A wear-resistant composite nylon material and a preparation method thereof

Abstract

The application provides a wear-resistant composite nylon material and a preparation method thereof. The wear-resistant composite nylon material comprises the following components in parts by mass: a nylon compound 50-90 parts, glass fibers 20-40 parts, a coupling agent 2-6 parts, polytetrafluoroethylene 3-8 parts, an antioxidant 1-3 parts, a wear-resistant agent 2-5 parts, a lubricant 0.1-2 parts, and an organic silicon surfactant 0.5-2 parts. The antioxidant is an aromatic amine antioxidant and a thio-phenol antioxidant. The wear-resistant composite nylon material provided by the application has a low friction coefficient, a high tensile strength and a simple supported beam notched impact strength, and even at low temperature, the wear-resistant composite nylon material has a high simple supported beam notched impact strength, excellent low-temperature resistance, a small color difference value at high temperature, and a relatively small change range of the color difference value even when the test temperature is increased, and the yellowing resistance at high temperature is better.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of wear-resistant nylon preparation, and particularly relates to a wear-resistant composite nylon material and a preparation method thereof. BACKGROUND

[0002] With the rapid development of modern industrial technology, the requirements for material performance are increasingly stringent, especially in the field of wear resistance. Nylon materials have attracted much attention due to their wear resistance and good mechanical strength. Such materials not only play an important role in extending the service life of equipment and reducing maintenance costs, but also have a significant effect on improving production efficiency and product quality. For example, in the automotive industry, this material is widely used to manufacture engine covers, intake systems, and fuel system components, etc. By improving the wear resistance of these components, their service life is significantly extended, and maintenance costs are reduced. In the textile machinery field, the application of composite nylon makes high-speed running parts such as spindles and yarn guides more wear-resistant, effectively preventing frequent replacement and production line downtime due to wear, thereby improving production efficiency. In addition, in the sports goods industry, wear-resistant composite nylon materials are also used to produce parts of high-performance sports equipment such as skis and ice skates, which not only improve the performance of the products, but also ensure the safety and comfort of athletes in extreme conditions. Although nylon materials have been widely concerned in the automotive industry, textile machinery field, and sports goods industry due to their wear resistance, the wear resistance and mechanical properties still need to be further improved, and the yellowing resistance of nylon materials is still relatively poor.

[0003] In order to improve the wear resistance and mechanical properties of nylon materials, as well as the yellowing resistance, the existing technology uses nylon resin, fiber material, wear-resistant agent, surface treatment agent, lubricant, antioxidant, etc. to prepare nylon composite materials to reduce the friction coefficient, improve the overall wear resistance of nylon materials, and improve the yellowing resistance of nylon materials. However, the wear resistance of the prepared nylon materials is improved, but the wear resistance still needs to be further improved, the notched impact strength is relatively low, the low-temperature resistance is poor, and the yellowing improvement is not obvious, especially at high temperatures, which is more prone to yellowing. SUMMARY

[0004] The present application aims to provide a wear-resistant composite nylon material and a preparation method thereof to solve the problem that the wear resistance of the prepared nylon material is improved, but the wear resistance still needs to be further improved, the notched impact strength is relatively low, the low-temperature resistance is poor, and the yellowing improvement is not obvious, especially at high temperatures, which is more prone to yellowing.

[0005] To achieve the above object, the present application provides the following technical solutions: on the one hand, the present application provides a wear-resistant composite nylon material, which comprises the following components in parts by mass: nylon composite 50-90 parts, glass fiber 20-40 parts, coupling agent 2-6 parts, polytetrafluoroethylene 3-8 parts, antioxidant 1-3 parts, wear-resistant agent 2-5 parts, lubricant 0.1-2 parts, and organic silicon surfactant 0.5-2 parts.

[0006] The antioxidant is an aromatic amine antioxidant and a thio-phenol antioxidant.

[0007] As a further improvement, the nylon composite is nylon 66 and nylon 6.

[0008] As a further improvement, the mass ratio of nylon 66 and nylon 6 is 1:0.3-0.5.

[0009] As a further improvement, the raw materials for preparing the organic silicon surfactant include octamethylcyclotetrasiloxane, 1,3-bis(3-glycidyl ether propyl)-1,1,3,3-tetramethyl disiloxane, meglumine, and silane coupling agent, wherein the CAS number of 1,3-bis(3-glycidyl ether propyl)-1,1,3,3-tetramethyl disiloxane is 126-80-7.

[0010] As a further improvement, the thio-phenol antioxidant has the following structure shown in formula I:

[0011]

[0012] I.

[0013] As a further improvement, the aromatic amine antioxidant is at least one of p-phenylenediamine and secondary diarylamine.

[0014] As a further improvement, the p-phenylenediamine includes but is not limited to antioxidant DAPD and antioxidant 4720.

[0015] As a further improvement, the wear-resistant agent is at least one of molybdenum disulfide and titanium dioxide.

[0016] As a further improvement, the wear-resistant agent is a mixture of molybdenum disulfide and titanium dioxide.

[0017] As a further improvement, the lubricant is at least one of ethylene bis-stearamide, silicone powder, calcium stearate, zinc stearate, and paraffin wax.

[0018] As a further improvement, the p-phenylenediamine is at least one of antioxidant DAPD and antioxidant 4720.

[0019] In another aspect, the present application also provides a preparation method of the wear-resistant composite nylon material, comprising the following steps:

[0020] (1) pretreating the glass fiber with a coupling agent;

[0021] (2) placing the nylon compound, polytetrafluoroethylene, antioxidant, wear-resistant agent, lubricant, and organic silicon surfactant into a high-speed mixer and stirring until mixed evenly;

[0022] (3) placing the substance of step (1) and the mixed substance of step (2) into a double-screw extruder, extruding and granulating through the double-screw extruder to obtain the wear-resistant composite nylon material.

[0023] Compared with the prior art, the wear-resistant composite nylon material provided by the present application has the advantages of low friction coefficient, high tensile strength, and Charpy notched impact strength, and even at low temperature, the Charpy notched impact strength is still high, the low-temperature resistance is excellent, and the color difference value at high temperature is small, and even if the test temperature is increased, the change range of the color difference value is relatively small, and the yellowing resistance at high temperature is better. DETAILED DESCRIPTION

[0024] The present application will be described below in conjunction with specific embodiments. It should be noted that the following examples are examples of the present application and are only used to illustrate the present application, but not to limit the present application. Other combinations and various modifications within the concept of the present application can be made without departing from the spirit or scope of the present application.

[0025] In the following examples, the used compound monomers and related reagents except for the organic silicon surfactant A and the thio-phenolic antioxidant A can be purchased from the market, wherein the thio-phenolic antioxidant A is prepared by the preparation method provided in the patent with the publication number "CN102786486B"; the surfactant is purchased from Beijing Kemite Science and Technology Development Co., Ltd., and the article number is 5840; the glass fiber is purchased from Hangzhou Gaokexuan Composite Material Co., Ltd., and the model number is EC; the nylon 6 is purchased from Shanghai Qiling Plasticizing Technology Co., Ltd., and the article number is PA6UBC13B01; the nylon 66 is purchased from Shanghai Qiling Plasticizing Technology Co., Ltd., and the article number is A3EG10A3EG301; the polytetrafluoroethylene is purchased from Foshan Shangjincheng New Material Technology Co., Ltd., and the brand is SGW-140; the antioxidant DAPD is purchased from Jiangsu Huaxing New Material Technology Co., Ltd.; and the antioxidant 300 is purchased from Shijiazhuang Tengchi Chemical Industry Co., Ltd., and the CAS number is 90-66-4.

[0026] The preparation method of the organic silicon surfactant A comprises the following steps:

[0027] (1) Put 1 kg of octamethylcyclotetrasiloxane, 11.8 g of 1,3-bis(3-glycidyl ether propyl)-1,1,3,3-tetramethyldisiloxane, and 0.5 g of tetramethylammonium hydroxide into a reactor for reaction. During the reaction, first react at a temperature of 90°C for 18 h, then increase the temperature to 150°C, continue to react for 1 h, and then

[0028] Distill under reduced pressure to obtain intermediate one;

[0029] (2) Put 288.5 g of intermediate one obtained in step (1), 15.6 g of meglumine, and 203 g of isopropyl alcohol into a reactor for reaction. The reaction temperature is 80°C, and after 12 h of reaction, intermediate two is obtained;

[0030] (3) Continue to add 31.8 g of γ-chloropropyltrimethoxysilane to step (2), and maintain the reaction temperature at 80°C. After 5 h of reaction, remove the solvent by rotary evaporation at 80°C to obtain a silicone surfactant.

[0031] The preparation method of the wear-resistant composite nylon material of examples 1-6 and comparative examples 1-2 comprises the following steps:

[0032] (1) Pretreat the glass fiber with silane coupling agent KH-560;

[0033] (2) Put the nylon composite, polytetrafluoroethylene, antioxidant, wear-resistant agent, lubricant, and silicone surfactant into a high-speed mixer and stir until uniform. The stirring speed is 450 r / min;

[0034] (3) Put the substance of step (1) and the mixed substance of step (2) into a double-screw extruder, and extrude and granulate through the double-screw extruder. The temperature of each zone of the double-screw extruder is controlled at 240°C, 255°C, 260°C, 265°C, 265°C, 255°C, 245°C, and 260°C. The speed of the main machine is 400 r / min, and the feeding rate is 30 r / min. After melt blending through the double-screw extruder, a wear-resistant composite nylon material is obtained.

[0035] The components required in examples 1-6 and comparative example 2 and the content of each component are shown in tables 1-2:

[0036] Table 1

[0037]

[0038] Table 2

[0039]

[0040]

[0041] The wear-resistant composite nylon materials prepared from Examples 1-6 and Comparative Examples 1-2 were melt-extruded through a single-screw extruder at a temperature of 245℃, 265℃, 265℃, 270℃, 270℃, 255℃, 255℃, 265℃ in each zone, a screw rotation speed of 30r / min, and were shaped through a die at a pulling speed of 18r / min to prepare the samples to be tested, and the Charpy notched impact strength, yellowing resistance, tensile strength, and dynamic friction coefficient were tested.

[0042] The test methods are as follows:

[0043] Charpy notched impact strength (23℃): the test standard is ISO 179 / 1eA-2010, 23℃, the notch type is A type; the unit is kJ / m 2 ;

[0044] Charpy notched impact strength (-10℃): the test standard is ISO 179 / 1eA-2010, -10℃, the notch type is A type; the unit is kJ / m 2 ;

[0045] Yellowing resistance (180℃): the color difference value change (△E) of the sample to be tested before and after being baked in an oven at 180℃ for 18h was tested by a HunterLab UltraScan PRO color difference meter from Beijing Jintongjian Environmental Technology Co., Ltd.;

[0046] Yellowing resistance (150℃): the color difference value change (△E) of the sample to be tested before and after being baked in an oven at 150℃ for 18h was tested by a HunterLab UltraScan PRO color difference meter from Beijing Jintongjian Environmental Technology Co., Ltd.;

[0047] Tensile strength: the test standard is ISO 527-2-2012, 5mm / min, the unit is MPa;

[0048] Friction coefficient: the test standard is GB-3960-83, the sample size is 30mm*6mm*7mm, the upper rotating shaft is kept stationary during the test, the lower rotating shaft rotates at 200r / min, the friction pair is sliding friction, the friction pair is worn for 2h, the load is 20kg, and the test environment temperature is 23℃.

[0049] The test results are shown in Table 3 as follows:

[0050] Table 3

[0051]

[0052] Table 4

[0053] Test item Tensile strength Friction coefficient Example 1 160 0.396 Example 2 152 0.405 Example 3 168 0.4 Example 4 158 0.403 Example 5 152 0.502 Example 6 148 0.612 Comparative Example 1 141 0.509 Comparative Example 2 143 0.507

[0054] It can be seen from the comparison of Example 1 and Comparative Examples 1-2 that the notched Charpy impact strength of the wear-resistant composite nylon material provided by the application is improved, the notched Charpy impact strength at low temperature does not decrease obviously, the color difference value at high temperature (temperature is 150°C) is relatively low, the color difference value does not change obviously even if the temperature is increased (temperature is 180°C), the yellowing resistance at high temperature is better, and the material has high tensile strength and low friction coefficient;

[0055] It can be seen from the comparison of Example 1 and Example 4 that when the antioxidant is an aromatic amine antioxidant and a thio-phenol antioxidant, and the thio-phenol antioxidant is the antioxidant of Formula I, the notched Charpy impact strength at room temperature (temperature is 23°C) and the notched Charpy impact strength at low temperature (temperature is -10°C) of the wear-resistant composite nylon material prepared are relatively small, the material has good low temperature resistance, and the color difference value at different high temperatures changes relatively little, and the yellowing resistance at high temperature is better;

[0056] It can be seen from the comparison of Example 1 and Example 5 that the wear-resistant composite nylon material prepared using the organic silicon surfactant A provided by the application not only has high tensile strength and low friction coefficient, but also has high notched Charpy impact strength at low temperature, good low temperature resistance, and small color difference value at high temperature, and the yellowing resistance at high temperature is better;

[0057] It can be seen from the comparison of Example 1 and Example 6 that the wear-resistant composite nylon material prepared using the organic silicon surfactant A and the antioxidant provided by the application not only has high tensile strength and low friction coefficient, but also has notched Charpy impact strength at low temperature and at room temperature that is not much different, good low temperature resistance, and a small color difference value at high temperature, and the yellowing resistance at high temperature is better even if the temperature is increased;

[0058] It can be seen from the comparison of Examples 1-3 that the wear-resistant composite nylon material prepared using the components and contents provided by the application not only has low friction coefficient, high tensile strength, and notched Charpy impact strength, but also has high notched Charpy impact strength at low temperature, excellent low temperature resistance, and a small color difference value at high temperature (temperature is 150°C), and the yellowing resistance at high temperature is better even if the test temperature is increased (temperature is 180°C).

[0059] The above embodiments are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the present application and implement it, and cannot limit the protection scope of the present application, and any equivalent changes or modifications made according to the spirit and principle of the present application shall be covered within the protection scope of the present application.

Claims

1. A wear-resistant composite nylon material, characterized by: The wear-resistant composite nylon material comprises the following components in parts by mass: 50-90 parts of nylon composite, 20-40 parts of glass fiber, 2-6 parts of coupling agent, 3-8 parts of polytetrafluoroethylene, 1-3 parts of antioxidant, 2-5 parts of wear-resistant agent, 0.1-2 parts of lubricant, and 0.5-2 parts of organic silicon surfactant; The antioxidants are aromatic amine antioxidants and thiophenol antioxidants; The thiophenol antioxidant has a structure shown in the following formula I: I； The raw materials for preparing the organosilicon surfactant include octamethylcyclotetrasiloxane, 1,3-bis(3-glycidyl ether propyl)-1,1,3,3-tetramethyldisiloxane, meglumine and a silane coupling agent; The aromatic amine antioxidant is the antioxidant DAPD; The preparation method of the organosilicon surfactant comprises the following steps: (1) 1 kg of octamethylcyclotetrasiloxane, 11.8 g of 1,3-bis(3-glycidyl ether propyl)-1,1,3,3-tetramethyldisiloxane, and 0.5 g of tetramethylammonium hydroxide were added to a reactor for reaction. During the reaction, the reaction temperature was first reacted at 90°C for 18 hours, then the temperature was raised to 150°C, and the reaction was continued for 1 hour, and then the reaction was distilled under reduced pressure to obtain intermediate 1; (2) 288.5 g of intermediate 1 prepared in step (1), 15.6 g of meglumine, and 203 g of isopropanol were added to a reactor for reaction at a temperature of 80° C. After 12 h of reaction, intermediate 2 was obtained; (3) Add 31.8 g of γ-chloropropyltrimethoxysilane to step (2), maintain the reaction temperature at 80°C, react for 5 hours, and then remove the solvent by rotary evaporation at 80°C to obtain an organosilicon surfactant; The mass ratio of the aromatic amine antioxidant to the thiophenol antioxidant is one of 1:3, 1.5:1, and 4:1; The nylon composite consists of nylon 66 and nylon 6.

2. The wear-resistant composite nylon material according to claim 1, characterized in that: The mass ratio of nylon 66 to nylon 6 is 1:0.3-0.

5.

3. The wear-resistant composite nylon material according to claim 1, characterized in that: The anti-wear agent is at least one of molybdenum disulfide and titanium dioxide.

4. The wear-resistant composite nylon material according to claim 1, characterized in that: The lubricant is at least one of ethylene bisstearamide, silicone powder, calcium stearate, zinc stearate, and paraffin.

5. The method for preparing the wear-resistant composite nylon material according to any one of claims 1 to 4, characterized in that: The following steps are involved: (1) Pre-treating the glass fiber with a coupling agent; (2) Place nylon compound, polytetrafluoroethylene, antioxidant, anti-wear agent, lubricant, and silicone surfactant into a high-pressure mixer and stir until uniformly mixed; (3) The material of step (1) and the mixed material of step (2) are placed into a twin-screw extruder, and granulated by extrusion through the twin-screw extruder to obtain a wear-resistant composite nylon material.

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