Antiskid wear-resistant nylon composite material and preparation method thereof

Abstract

The invention relates to an antiskid wear-resistant nylon composite material and a preparation method thereof. The antiskid wear-resistant nylon composite material comprises the following components in parts by mass: 50-70 parts of nylon resin, 5-10 parts of polytetrafluoroethylene, 20-50 parts of modified solid particles, 0.1-2 parts of an antioxidant, 0.1-2 parts of an anti-aging agent and 0.1-2 parts of a lubricant. Wherein the modified solid particles are body type macromolecules formed by copolymerizing an intermediate product formed by hydroxylated magnesium oxide, hydroxylated glass fibers and grafted acrylic acid with hexafluorobutyl methacrylate and ethylene glycol diacrylate. According to the invention, not only is the combination effect between the nylon resin and the reinforced filling material improved, but also the compatibility between the fluororesin and other components can be improved, and the compatibilization function is played, so that the skid resistance, wear resistance, weather resistance and stability of the composite material are ensured, and the reduction of the mechanical strength of the product is avoided.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer composite materials, in particular to a kind of antiskid wear-resistant nylon composite material and preparation method thereof. BACKGROUND

[0002] Nylon is widely used in many fields due to its high strength, wear resistance, corrosion resistance and self-lubricating advantages, such as manufacturing bearing retainer, gasket, bearing, shaft sleeve and pulley products. However, due to the existence of a large number of amide bonds in the molecular chain of nylon, it has strong polarity and water absorption, which not only causes poor dimensional stability of finished products, but also due to the hydrogen bond effect between and within the molecular chain, the surface energy is higher than that of common plastics, and the adhesion and friction coefficient are high when contacting with other substances, which further leads to insufficient wear resistance, greatly limiting the in-depth application in load-bearing field.

[0003] Currently, in order to improve the wear resistance of nylon surface, the industry mainly adopts the methods of increasing the rigidity of the matrix, adding wear-resistant fillers and directly modifying the surface of the product. Adding reinforcing fibers such as glass fiber, carbon fiber and aramid fiber in nylon can enhance the rigidity of nylon composite material and improve the surface hardness of the material, but the effect of improving the wear resistance of the composite material is limited. Adding wear-resistant fillers such as molybdenum disulfide, carbon black, polytetrafluoroethylene powder and silicone powder can improve the wear resistance of nylon composite material to some extent, however, such wear-resistant fillers often need a large amount of addition, and both reinforcing fibers and wear-resistant fillers will reduce the melt flowability of the composite material, making the material processing performance worse, which is not conducive to the preparation of complex structure products.

[0004] At the same time, with the continuous progress of industrial technology and the continuous expansion of application field, the performance requirements of nylon composite materials are becoming increasingly stringent. In actual application, many nylon composite materials are prone to wear, deformation and even fracture when used for a long time or under heavy load. For example, the wear resistance of nylon caster used in high friction and high wear working environment such as factory is difficult to meet the long-term use demand, and the mechanical properties are low, which may cause deformation or damage under high load or heavy pressure, which greatly limits the application of nylon caster in occasions that need to bear large impact load. In addition, in nylon composite materials, a large amount of glass fiber, metal oxide and fluororesin filling materials have poor combination effect with the matrix resin, and it is difficult to obtain a uniform and sufficient mixing system, which not only makes the reinforcing effect of the composite material not ideal, but also affects the surface anti-sticking ability and chemical stability of the product under extreme conditions such as high humidity, high salt and high temperature, further reducing the service life and safety of the product.

[0005] In summary, the shortcomings of existing nylon materials in terms of mechanical properties and durability can no longer meet the growing demands of practical applications. Developing a nylon material with excellent anti-slip and wear-resistant properties, while effectively improving mechanical properties and durability, has become a critical issue that urgently needs to be addressed.

[0006] In conclusion, it is necessary to develop a new technical solution to overcome the shortcomings of existing technologies. Summary of the Invention

[0007] Based on this, the present invention provides an anti-slip and wear-resistant nylon composite material and its preparation method. The present invention modifies metal oxides and glass fibers with acrylic acid, then further polymerizes them with fluorinated acrylates and a crosslinking agent to obtain modified solid particles with a three-dimensional structure. This not only improves the bonding effect between nylon resin and reinforcing fillers, but also improves the compatibility between fluoropolymers and other components, thus playing a compatibilizing role. This ensures the anti-slip, wear-resistant, weather-resistant, and stable properties of the composite material, while avoiding a reduction in the product's mechanical strength.

[0008] One object of the present invention is to provide an anti-slip and wear-resistant nylon composite material, wherein the anti-slip and wear-resistant nylon composite material comprises the following components in parts by weight:

[0009]

[0010] The modified solid particles are macromolecules formed by copolymerizing hydroxylated magnesium oxide, hydroxylated glass fiber, and acrylic acid grafted intermediates with hexafluorobutyl methacrylate and ethylene glycol diacrylate.

[0011] Furthermore, the mass ratio of the intermediate product, hexafluorobutyl methacrylate, and ethylene glycol diacrylate is 10-30:10-20:0.5-2.

[0012] Furthermore, the mass ratio of the hydroxylated magnesium oxide to the hydroxylated glass fiber is 1:1 to 1:4.

[0013] This invention uses magnesium oxide and glass fiber composite as inorganic reinforcing material. Magnesium oxide can improve the surface friction coefficient and enhance anti-slip properties by forming a micro-rough structure. It can also act as a rigid filler to synergistically improve tensile and flexural strength and inhibit creep, thus playing a reinforcing role. It also has strong thermal stability and auxiliary effects in improving anti-aging and anti-oxidation properties, which is beneficial to improving the overall performance of composite materials.

[0014] Furthermore, the nylon resin is selected from one or more of PA6, PA66, PA46, PA6T, PA9T, PA10T, and PA13T.

[0015] Another object of the present application is to provide a preparation method of the anti-skid and wear-resistant nylon composite material, which comprises the following steps:

[0016] S1, hydroxylating magnesium oxide and glass fiber to obtain hydroxylated magnesium oxide and hydroxylated glass fiber;

[0017] S2, mixing and heating the hydroxylated magnesium oxide and the hydroxylated glass fiber with acrylic acid and a polymerization inhibitor to obtain an intermediate product;

[0018] S3, mixing the intermediate product with hexafluorobutyl methacrylate and ethylene glycol diacrylate, and adding an initiator to react under the protection of inert gas to obtain modified solid particles.

[0019] Further, it further comprises:

[0020] S4, mixing the modified solid particles with nylon resin, polytetrafluoroethylene, antioxidant, anti-aging agent and lubricant, and adding them into an extruder to melt and extrude to obtain a product.

[0021] Further, the hydroxylating treatment is to add magnesium oxide and glass fiber into a mixed solution of concentrated sulfuric acid and concentrated nitric acid, and then ultrasonic reaction to obtain hydroxylated magnesium oxide and hydroxylated glass fiber.

[0022] Further, the temperature of the ultrasonic reaction is 60-90℃.

[0023] Further, in step S2, the temperature of the heating reaction is 50-100℃.

[0024] Further, in step S3, the temperature of the heating reaction is 50-100℃.

[0025] The present application has the following beneficial effects:

[0026] The anti-slip and wear-resistant nylon composite material provided by this invention uses polytetrafluoroethylene (PTFE) as the wear-resistant material, compounded with nylon resin, and chemically modifies the reinforcing materials, glass fiber and metal oxide. The modified solid particles of this invention first undergo hydroxylation treatment of magnesium oxide and glass fiber, then undergo an esterification reaction with acrylic acid to introduce double bonds into the surface of the solid particles. Subsequently, they undergo free radical polymerization with hexafluorobutyl methacrylate and the crosslinking agent ethylene glycol diacrylate. The resulting product introduces fluorocarbon segments into the surface of the glass fiber and oxide, thereby playing a compatibilizing role and improving the defects of conventional PTFE, inorganic materials, and nylon resin, where the large polarity difference between different components easily leads to phase separation and uneven distribution after mixing. Furthermore, this invention also uses multifunctional ethylene glycol diacrylate to act as a bridging bond, allowing the glass fiber, magnesium oxide, and hexafluorobutyl methacrylate with introduced double bonds to be more fully crosslinked, resulting in a three-dimensional, network structure that helps to further improve tensile, bending, and other mechanical properties. This invention achieves synergistic effects through the physical properties of multiple components and the chemical structure obtained from the reaction. While ensuring anti-slip and wear-resistant properties, it promotes the improvement of the strength and chemical stability of the composite material, resulting in better durability and service life. This provides a new approach for the development of nylon composite materials and has good application prospects. Detailed Implementation

[0027] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0028] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0029] It should be understood that, except in any operational instance or otherwise indicated, the amounts or all figures representing ingredients used, for example, in the specification and claims, should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximate values ​​varying according to the desired performance to be obtained according to the invention.

[0030] The nylon resin used in this embodiment of the invention is PA6, BASF B30S.

[0031] The polytetrafluoroethylene used in this embodiment of the invention is Shanghai Sanaifu FR002A.

[0032] The glass fiber in the embodiment of the application is giant stone fiberglass 568H with a diameter of 10 microns; and the magnesium oxide has a particle size of about 50 nm.

[0033] The concentration of the concentrated sulfuric acid is 98 wt%, and the concentration of the concentrated nitric acid is 68 wt%.

[0034] The antioxidant is 1010, the anti-aging agent is DPPD, and the lubricant is sodium stearate.

[0035] The "parts" in the embodiment of the application refer to mass parts.

[0036] Embodiment 1

[0037] A kind of anti-skid wear-resistant nylon composite material, the anti-skid wear-resistant nylon composite material includes the following components by mass parts:

[0038]

[0039] The preparation method of the anti-skid wear-resistant nylon composite material includes the following steps:

[0040] S1, the concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 1:5 are mixed to obtain a mixed solution, then the magnesium oxide is immersed in the mixed solution, and ultrasonic reaction is carried out at 80 DEG C for 4h, and after washing and drying, the hydroxylated magnesium oxide is obtained;

[0041] The concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 1:5 are mixed to obtain a mixed solution, then the glass fiber is immersed in the mixed solution, and ultrasonic reaction is carried out at 80 DEG C for 4h, and after washing and drying, the hydroxylated glass fiber is obtained;

[0042] S2, the hydroxylated magnesium oxide, the hydroxylated glass fiber, the polymerization inhibitor hydroquinone and the acrylic acid with a mass ratio of 1:4:0.1:20 are mixed, stirred and uniformly dispersed, and ultrasonic reaction is carried out at 100 DEG C for 6h, and after filtration and drying, the intermediate product is obtained;

[0043] S3, the intermediate product, hexafluorobutyl methacrylate and ethylene glycol diacrylate are uniformly mixed with 1, 4-dioxane as a solvent, then the initiator azobisisobutyronitrile (the mass ratio of the intermediate product, hexafluorobutyl methacrylate, ethylene glycol diacrylate and azobisisobutyronitrile is 25:10:1:1.5) is added, and reaction is carried out at 70 DEG C for 8h under nitrogen protection, and after filtration, washing and drying, the modified solid particles are obtained;

[0044] S4, the modified solid particles and the nylon resin, polytetrafluoroethylene, antioxidant, anti-aging agent, lubricant and initiator dicumyl peroxide are added to a double screw extruder according to the above mass parts, and melt extrusion is carried out at 240-250 DEG C to obtain the anti-skid wear-resistant nylon composite material.

[0045] Example 2

[0046] A kind of anti-skid wear-resistant nylon composite material, the anti-skid wear-resistant nylon composite material includes the ingredients of mass fraction as follows:

[0047]

[0048] The preparation method of the anti-skid wear-resistant nylon composite material includes the following steps:

[0049] S1, the concentrated sulfuric acid and concentrated nitric acid of volume ratio 1:5 are mixed to obtain a mixed solution, then magnesium oxide is immersed in the mixed solution, ultrasonic reaction is carried out at 80 DEG C for 4h, after washing and drying, hydroxylated magnesium oxide is obtained;

[0050] The concentrated sulfuric acid and concentrated nitric acid of volume ratio 1:5 are mixed to obtain a mixed solution, then glass fiber is immersed in the mixed solution, ultrasonic reaction is carried out at 80 DEG C for 4h, after washing and drying, hydroxylated glass fiber is obtained;

[0051] S2, the hydroxylated magnesium oxide, hydroxylated glass fiber, polymerization inhibitor hydroquinone and acrylic acid of mass ratio 1:4:0.1:20 are mixed, stirred and uniformly dispersed, ultrasonic reaction is carried out at 100 DEG C for 6h, after filtration and drying, an intermediate product is obtained;

[0052] S3, the intermediate product, hexafluorobutyl methacrylate and ethylene glycol diacrylate are mixed uniformly with 1,4-dioxane as solvent, then initiator azobisisobutyronitrile (the mass ratio of intermediate product, hexafluorobutyl methacrylate, ethylene glycol diacrylate and azobisisobutyronitrile is 25:10:1:1.5) is added, reaction is carried out at 70 DEG C for 8h under nitrogen protection, after filtration, washing and drying, modified solid particles are obtained;

[0053] S4, the modified solid particles and nylon resin, polytetrafluoroethylene, antioxidant, anti-aging agent, lubricant and initiator dicumyl peroxide are added into a double screw extruder according to the above mass fraction, melt extrusion is carried out at 240-250 DEG C, and an anti-skid wear-resistant nylon composite material is obtained.

[0054] Example 3

[0055] A kind of anti-skid wear-resistant nylon composite material, the anti-skid wear-resistant nylon composite material includes the ingredients of mass fraction as follows:

[0056]

[0057]

[0058] The preparation method of the anti-skid wear-resistant nylon composite material includes the following steps:

[0059] S1, mixing concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 1:5 to obtain a mixed solution, then immersing magnesium oxide into the mixed solution, ultrasonic reaction at 80°C for 4h, washing and drying to obtain hydroxylated magnesium oxide;

[0060] Mixing concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 1:5 to obtain a mixed solution, then immersing glass fiber into the mixed solution, ultrasonic reaction at 80°C for 4h, washing and drying to obtain hydroxylated glass fiber;

[0061] S2, mixing the hydroxylated magnesium oxide, hydroxylated glass fiber, polymerization inhibitor hydroquinone and acrylic acid with a mass ratio of 1:4:0.1:20, stirring and dispersing uniformly, ultrasonic reaction at 100°C for 6h, filtering and drying to obtain an intermediate product;

[0062] S3, mixing the intermediate product, hexafluorobutyl methacrylate and ethylene glycol diacrylate uniformly with 1,4-dioxane as the solvent, then adding initiator azobisisobutyronitrile (the mass ratio of the intermediate product, hexafluorobutyl methacrylate, ethylene glycol diacrylate and azobisisobutyronitrile is 25:10:1:1.5), reacting at 70°C for 8h under nitrogen protection, filtering, washing and drying to obtain modified solid particles;

[0063] S4, adding the modified solid particles and nylon resin, polytetrafluoroethylene, antioxidant, anti-aging agent, lubricant and initiator dicumyl peroxide into a twin-screw extruder according to the above mass fraction, melt extruding at 240-250°C to obtain a slip-resistant and wear-resistant nylon composite material.

[0064] Comparative Example 1

[0065] A slip-resistant and wear-resistant nylon composite material, the difference between this comparative example and Example 1 is that in step S3, ethylene glycol diacrylate is not added, and other components and preparation methods are the same as those of Example 1.

[0066] Comparative Example 2

[0067] A slip-resistant and wear-resistant nylon composite material, the difference between this comparative example and Example 1 is that steps S2 and S3 are deleted, and a mixture of hydroxylated magnesium oxide and hydroxylated glass fiber with a mass ratio of 1:4 is used as a modified solid particle, and other components and preparation methods are the same as those of Example 1.

[0068] Test Example

[0069] The slip-resistant and wear-resistant nylon composite materials prepared in Examples 1-3 and Comparative Examples 1-2 were tested for performance.

[0070] Tensile strength (10mm / min) and Izod notched impact strength (23°C) tests were performed according to ISO 527 and ISO 180 standards.

[0071] The dynamic friction coefficient was measured by a friction tester (room temperature 25℃, humidity 40%, load 100N).

[0072] After the samples of the examples and the comparative examples were placed at 60℃ for 60 days, the room temperature was recovered, and the mechanical properties were retested.

[0073] The test results are shown in Table 1.

[0074] Table 1 Performance test results

[0075]

[0076] According to Table 1, it can be seen that the anti-skid wear-resistant nylon composite material prepared in Examples 1-3 has high tensile strength and notched impact strength, and the friction coefficient is high, and after long-term storage at high temperature, the impact strength is still high, thereby prolonging the service life of the product in extreme environments. Comparative Example 1 removes the crosslinking agent, which makes it difficult for the modified solid particles to form a fully crosslinked body structure, and the mechanical properties are reduced, and the mechanical properties after high-temperature storage are also more obviously reduced; Comparative Example 2 uses hydroxylated glass fibers and magnesium oxide to replace the modified solid particles, which not only causes the inorganic particles to easily agglomerate, but also makes it difficult to play a compatibilization effect on the polytetrafluoroethylene and other components, which seriously affects the performance of the composite material, and the mechanical properties, anti-skid property and stability are all significantly reduced.

[0077] It is apparent to those skilled in the art that the present application is not limited to the details of the foregoing exemplary embodiments, and that the present application can be implemented in other particular forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be considered in all respects as illustrative and not restrictive, and the scope of the present application should be defined by the appended claims rather than the above description, and it is intended to encompass all changes falling within the meaning and range of equivalents of the claims.

[0078] In addition, it should be understood that although the present specification is described in terms of embodiments, each embodiment does not contain only one independent technical solution, and the description manner of the specification is only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.

Claims

1. A non-slip, wear-resistant nylon composite material, characterized in that, The antiskid wear-resistant nylon composite material comprises ingredients in mass fractions as follows: The modified solid particles are macromolecules formed by copolymerization of an intermediate product of acrylic acid grafted with hydroxylated magnesium oxide and hydroxylated glass fiber, hexafluorobutyl methacrylate and ethylene glycol diacrylate.

2. The anti-slip and wear resistant nylon composite material according to claim 1, characterized in that, The mass ratio of the intermediate product, hexafluorobutyl methacrylate and ethylene glycol diacrylate is 10-30:10-20:0.5-2.

3. The anti-slip and wear resistant nylon composite material according to claim 1, wherein, The mass ratio of the hydroxylated magnesium oxide and the hydroxylated glass fiber is 1:1-1:

4.

4. The anti-slip and wear resistant nylon composite material according to claim 1, wherein, The nylon resin is selected from one or more of PA6, PA66, PA46, PA6T, PA9T, PA10T and PA13T.

5. The method of making the anti-slip, wear-resistant nylon composite of any one of claims 1-4, characterized in that, The preparation method of the antiskid wear-resistant nylon composite material comprises the following steps: S1, hydroxylating magnesium oxide and glass fiber to obtain hydroxylated magnesium oxide and hydroxylated glass fiber; S2, mixing and heating the hydroxylated magnesium oxide and the hydroxylated glass fiber with acrylic acid and a polymerization inhibitor to obtain an intermediate product; S3, mixing the intermediate product with hexafluorobutyl methacrylate, ethylene glycol diacrylate and an initiator, and heating and reacting under inert gas protection to obtain modified solid particles.

6. The method for preparing the anti-slip and wear-resistant nylon composite material according to claim 5, characterized in that, Further comprising: S4, mixing the modified solid particles with nylon resin, polytetrafluoroethylene, antioxidant, anti-aging agent and lubricant, feeding into an extruder, melt extruding to obtain a product.

7. The method for preparing the anti-slip and wear-resistant nylon composite material according to claim 5, characterized in that, The hydroxylating treatment is: adding magnesium oxide and glass fiber into a mixed solution of concentrated sulfuric acid and concentrated nitric acid, and ultrasonic reaction to obtain hydroxylated magnesium oxide and hydroxylated glass fiber.

8. The method for preparing the anti-slip and wear-resistant nylon composite material according to claim 7, characterized in that, The temperature of the ultrasonic reaction is 60-90℃.

9. The method for preparing the anti-slip and wear-resistant nylon composite material according to claim 5, characterized in that, In step S2, the heating reaction temperature is 50-100℃.

10. The method for preparing the anti-slip and wear-resistant nylon composite material according to claim 5, characterized in that, In step S3, the heating reaction temperature is 50-100℃.

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