A wear-resistant additive for wear-resistant NMT plastic materials, and its preparation method and application

Abstract

This invention, belonging to the field of materials, discloses a wear-resistant additive for wear-resistant NMT plastic materials, its preparation method, and application. The wear-resistant additive comprises the following raw materials in parts by weight: 15-30 parts molybdenum disulfide; 15-30 parts bismuth sulfide; 40-60 parts copper sulfate; 2-5 parts organic amine; and 2-5 parts silane coupling agent. The modified metal sulfide for wear-resistant NMT plastic materials provided herein can improve the wear resistance of NMT plastics while maintaining their NMT bonding strength. Furthermore, it can improve the wear resistance of NMT plastics at relatively low addition levels without significantly degrading the material's mechanical properties. Furthermore, the preparation method of the present invention is simple and easy to implement, making it suitable for large-scale production.

Description

Technical Field

[0001] The present invention belongs to the field of materials, and in particular relates to a wear-resistant additive that can be used for wear-resistant NMT plastic materials, a preparation method thereof, and an application thereof. Background Art

[0002] The nanomolding process (NMT), invented by Taisei Corporation of Japan, allows materials such as modified polyphenylene sulfide (PPS) and modified butylene terephthalate (PBT) to be directly bonded to nano-processed metal surfaces through injection molding (patent WO 2007 / 040245, etc.). Subsequent patent publications (CN111117232A, CN202210592626.0, etc.) describe improved NMT technology that can bond not only metals but also ceramics. NMT technology has rapidly gained popularity in the mobile phone industry. With the rapid development of foldable screen phones, NMT technology has been widely applied to foldable screen hinge structures. In actual applications, it has been found that current NMT materials are prone to surface wear and debris shedding after repeated opening and closing of the hinge, which not only affects the appearance but also causes secondary damage to the hinge structure due to the detached debris. Therefore, the industry has placed higher requirements on the wear resistance of NMT plastics.

[0003] Polytetrafluoroethylene (PTFE) and molybdenum disulfide are commonly used wear-resistant plastic additives that can effectively reduce the friction coefficient and wear rate of plastics. However, significant effects require a relatively high addition level, generally exceeding 10%. Furthermore, experiments have shown that the addition of high levels of PTFE and molybdenum disulfide significantly reduces the bonding strength of NMT and the mechanical properties of the material, leading to cracking of the metal-plastic bond or the plastic itself during subsequent manufacturing processes. Therefore, PTFE and molybdenum disulfide are not suitable for wear-resistant NMT plastic materials. Currently, there are no mature wear-resistant additives suitable for NMT plastic materials on the market. Summary of the Invention

[0004] In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the primary object of the present invention is to provide a wear-resistant additive (modified metal sulfide) that can be used for wear-resistant NMT plastic materials.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned wear-resistant additive that can be used for wear-resistant NMT plastic materials.

[0006] Another object of the present invention is to provide an application of the above-mentioned wear-resistant additive for wear-resistant NMT plastic materials.

[0007] The purpose of the present invention is achieved through the following solutions:

[0008] A wear-resistant additive for wear-resistant NMT plastic materials, comprising the following raw materials in parts by weight:

[0009]

[0010] Furthermore, the wear-resistant additive that can be used for wear-resistant NMT plastic materials includes the following raw materials in parts by weight:

[0011]

[0012] Furthermore, the wear-resistant additive that can be used for wear-resistant NMT plastic materials includes the following raw materials in parts by weight:

[0013]

[0014] The organic amine is at least one of triethylamine and hydrazine hydrate, preferably triethylamine.

[0015] The silane coupling agent is at least one of vinyl silane, amino silane, methacryloxy silane and epoxy silane, preferably glycidyloxypropyltrimethoxysilane.

[0016] A method for preparing the wear-resistant additive that can be used for wear-resistant NMT plastic materials comprises the following steps:

[0017] (1) Molybdenum disulfide, bismuth sulfide, and copper sulfate are mixed, vacuumized, and then heated for reaction. After the reaction is completed, the mixture is naturally cooled, taken out, and ground into powder;

[0018] (2) The powder obtained by grinding in step (1), a monohydric alcohol, an organic amine and a silane coupling agent are mixed, and then heated under reflux for reaction. After the reaction is completed, the mixture is naturally cooled, filtered and then aged to obtain a modified metal sulfide, which can be used as a wear-resistant additive for wear-resistant NMT plastic materials.

[0019] The heating reaction in step (1) refers to the reaction at 700-900° C. for 20-30 hours;

[0020] The organic amine in step (2) is a small molecule polar substance that can better adhere to the surface of the sulfide powder, forming hydrogen bonds with the coupling agent or reacting with the active groups of the coupling agent. The silane coupling agent modifies the reactants in step (1) to facilitate the formation of a good interface with the plastic.

[0021] The monohydric alcohol described in step (2) is a monohydric alcohol with less than 6 carbon atoms, preferably ethanol; the role of the monohydric alcohol is mainly to disperse, so the amount of ethanol used is not limited.

[0022] The heating reflux time in step (2) is 10-15h.

[0023] The aging described in step (2) refers to aging at 150-180° C. for 2-6 hours.

[0024] The above-mentioned wear-resistant additives that can be used for wear-resistant NMT plastic materials are used as wear-resistant additives in NMT plastic materials.

[0025] The wear-resistant additive that can be used for wear-resistant NMT plastic material is used as a wear-resistant additive in NMT plastic material, wherein the addition amount of the wear-resistant additive that can be used for wear-resistant NMT plastic material is less than 10%, preferably 5%.

[0026] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0027] (1) The modified metal sulfide provided by the present invention can be used for wear-resistant NMT plastic materials, which can improve the wear resistance of NMT plastics while maintaining the NMT bonding strength.

[0028] (2) The modified metal sulfide provided by the present invention that can be used for wear-resistant NMT plastic materials can improve the wear resistance of NMT plastics at a relatively low addition amount without significantly reducing the mechanical properties of the material.

[0029] (3) The preparation method of the present invention is simple and easy to implement and is suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 Schematic diagram of the structure of the metal-plastic test piece; 1. Metal part; 2. Plastic part.

[0031] Figure 2 IR spectra of the mixture of molybdenum disulfide, bismuth sulfide and copper sulfate in Example 2 before and after calcination at 800°C for 24 hours.

[0032] Figure 3 These are physical images and scanning electron microscope images of the mixture of molybdenum disulfide, bismuth sulfide and copper sulfate in Example 2 before and after calcination at 800°C for 24 hours, where (a) represents before calcination and (b) represents after calcination.

[0033] Figure 4 This is the XRF elemental analysis characterization of the mixture of molybdenum disulfide, bismuth sulfide and copper sulfate in Example 2 before and after calcination at 800°C for 24 hours, where (a) represents before calcination and (b) represents after calcination. DETAILED DESCRIPTION

[0034] The present invention will be described in further detail below in conjunction with the examples and accompanying drawings, but embodiments of the present invention are not limited thereto. It should be understood that the specific embodiments described herein are only intended to explain the present invention and are not intended to limit the present invention. That is, the embodiments described are only some embodiments of the present invention, rather than all embodiments. In the examples, if specific conditions are not specified, the conditions are carried out according to conventional conditions or manufacturer recommendations. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0035] The modified metal sulfide of the present application, its preparation method and application examples are described in detail below using examples.

[0036] All raw materials used can be obtained commercially, as follows: molybdenum disulfide was purchased from Hubei Watson Technology Co., Ltd., bismuth sulfide was purchased from Wuhan Jiyesheng Chemical Co., Ltd., copper sulfate was purchased from Jinan Boyang Chemical Co., Ltd., triethylamine was purchased from Sinopharm Chemical Pure, silane coupling agent was purchased from Lida Chemical LD-560, ethanol was purchased from Sinopharm Analytical Pure, PBT was Bluestar Chemical 1110, PTFE was purchased from Daikin M532, glass fiber was Chongqing International ECS3031H, and ethylene methyl acrylate copolymer was Arkema AX8900.

[0037] In the following examples, the tensile strength was tested using the ISO 527 standard method, the notched impact strength was tested using the ISO 179 standard method, and the abrasion resistance was tested using the GBT 3960-2016 standard method.

[0038] The metal nano-injection-molded ceramic sample used in the present invention is prepared by the following process: 6061 aluminum alloy material, size specifications, length 45mm, width 18mm, thickness 1.6mm; T treatment process: sequentially alkali washing in NaOH solution (1.5mol / L, 60℃, 30 seconds), hydrochloric acid corrosion (1mol / L, 30℃, 30 seconds), and soaking in triethylamine solution (T treatment solution) (1.5mol / L, 30℃, 3 minutes), then the soaked sample is cleaned with water and dried to obtain a metal sample with nanopores on the surface.

[0039] Preparation of the plastic-metal test monolith used in the present invention:

[0040] The present invention refers to the method of Japanese Taisei Nano Injection Molding related patent (US8057890 (B2)) to prepare the plastic metal test integral part. Figure 1 This is a schematic diagram of the structure of the metal-plastic test piece. The metal sheet measures 18mm×45mm×1.6mm, the plastic part measures 10mm×45mm×3mm, and the bonding area between the plastic and the metal is 0.5cm. 2In all experiments, the injection molding conditions were kept the same, with a barrel temperature of 260-280°C and a mold temperature of 140°C, and the plastic compound was injected onto the metal sheet to obtain a plastic-metal test piece.

[0041] Plastic-metal bonding performance test:

[0042] The metal-plastic adhesion test standard used in this invention refers to the standard in Japan Daisei Chemical Patent (US8057890(B2)), and the plastic-metal bonding area is 0.5 cm 2 , a biaxial tensile test is performed on the test piece.

[0043] The preparation process of the plastic composite material is as follows: the components in corresponding amounts are weighed according to weight percentage, and then the components are mixed and granulated using a twin-screw extruder to obtain the plastic composite. The granulation temperature is 240-320°C.

[0044] Example 1

[0045] Mix 100g of molybdenum disulfide, 400g of bismuth sulfide, and 500g of copper sulfate, add to a reaction tube, and evacuate. Heat to 800°C and hold for 24 hours. Cool naturally and remove the reactants. Grind the reactants into a powder, add 2L of ethanol, 30g of triethylamine, and 30g of a silane coupling agent, and heat under reflux for 12 hours. Cool naturally, filter, and age at 160°C for 4 hours to obtain the final product A.

[0046] Example 2

[0047] Combine 250g of molybdenum disulfide, 250g of bismuth sulfide, and 500g of copper sulfate in a reaction tube and evacuate. Heat to 800°C for 24 hours. Cool naturally and remove the reactants. Grind the reactants into a powder, add 2L of ethanol, 30g of triethylamine, and 30g of a silane coupling agent, and heat under reflux for 12 hours. Cool naturally, filter, and age at 160°C for 4 hours to obtain the final product, Product B.

[0048] The infrared spectra of the mixture of molybdenum disulfide, bismuth sulfide and copper sulfate before and after calcination at 800℃ for 24h are as follows: Figure 2 As shown, the SO4 peak at position 1197 disappears, indicating that copper sulfate decomposes at high temperatures to produce CuO and SO3. A clear absorption peak appears at position 1080 after high-temperature calcination, indicating the formation of metal persulfate components. The high-temperature reaction process includes chemical reaction and physical doping.

[0049] During the high-temperature reaction, the mixture undergoes a distinct phase transition. No powdery white material is observed at 1000x magnification after calcination, indicating that the copper sulfate is almost completely decomposed, generating copper oxide at high temperatures. Physical doping of copper oxide and sulfide occurs, producing sulfide-doped copper oxide.

[0050] Example 2A

[0051] Combine 250g of molybdenum disulfide, 250g of bismuth sulfide, and 500g of copper sulfate, add to a reaction tube, and evacuate. Heat to 800°C for 24 hours. Allow to cool naturally, remove the reactants, and grind into a powder to obtain the final product, B1.

[0052] Example 2B

[0053] Combine 250g of molybdenum disulfide, 250g of bismuth sulfide, and 500g of copper sulfate in a reaction tube and evacuate. Heat to 800°C for 24 hours. Allow to cool naturally and remove the reactants. Grind the reactants into a powder, add 2L of ethanol, 30g of triethylamine, and 30g of a silane coupling agent, and heat under reflux for 12 hours. Allow to cool naturally, filter, and age at 100°C for 2 hours to obtain the final product, B2.

[0054] Example 3

[0055] Mix 400g of molybdenum disulfide, 100g of bismuth sulfide, and 500g of copper sulfate, add to a reaction tube, and evacuate. Heat to 800°C and hold for 24 hours. Cool naturally and remove the reactants. Grind the reactants into a powder, add 2L of ethanol, 30g of triethylamine, and 30g of a silane coupling agent, and heat under reflux for 12 hours. Cool naturally, filter, and age at 160°C for 4 hours to obtain the final product, C.

[0056] Example 4

[0057] Mix 400g of molybdenum disulfide, 400g of bismuth sulfide, and 200g of copper sulfate, add to a reaction tube, and evacuate. Heat to 800°C and hold for 24 hours. Cool naturally and remove the reactants. Grind the reactants into a powder, add 2L of ethanol, 30g of triethylamine, and 30g of a silane coupling agent, and heat under reflux for 12 hours. Cool naturally, filter, and age at 160°C for 4 hours to obtain the final product D.

[0058] Example 5

[0059] PBT resin, modified metal sulfide, toughening agent, and glass fiber were mixed in the weight ratios shown in Table 1 and pelletized using a twin-screw extruder at a pelletizing temperature of 240-260° C. The properties of the resulting PBT composite are shown in Table 1.

[0060] Table 1 Component weight percentage and performance data of PBT composite

[0061]

[0062] It can be found from Table 1 that when a suitable ratio of molybdenum disulfide / bismuth sulfide / copper sulfate is used and a suitable surface treatment process is adopted, the modified metal sulfide B (Test Example 6) can well maintain the mechanical strength and NMT bonding strength of the PBT composite material (Test Example 1) while significantly reducing the wear rate of the material.

[0063] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A wear-resistant additive that can be used for wear-resistant NMT plastic materials, characterized in that The following raw materials are included in parts by weight: 15-30 parts of molybdenum disulfide; 15-30 parts of bismuth sulfide; 40-60 parts of copper sulfate; 2-5 parts of organic amine; Silane coupling agent 2-5 parts; The preparation method of the wear-resistant additive that can be used for wear-resistant NMT plastic materials comprises the following steps: (1) Molybdenum disulfide, bismuth sulfide and copper sulfate are mixed, vacuumized, and then heated for reaction. After the reaction is completed, the mixture is naturally cooled, taken out and ground into powder; (2) mixing the powder obtained by grinding in step (1), a monohydric alcohol, an organic amine, and a silane coupling agent, and then heating and refluxing the mixture for reaction. After the reaction is completed, the mixture is naturally cooled, filtered, and then aged to obtain a wear-resistant additive that can be used for wear-resistant NMT plastic materials; The heating reaction in step (1) refers to the reaction at 700-900°C for 20-30h; The aging described in step (2) refers to aging at 150-180°C for 2-6 hours.

2. The wear-resistant additive for wear-resistant NMT plastic materials according to claim 1, characterized in that The following raw materials are included in parts by weight: 20-30 parts of molybdenum disulfide; 20-30 parts of bismuth sulfide; 45-55 parts of copper sulfate; 2-4 parts of organic amine; 2-4 parts of silane coupling agent.

3. The wear-resistant additive for wear-resistant NMT plastic materials according to claim 1, characterized in that The following raw materials are included in parts by weight: 25 parts of molybdenum disulfide; 25 parts of bismuth sulfide; 50 parts of copper sulfate; 3 parts of organic amine; 3 parts of silane coupling agent.

4. The wear-resistant additive for wear-resistant NMT plastic materials according to claim 1, characterized in that: The organic amine is triethylamine; The silane coupling agent is at least one of vinyl silane, amino silane, methacryloxy silane and epoxy silane.

5. The wear-resistant additive for wear-resistant NMT plastic materials according to claim 1, characterized in that: The monohydric alcohol described in step (2) is a monohydric alcohol with less than 6 carbon atoms; The heating reflux time in step (2) is 10-15 hours.

6. Use of the wear-resistant additive for wear-resistant NMT plastic materials according to any one of claims 1 to 4 in NMT plastic materials.

7. Use of the wear-resistant additive for wear-resistant NMT plastic materials according to claim 6 in NMT plastic materials, characterized in that: The amount of the wear-resistant additive that can be used for the wear-resistant NMT plastic material is less than 10%.

8. Use of the wear-resistant additive for wear-resistant NMT plastic materials according to claim 7, characterized in that: The added amount of the wear-resistant additive that can be used for the wear-resistant NMT plastic material is 5%.

Images