0037] S1: Add 500 mL of toluene to a reaction vessel equipped with a stirrer, thermometer, and reflux condenser, and heat to 80 °C.

[0038] S2: Add 5g of ethyl oleate to the reaction vessel of step S1 and stir to dissolve it completely. Then slowly add 1g of bis(acetylacetonyl)diisopropyl titanate while stirring at a speed of 200 rpm. After the addition is complete, the reaction temperature is 80℃ and the reaction is carried out for 2 hours.

[0039] S3: After the reaction is complete, slowly add 1g of tea polyphenols in batches to the reaction vessel of step S2, raise the reaction temperature to 100℃, and the reaction time is 4 hours.

[0040] S4: After the reaction is complete, the reaction product is cooled to room temperature, then filtered, distilled and purified to obtain the water and oxygen barrier modifier.

[0041] Preparation of water and oxygen barrier modifier B:

[0042] The difference between this preparation and that of water and oxygen barrier modifier A is that the 5g ethyl oleate and 1g bis(acetylacetonyl)diisopropyl titanate in step S2 are replaced with 10g ethyl oleate and 1g bis(acetylacetonyl)diisopropyl titanate. Preparation of water and oxygen barrier modifier C:

[0043] The difference between this preparation and that of water and oxygen barrier modifier A is that the 5g ethyl oleate and 1g bis(acetylacetonyl)diisopropyl titanate in step S2 are replaced with 3g ethyl oleate and 3g bis(acetylacetonyl)diisopropyl titanate. Preparation of water and oxygen barrier modifier D:

[0044] The difference between this preparation and that of water and oxygen barrier modifier A is that the 5g ethyl oleate and 1g bis(acetylacetonyl)diisopropyl titanate in step S2 are replaced with 12g ethyl oleate and 0.5g bis(acetylacetonyl)diisopropyl titanate. Preparation of water and oxygen barrier modifier E:

[0045] The difference between this preparation and the water and oxygen barrier modifier A is that 1g of tea polyphenols in step S3 is replaced with 5g of tea polyphenols.

[0046] Preparation of anti-xenon lamp exposure aging black halogen-free flame-retardant nylon:

[0047] Step 1: Add polyamide resin, halogen-free flame retardant compound, antioxidant, water and oxygen barrier modifier and black masterbatch to a high-speed mixer for premixing. The speed of the high-speed mixer is 800 rpm and the mixing time is 10 minutes.

[0048] Step 2: Soak the glass fiber in a 1% (w / w) vinyltriethoxysilane-ethanol solution for 10 minutes. After soaking, remove the glass fiber, let it air dry, and set it aside for later use.

[0049] Step 3: Add the premixed material from Step 1 and the soaked glass fiber from Step 2 into a twin-screw extruder for extrusion granulation. The extrusion temperature is 260℃ and the screw speed is 250 rpm.

[0050] Step 4: After extruding the material, it is cooled by water cooling and vacuum dried to obtain black halogen-free flame-retardant nylon that is resistant to xenon lamp exposure aging.

[0051] Examples 1-6

[0052] According to the above preparation method of anti-xenon lamp exposure aging black halogen-free flame retardant nylon, Table 1 is the ingredient list of anti-xenon lamp exposure aging black halogen-free flame retardant nylon in Examples 1 to 6 by percentage.

[0053] Table 1

[0054]

[0055] Comparative Example 1:

[0056] Comparative Example 1 was prepared according to the above-described method for preparing black halogen-free flame-retardant nylon exposed to xenon lamps. The difference between this preparation and Example 2 is that no halogen-free flame retardant compound was added.

[0057] Comparative Example 2:

[0058] Comparative Example 2 was prepared according to the above-described method for preparing black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging. The difference between this preparation and Example 2 is that water and oxygen barrier modifier A was not added.

[0059] Comparative Example 3:

[0060] The difference between this preparation and Example 2 is that in the preparation of the xenon lamp exposure-resistant black halogen-free flame-retardant nylon, step two directly uses glass fiber without soaking it.

[0061] Performance testing: The nylon materials prepared in Examples 1-6 and Comparative Examples 1-3 were subjected to xenon lamp exposure aging, flame retardancy, and Shore hardness tests. The specific test methods are as follows:

[0062] 1. Xenon Lamp Exposure Aging: Tests were conducted according to standard SAE J2527. Nylon materials prepared in Examples 1-6 and Comparative Examples 1-3 were molded into 2×5×10cm strip samples. Before the xenon lamp exposure aging test, the samples underwent pretreatment such as cleaning and drying to remove surface contaminants and moisture, ensuring the accuracy of the test results. The prepared samples were installed on the sample rack inside the test chamber, ensuring uniform exposure to the xenon lamp and the environmental conditions within the chamber. The lamp irradiance level reached 0.55 W / m²·nm. During the illumination cycle, the air temperature inside the chamber was maintained at 47℃; during the dark cycle, the air temperature was 38℃. The relative humidity was 50% during the illumination cycle and increased to 95% during the dark cycle. During the illumination cycle, the black panel temperature needed to reach 70℃. Before the test, a 18-hour illumination and 6-hour darkness cycle was set, repeated 10 times. Water was sprayed onto the sample surface during both illumination and darkness cycles. The test results were evaluated using materials purchased from Shenzhen... The Ci7800 colorimeter from Source Instrument Equipment Co., Ltd. quantitatively measured the color change of samples after 10 cycles of light and dark. When the color difference ΔE is less than 1, the color change is almost imperceptible to the human eye; when ΔE is between 1 and 2, only professionally trained personnel or under specific conditions can perceive the slight color change; when ΔE is between 2 and 3, the color change is clearly perceptible to the human eye; when ΔE is between 3 and 5, the color change is relatively significant; when ΔE is greater than 5, the color change is very large and is generally considered unacceptable. The Shore hardness of the samples after 10 cycles of light and dark was tested using the OU2700 hardness tester from Cangzhou Oupu Testing Instrument Co., Ltd.

[0063] 2. Flame Retardancy Test: The nylon materials prepared in Examples 1-6 and Comparative Examples 1-3 were used to prepare strips with dimensions of 125mm × 13mm × 3mm. The strips were vertically fixed on the clamps of the combustion chamber, ensuring that the lower end of the strip was 5cm from the top of the burner. According to standard requirements, the flame height and temperature of the burner were adjusted: the blue inner flame height was 20mm, the outer flame height was 40mm, and the temperature was 550℃. A combustion test was conducted by igniting the lower end of the strip and observing its combustion behavior. The burning time and burning length of the strip were recorded. Rating: The flame retardancy performance of the strips was evaluated according to the standard based on the burning time and burning length. Ratings were divided into V-0, V-1, and V-2 grades, where V-0 indicates the best flame retardancy, V-1 indicates moderate flame retardancy, and V-2 indicates the worst flame retardancy.

[0064] Table 2: Test Results Table

[0065] Material Color difference ΔE hardness Flame retardant rating Example 1 1.2 D85 V-0 Example 2 1.1 D88 V-0 Example 3 1.2 D85 V-0 Example 4 1.8 D75 V-1 Example 5 2.0 D77 V-1 Example 6 2.1 D72 V-1 Comparative Example 1 2.5 D80 V-2 Comparative Example 2 3.0 D64 V-2 Comparative Example 3 1.8 D76 V-2

[0066] The data above show that the black halogen-free flame-retardant nylons prepared in Examples 1-3 exhibit excellent resistance to xenon lamp exposure aging and flame retardant properties. A comparison between Example 4 and Example 2 reveals that an improper mass ratio of ethyl oleate to bis(acetylacetonyl)diisopropyl titanate in the preparation of the water-oxygen barrier modifier leads to increased color difference, decreased hardness, and reduced flame retardant properties in the prepared black halogen-free flame-retardant nylons. A comparison between Example 5 and Example 2 shows that excessive ethyl oleate in the preparation of the water-oxygen barrier modifier results in increased color difference, decreased hardness, and reduced flame retardant properties in the prepared black halogen-free flame-retardant nylons. A comparison between Example 6 and Example 2 shows that increasing the amount of tea polyphenols, ethyl oleate, and bis(acetylacetonyl)diisopropyl titanate in the preparation of the water-oxygen barrier modifier... An unreasonable mass ratio of diisopropyl titanate and tea polyphenols will cause the color difference, hardness, and flame retardant properties of the prepared xenon lamp-resistant black halogen-free flame-retardant nylon to deteriorate under xenon lamp exposure aging. A comparison between Comparative Example 1 and Example 2 shows that the absence of the halogen-free flame retardant compound will result in a deterioration in the flame retardant properties of the prepared xenon lamp-resistant black halogen-free flame-retardant nylon under xenon lamp exposure aging. A comparison between Comparative Example 2 and Example 2 shows that the absence of a water-oxygen barrier modifier will result in a greater color difference and a decrease in hardness of the prepared xenon lamp-resistant black halogen-free flame-retardant nylon under xenon lamp exposure aging, failing to achieve the expected results. A comparison between Comparative Example 3 and Example 2 shows that the absence of glass fiber soaking will result in a greater color difference, a decrease in hardness, and a deterioration in the flame retardant properties of the prepared xenon lamp-resistant black halogen-free flame-retardant nylon under xenon lamp exposure aging, failing to achieve the expected results.

[0067] This invention can also be implemented in various other ways. Without departing from the spirit and essence of this invention, those skilled in the art can make various corresponding changes and modifications according to this invention, but these corresponding changes and modifications should all fall within the protection scope of the appended claims.

Claims

1. A method for preparing a black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging, characterized in that, The raw materials for preparing the anti-xenon lamp exposure aging black halogen-free flame-retardant nylon, by weight percentage (100%), include the following components: 30-50% polyamide resin, 10-30% glass fiber, 10-30% halogen-free flame retardant compound, 1-3% antioxidant, 5-15% water and oxygen barrier modifier, and 1-3% black masterbatch; The halogen-free flame retardant compound is prepared by mixing nano-silica, zinc borate, magnesium hydroxide and ammonium polyphosphate. The mass ratio of the nano-silica, zinc borate, magnesium hydroxide, and ammonium polyphosphate is 10~20:1:2~5:8~20; The water and oxygen barrier modifier is prepared by reacting ethyl oleate, bis(acetylacetonyl) diisopropyl titanate, and tea polyphenols. The mass ratio of ethyl oleate, bis(acetylacetonyl) diisopropyl titanate, and tea polyphenols is 5~10:0.5~2:

1.

2. The preparation method of the xenon lamp exposure-resistant black halogen-free flame-retardant nylon according to claim 1, characterized in that, The polyamide resin has a weight-average molecular weight of 18-25 kDa.

3. The method for preparing the xenon lamp exposure-resistant black halogen-free flame-retardant nylon according to claim 1, characterized in that, The preparation of the water-oxygen barrier modifier includes the following steps: S1: Add an appropriate amount of toluene to a reaction vessel equipped with a stirrer, thermometer, and reflux condenser, and heat it to a certain temperature; S2: Add ethyl oleate to the reaction vessel of step S1, stir to dissolve it completely, and then slowly add bis(acetylacetonyl) diisopropyl titanate dropwise while stirring during the dropwise addition. After the dropwise addition is complete, react at a certain temperature for a period of time. S3: After the reaction is complete, add tea polyphenols slowly in batches to the reaction vessel of step S2, and raise the temperature to react for a period of time. S4: After the reaction is complete, the reaction product is cooled to room temperature, then filtered, distilled and purified to obtain the water and oxygen barrier modifier. The heating temperature in step S1 is 80~100℃; the stirring speed in step S2 is 100~300 rpm, the reaction temperature is 80~100℃, and the reaction time is 2~4 hours; the reaction temperature in step S3 is 100~120℃, and the reaction time is 4~6 hours.

4. The method for preparing the xenon lamp exposure-resistant black halogen-free flame-retardant nylon according to claim 1, characterized in that, Includes the following steps: Step 1: Add polyamide resin, halogen-free flame retardant compound, antioxidant, water and oxygen barrier modifier and black masterbatch to a high-speed mixer for premixing. The speed of the high-speed mixer is 500~1000 rpm and the mixing time is 5~10 minutes. Step 2: Soak the glass fiber in a 1-3% (w / w) silane coupling agent solution for 10-30 minutes. After soaking, remove the glass fiber, air dry it, and set it aside. Step 3: Add the premixed material from Step 1 and the soaked glass fiber from Step 2 into a twin-screw extruder for extrusion granulation. The extrusion temperature is 200~260℃ and the screw speed is 100~300 rpm. Step 4: After extruding the material, cool and vacuum dry to obtain black halogen-free flame-retardant nylon resistant to xenon lamp exposure aging.

5. The method for preparing the xenon lamp-resistant, aging-resistant black halogen-free flame-retardant nylon according to claim 1, characterized in that, The antioxidant is one or more of antioxidant 1098, antioxidant 1010, antioxidant 1216, and antioxidant 1330.

6. The application of the xenon lamp exposure aging resistant black halogen-free flame-retardant nylon prepared by the method of any one of claims 1-5 in automotive plastic parts or automotive engine peripheral parts.

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