Environmentally friendly, wear-resistant and noise-reducing engineering plastic composition, preparation method therefor and use thereof

Abstract

An environmentally friendly, wear-resistant and noise-reducing engineering plastic composition, a preparation method therefor and a use thereof. The composition comprises the following components: a thermoplastic resin, a reinforcing filler, a wear-resistant and noise-reducing auxiliary agent, a wear-resistant auxiliary agent, and other auxiliary agents. The wear-resistant and noise-reducing auxiliary agent comprises at least one of a polyolefin-styrene graft copolymer or a polyolefin-styrene graft copolymer modified with a reactive functional group. The wear-resistant auxiliary agent is selected from among one of UHMWPE, polysiloxane, molybdenum disulfide, graphite, and a modified fatty acid ester. The reinforcing filler comprises at least one of fiberglass, carbon fibers, and an inorganic mineral. The wear-resistant and noise-reducing auxiliary agent and the wear-resistant auxiliary agent are used in combination, so that the wear resistance and noise reduction performance of the modified engineering plastic can be significantly improved, the composition is environmentally friendly, and the mechanical properties of the modified material can be maintained.

Description

Environment-friendly wear-resistant noise-reducing engineering plastic composition and preparation method and application thereof TECHNICAL FIELD

[0001] TECHNICAL FIELD

[0002] The present application belongs to the technical field of polymer material modification, and relates to an environment-friendly wear-resistant noise-reducing thermoplastic engineering plastic and a preparation method thereof. BACKGROUND

[0003] Wear resistance is one of the main mechanical properties of thermoplastic engineering plastics, and wear-resistant engineering plastics can be used to manufacture various mechanical parts, such as gears, pulleys, sliding blocks, carrier rollers and the like, and thus have a very wide range of applications in social production.

[0004] There are various types of wear-resistant agents for polymer materials, such as molybdenum disulfide (MoS2), graphite, carbon fiber, polytetrafluoroethylene (PTFE), silicone (silicone oil), ultra-high molecular weight polyethylene (UHMWPE) and the like, but each type of wear-resistant and friction-reducing component has its own characteristics, such as PTFE which has high versatility and has a very low friction coefficient; silicone generally needs to be used in combination with PTFE to achieve better results; graphite is more suitable for water environments, and has poor adhesion to the base material in dry conditions and is easy to fall off; molybdenum disulfide is widely used as a solid lubricant, but the friction coefficient is not low enough. However, from a comprehensive analysis of various use scenarios, the most representative wear-resistant additive is still PTFE. For example, the wear-resistant nylon composition in CN116478534A reduces the permeability of the nylon composition by selecting an epoxy resin with a specific epoxy value to react with the end group of PA66, thereby reducing the penetration of the lubricating grease component, and the combination of the PA66 resin and PTFE can fully exert the lubricating and wear-resistant properties of PTFE, so that the nylon composition still has excellent wear resistance under the action of high-temperature lubricating grease.

[0005] PTFE is used as an anti-wear agent, but it has many defects. First, the anti-wear effect of the modified material is not obvious when the content of PTFE in the plastic formula is low. Second, PTFE is a completely non-polar material, which has poor compatibility with most thermoplastic engineering plastics, and is difficult to extrude and granulate, has serious surface defects, and has obvious decrease in mechanical properties. Third, PTFE belongs to perfluoro and polyfluoro alkyl substances (PFAS), and fluorine-containing polymers have very high chemical stability. Once released into the environment, they can stay for a long time and cause environmental damage. The new EU restriction proposal considers that all PFAS must be regulated, the purpose of which is to prohibit the use and production of all PFAS in the EU, including PTFE. Furthermore, PFOA (perfluorooctanoic acid and its salts and related compounds) or PFOS (perfluorooctanesulfonyl compounds) and other substances that have been banned by the EU are used in the production of PTFE. Therefore, from the perspective of environmental protection, PTFE is no longer a suitable choice.

[0006] Thermoplastic engineering plastics are widely used in the fields of automobiles and household appliances due to their many advantages, but they also bring some problems. For example, the abnormal sound problem in current household appliances and automobile products has become one of the focuses of attention in the two industries. Since most household appliances generate heat or cool during operation, the different parts are extruded due to thermal expansion and contraction, resulting in "creaking" abnormal sound. This situation frequently occurs in air conditioning products. In automobile products, the parts are also extruded due to the vibration of the automobile or external force, which causes the parts to rub against each other and produce "creaking" abnormal sound. This abnormal sound may come from the friction between plastic parts and plastic parts, or from the friction between plastic parts and leather parts or metal parts. Therefore, how to solve the noise reduction problem of thermoplastic materials has also become one of the focuses of the industry. TECHNICAL PROBLEM

[0007] The present application provides an environmentally friendly wear-resistant and noise-reducing engineering plastic and a preparation method thereof. A new formula is used, in which environmentally friendly wear-resistant and noise-reducing additives and wear-resistant and noise-reducing aids are used as a compounding technology. The technology not only improves the tribological properties of some engineering plastics, but also has the function of noise reduction and sound elimination in some thermoplastic resins. In particular, the modified engineering plastics used in the fields of automobiles and household appliances have significant improvement effect. TECHNICAL SOLUTION

[0008] The object of the present application can be achieved by the following technical solutions:

[0009] An environmentally friendly wear-resistant and noise-reducing engineering plastic composition comprises the following components: thermoplastic resin, wear-resistant and noise-reducing additive, wear-resistant and noise-reducing aid, and processing aid. Further, it further comprises reinforcing filler.

[0010] In the present application, the weight ratio of the thermoplastic resin, the reinforcing filler, the wear-resistant noise-reducing additive, the wear-resistant additive, and the processing aid is 100:(0-60):(1-20):(0.1-10):(0.1-20), preferably, the weight ratio of the thermoplastic resin, the reinforcing filler, the wear-resistant noise-reducing additive, the wear-resistant additive, and the processing aid is 100:(0-60):(2-15):(0.5-5):(0.1-20).

[0011] The present application discloses a preparation method of the above-mentioned environmentally friendly wear-resistant noise-reducing engineering plastic composition, which is prepared from a thermoplastic resin, a reinforcing filler, a wear-resistant noise-reducing additive, a wear-resistant additive, and a processing aid; specifically, these raw materials are prepared into the above-mentioned environmentally friendly wear-resistant noise-reducing engineering plastic composition through an extrusion processing technology.

[0012] In the present application, the wear-resistant noise-reducing additive is at least one selected from a polyolefin-styrene graft copolymer or a polyolefin-styrene graft copolymer modified with a reactive functional group. The polyolefin-styrene graft copolymer is obtained by grafting a styrene-based polymer on a substituted or unsubstituted polyolefin molecular backbone; the polyolefin-styrene graft copolymer modified with a reactive functional group is a graft copolymer in which an acid anhydride, an epoxy, an acrylic acid, or a carboxylic acid, etc. is introduced into the polyolefin-styrene graft copolymer, and the reactive functional group is selected from one or more of acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, maleic acid dibutyl ester, citric acid, itaconic acid, and glycidyl methacrylate groups; the polyolefin is at least one selected from low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-high molecular weight polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene-α-olefin copolymer, ethylene-vinyl acetate, and ethylene-acrylate copolymer; the styrene-based polymer includes styrene, alkyl-substituted styrene with 1-10 carbon atoms, and halogen-substituted styrene.

[0013] In the present application, the polyolefin-styrene graft copolymer modified with a reactive functional group is prepared by reacting a polyolefin with a styrene-based polymer containing a reactive functional group.

[0014] Preferably, in the polyolefin-styrene graft copolymer or the polyolefin-styrene graft copolymer modified with a reactive functional group, the polyolefin accounts for 50-95% by weight, and the styrene-based polymer or the styrene-based polymer with a reactive functional group accounts for 5-50% by weight.

[0015] In the present application, the thermoplastic resin is selected from one or more of nylon, polyformaldehyde, polyphenylene sulfide, polycarbonate or its alloy; preferably, the nylon is one or more of aliphatic nylon, aromatic nylon, long carbon chain nylon or copolymer nylon; and the alloy is one of PC / ABS, PC / ASA, PC / PBT or PC / PET alloy.

[0016] In the present application, the reinforcing filler is selected from one or more of glass fiber, carbon fiber or other inorganic minerals.

[0017] In the present application, the processing aid includes at least one of antioxidants, lubricants, antibacterial agents, nucleating agents, antistatic agents, ultraviolet absorbers, colorants, compatibilizers, coupling agents, impact modifiers.

[0018] In the present application, the wear-resistant aid is selected from one or more of UHMWPE, polysiloxane, molybdenum disulfide, graphite, modified fatty acid ester.

[0019] The application discloses application of the above-mentioned environment-friendly wear-resistant and noise-reducing engineering plastic composition in preparation of wear-resistant materials.

[0020] The application discloses an environment-friendly wear-resistant and noise-reducing plastic prepared from the above-mentioned environment-friendly wear-resistant and noise-reducing engineering plastic composition. Further disclosed is application of the above-mentioned environment-friendly wear-resistant and noise-reducing plastic in preparation of high-molecular wear-resistant products. Beneficial effects

[0021] Compared with the prior art, the present application has the following beneficial effects: the present application adds at least one of polyolefin-styrene graft copolymer or polyolefin-styrene graft copolymer modified with a reactive functional group as a wear-resistant and noise-reducing aid, the styrene or styrene structure with a reactive functional group of the graft copolymer can be effectively combined with the main body of the engineering plastic through end group reaction, hydrogen bonding or similar polar structure, and the polyolefin structure of the main chain can form a wear-resistant layer on the surface of the modified engineering plastic, and does not delaminate with the main body of the engineering plastic, thereby providing durable wear resistance.

[0022] The present application further improves the wear resistance and noise reduction effect of the engineering plastic by compounding the polyolefin-styrene graft copolymer or the polyolefin-styrene graft copolymer modified with a reactive functional group with relatively environment-friendly wear-resistant aids such as UHMWPE, silicone, molybdenum disulfide and modified fatty acid ester.

[0023] The polyolefin-styrene graft copolymer or the polyolefin-styrene graft copolymer modified with a reactive functional group used in the present application replaces the traditional PTFE with environmental risks, and is a technical solution suitable for green industrial application. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 is an infrared spectrum of the ethylene-octene-styrene-glycidyl methacrylate graft copolymer in Example 1; wherein 1730 cm -1 is the carbonyl stretching vibration absorption peak in glycidyl methacrylate, 1492 cm -1 , 1452 cm -1 is the skeleton vibration absorption peak of aromatic ring, 1378 cm -1 and 719 cm -1 are ethylene-octene characteristic peaks, 698 cm -1 is the out-of-plane bending vibration of C-H on the aromatic ring.

[0025] Figure 2 is the friction performance test results, wherein (a), (b), (c) respectively correspond to the friction scar width comparison chart of the friction sample after the friction test in Example 2, Comparative Example 2 and Comparative Example 2'. Embodiments of the present application

[0026] The raw materials are prepared into the above-mentioned environmentally friendly wear-resistant and noise-reducing engineering plastic composition by an extrusion process. Specifically, the preparation method of the environmentally friendly wear-resistant and noise-reducing engineering plastic composition comprises the following steps:

[0027] (1) uniformly mix the thermoplastic resin, wear-resistant and noise-reducing additives, wear-resistant and noise-reducing aids, and processing aids in proportion to obtain a premix, and feed from the main feeding port of the extruder;

[0028] (2) add the reinforcing filler (if any) to the extruder through the side feeding port of the extruder after metering;

[0029] (3) the above-mentioned materials are melt blended and extruded to obtain the environmentally friendly wear-resistant and noise-reducing engineering plastic composition by a granulator;

[0030] As an example, the length-diameter ratio of the twin-screw extruder used is (36-52):1, the processing temperature is 150-320℃, and the rotation speed is 250-600 rpm.

[0031] The present application will be described in detail below in conjunction with specific examples. The following examples will help those skilled in the art to further understand the present application, but do not limit the present application in any form. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present application. These all belong to the protection scope of the present application. The raw materials used in the present application are all existing products, and the specific preparation operation and performance test are conventional techniques.

[0032] The preparation of the polyolefin-styrene graft copolymer or the polyolefin-styrene graft copolymer modified with a reactive functional group is a conventional technique. For example, the polyolefin-styrene graft copolymer modified with a reactive functional group is prepared by the following method: a corresponding functional polymer is synthesized by a two-step method, in the first step, a styrene-based polymer containing a reactive functional group is prepared by a bulk, solution or suspension polymerization method, and in the second step, different types of polyolefins are reacted with the reaction product of the first step by a reactive extrusion method under the action of ultrasonic waves and a catalyst to obtain the final target product.

[0033] For example, the preparation of the glycidyl methacrylate graft copolymer is as follows:

[0034] (1) A reaction kettle is charged with styrene monomers, glycidyl methacrylate monomers, oil-soluble initiators, dispersants, co-dispersants, molecular weight regulators and deionized water in a weight ratio, and stirred and heated to 75-85°C, and reacted for 4-6 hours, and then heated to 85-90°C for 1-3 hours of curing. After the reaction is completed, the obtained material is filtered, washed with deionized water, dried to constant weight, and sieved to obtain an intermediate.

[0035] (2) The polyolefin, the intermediate, the imidazole catalyst, the reactive monomer and the processing aid are weighed and mixed uniformly, and then fed into a twin-screw extruder, melted, mixed, extruded, devolatilized, granulated and dried to obtain the target functional polymer. The length-diameter ratio of the twin-screw extruder is 44-56:1, the extrusion temperature is 160-240°C, and the screw rotation speed is 200-400 rpm.

[0036] Referring to the above method, the styrene monomers are replaced with other styrene monomers or the glycidyl methacrylate monomers are replaced with other reactive functional monomers to obtain different polyolefin-styrene graft copolymers modified with a reactive functional group.

[0037] Example 1

[0038] The preparation of the ethylene-octene-styrene-glycidyl methacrylate graft copolymer is as follows:

[0039] (1) A reaction kettle is charged with 38 parts of styrene monomers, 2 parts of glycidyl methacrylate monomers, 0.2 parts of oil-soluble initiator azobisisobutyronitrile, 0.4 parts of dispersant polyvinyl alcohol, 0.02 parts of co-dispersant sodium dodecyl sulfate, 0.2 parts of molecular weight regulator dodecyl mercaptan and deionized water in a weight ratio of 2:1, and stirred and heated to 80°C, and reacted for 5 hours, and then heated to 90°C for 2 hours of curing. After the reaction is completed, the obtained material is filtered, washed with deionized water for 3 times, dried to constant weight at 80°C, and sieved to obtain an intermediate.

[0040] (2) by weight, 60 parts of ethylene-octene copolymer (POE Engage 8200), 40 parts of the above intermediate, 0.2 parts of imidazole catalyst (2-methyl imidazole), 0.5 parts of reactive monomer acrylic acid and processing aid (0.2 parts of antioxidant 168, 0.2 parts of 1010, 0.3 parts of lubricant EBS) are weighed and mixed uniformly, then put into a twin-screw extruder, melt mixed, extruded, reacted and devolatilized, then granulated and dried to obtain the target functional polymer: ethylene-octene-styrene-glycidyl methacrylate graft copolymer. The product's infrared test is shown in Figure 1; the length-diameter ratio of the twin-screw extruder is 50:1, the extrusion temperature is 160-240°C, and the screw speed is 300 rpm.

[0041] An environmentally friendly wear-resistant and noise-reducing engineering plastic composition is prepared from the following components by weight: 100 parts of PPS resin (Zhejiang Xinheng), 45 parts of glass fiber (584), 5 parts of ethylene-octene-styrene-glycidyl methacrylate graft copolymer as a wear-resistant and noise-reducing additive, 3 parts of graphite as a wear-resistant additive, and 0.5 parts of antioxidant 1790.

[0042] After the above raw materials are uniformly mixed, they are put into an extruder with a length-diameter ratio of 40:1. The glass fiber is added through a side feeding port. The processing temperature is 280-320°C, the speed is 250 rpm, and the sample is obtained by extrusion granulation. After the particles are dried, they are injection molded into a sample bar for testing.

[0043] Example 2

[0044] An environmentally friendly wear-resistant and noise-reducing engineering plastic composition is prepared from the following components by weight: 100 parts of PA66 (EPR27), 30 parts of glass fiber (560A), 10 parts of linear low density polyethylene-styrene graft copolymer (BP-231, Jiaiyirong Polymer (Shanghai) Co., Ltd.) as a wear-resistant and noise-reducing additive, 0.5 parts of silicone masterbatch (GENIOPLAST Pellets S, Wacker Chemical) as a wear-resistant additive, 0.2 parts of antioxidant 1098, and 0.2 parts of antioxidant 168; wherein the linear low density polyethylene-styrene graft copolymer is prepared from 70 parts of linear low density polyethylene and 30 parts of styrene.

[0045] After the above raw materials are uniformly mixed, they are put into an extruder with a length-diameter ratio of 40:1. The glass fiber is added through a side feeding port. The processing temperature is 250-270°C, the speed is 300 rpm, and the sample is obtained by extrusion granulation. After the particles are dried, they are injection molded into a sample bar for testing.

[0046] Example 3

[0047] An environment-friendly wear-resistant and noise-reducing engineering plastic composition is prepared from the following components in parts by weight: 100 parts of PA6 (1013B, Japan Ube), 60 parts of carbon fiber (HTC413), 15 parts of low-density polyethylene-styrene-maleic anhyter graft copolymer as a wear-resistant and noise-reducing additive, 5 parts of molybdenum disulfide as a wear-resistant additive, 0.2 parts of antioxidant 1098, 0.2 parts of antioxidant 168, 8 parts of impact modifier (FB521A, Jia Yirong Polymer (Shanghai) Co., Ltd.), and 0.4 parts of lubricant (erucic acid amide); wherein the low-density polyethylene-styrene-maleic anhyter graft copolymer is prepared from 90 parts of linear low-density polyethylene, 9.5 parts of styrene, and 0.5 part of maleic anhydride, and the preparation method thereof is referred to Example 1, wherein the ethylene-octene copolymer is replaced by low-density polyethylene (Yanshan Petrochemical 1150A), and the glycidyl methacrylate monomer is replaced by maleic anhydride.

[0048] After the above raw materials are uniformly mixed, they are put into an extruder with a length-diameter ratio of 44:1, the carbon fiber is added through a side feeding port, the processing temperature is 230-250°C, the rotating speed is 400 rpm, the sample is obtained by extrusion granulation, the particles are dried, and then the sample bar is formed by conventional injection molding for testing.

[0049] Example 4

[0050] An environment-friendly wear-resistant and noise-reducing engineering plastic composition is prepared from the following components in parts by weight: 100 parts of POM (F20-03, South Korea KEP), 2 parts of ethylene-vinyl acetate-styrene-acrylic acid graft copolymer as a wear-resistant and noise-reducing additive, 2 parts of UHMWPE (T0604F, Sinopec) as a wear-resistant additive, 0.2 parts of antioxidant 245, and 1 part of carbon black master batch (Cabot UN2014); wherein the ethylene-vinyl acetate-styrene-acrylic acid graft copolymer is prepared from 50 parts of ethylene-vinyl acetate, 49 parts of styrene, and 1 part of acrylic acid, and the preparation method thereof is referred to Example 1, wherein the ethylene-octene copolymer is replaced by ethylene-vinyl acetate copolymer (Yanshan Petrochemical EVA V5110J), and the glycidyl methacrylate monomer is replaced by acrylic acid.

[0051] After the above raw materials are uniformly mixed, they are put into an extruder with a length-diameter ratio of 36:1, the processing temperature is 150-170°C, the rotating speed is 250 rpm, the sample is obtained by extrusion granulation, the particles are dried, and then the sample bar is formed by conventional injection molding for testing.

[0052] Example 5

[0053] An environment-friendly wear-resistant and noise-reducing engineering plastic composition is prepared from the following components by weight parts: 100 parts of PC (1100, Letian Chemical), 5 parts of a compounded product of ultra-high molecular weight polyethylene-styrene (BP-2301, Jia Yirong Polymer (Shanghai) Co., Ltd.) and 5 parts of low-density polyethylene-styrene-glycidyl methacrylate graft copolymer as a wear-resistant and noise-reducing additive, 1 part of high-purity fatty acid ester (M-B96R, Japan Oil) as a wear-resistant additive, 0.3 parts of antioxidant 923; wherein the ultra-high molecular weight polyethylene-styrene is prepared from 60 parts of ultra-high molecular weight polyethylene and 40 parts of styrene; the low-density polyethylene-styrene-glycidyl methacrylate graft copolymer is prepared from 75 parts of low-density polyethylene (Yanshan Petrochemical 1150A), 20 parts of styrene and 5 parts of glycidyl methacrylate, and the preparation method refers to Example 1, and the ethylene-octene copolymer in the second step is replaced with low-density polyethylene.

[0054] After the above raw materials are uniformly mixed, they are put into an extruder with a length-diameter ratio of 52:1, the processing temperature is 250-280°C, the rotating speed is 600 rpm, the sample is obtained through extrusion granulation, the particles are dried, and then the sample bar is formed through normal injection molding for testing.

[0055] Example 6

[0056] An environment-friendly wear-resistant and noise-reducing engineering plastic composition is prepared from the following components by weight parts: 70 parts of PC (1220, Letian Chemical), 30 parts of ABS (8434, Takachiho Petrochemical), 2 parts of a compounded product of ethylene-methyl acrylate-styrene-glycidyl methacrylate graft copolymer and 3 parts of low-density polyethylene-styrene graft copolymer (BP-2305, Jia Yirong Polymer (Shanghai) Co., Ltd.) as a wear-resistant and noise-reducing additive, 1 part of silicone (MB50-001) as a wear-resistant additive, 0.3 parts of antioxidant 1076 and 0.2 parts of antioxidant 168, 1 part of a compatibilizer (SAG-002, Jia Yirong Polymer (Shanghai) Co., Ltd.), 4 parts of an impact modifier (SBG-715, Jia Yirong Polymer (Shanghai) Co., Ltd.); wherein the ethylene-methyl acrylate-styrene-glycidyl methacrylate graft copolymer is prepared from 50 parts of ethylene-methyl acrylate, 48 parts of styrene and 2 parts of glycidyl methacrylate, and the preparation method refers to Example 1, and the ethylene-octene copolymer in the second step is replaced with ethylene-methyl acrylate copolymer (29MA03, SK Chemicals); the low-density polyethylene-styrene graft copolymer is prepared from 65 parts of low-density polyethylene and 35 parts of styrene.

[0057] After the above raw materials are uniformly mixed, they are put into an extruder with a length-diameter ratio of 52:1, the processing temperature is 230-260°C, the rotating speed is 500 rpm, the sample is obtained through extrusion granulation, the particles are dried, and then the sample bar is formed through normal injection molding for testing.

[0058] Comparative Example 1

[0059] The ethylene-octene-styrene-glycidyl methacrylate graft copolymer was replaced with 5 parts of graphite, and the rest was the same as Example 1.

[0060] Comparative Example 2

[0061] The wear-reducing and noise-reducing aid was replaced with an equal amount of PTFE (L-5, Daikin, Japan), and the rest was the same as Example 2.

[0062] Comparative Example 2'

[0063] No wear-reducing and noise-reducing aid and wear-reducing aid were added, and the rest was the same as Example 2.

[0064] Comparative Example 3

[0065] No low-density polyethylene-styrene-maleic anhydride graft copolymer was added as a wear-reducing and noise-reducing aid, and the rest was the same as Example 3.

[0066] Comparative Example 4

[0067] The wear-reducing and noise-reducing aid was replaced with an equal amount of PTFE (L-5, Daikin, Japan), and the rest was the same as Example 4.

[0068] Comparative Example 4'

[0069] Only 4 parts of ethylene-vinyl acetate-styrene-acrylic acid graft copolymer were used as a wear-reducing and noise-reducing aid, and no wear-reducing aid was added, and the rest was the same as Example 4.

[0070] Comparative Example 5

[0071] No ultra-high molecular weight polyethylene-styrene graft copolymer and low-density polyethylene-styrene-glycidyl methacrylate graft copolymer was added as a wear-reducing and noise-reducing aid, and was replaced with 10 parts of UHMWPE, and the rest was the same as Example 5.

[0072] Comparative Example 5'

[0073] Only 10 parts of ultra-high molecular weight polyethylene-styrene graft copolymer were added as a wear-reducing and noise-reducing aid, and the rest was the same as Example 5.

[0074] Comparative Example 6

[0075] No low-density polyethylene-styrene graft copolymer was used, and only 5 parts of ethylene-methyl acrylate-styrene-glycidyl methacrylate graft copolymer was added as a wear-reducing and noise-reducing aid, and the rest was the same as Example 6.

[0076] Comparative Example 6'

[0077] PTFE (L-5, Japan Daikin) was used to replace the wear-resistant and noise-reducing additives in Example 6, and the rest was the same as Example 6.

[0078] The part of the raw materials and additives in the above formula which are not marked with manufacturers are all conventional products on the market.

[0079] Performance test

[0080] Tensile strength: tested according to ISO 527 standard, test speed 50 mm / min;

[0081] Bending strength: tested according to ISO 178 standard, test speed 2 mm / min;

[0082] Charpy notched impact strength: tested according to ISO 179-1 standard, impact energy 4 J;

[0083] Tribological test: tested according to GB / T 3960-2016 standard, test time 2 h, load 196 N;

[0084] Rattling noise (RPN) test: according to VDA 230-206 method, RPN values under different sliding speeds of 1 mm / s and 4 mm / s and different loads of 10 N and 40 N were measured to evaluate the friction noise of the material; according to the standard VDA 230-206, the possibility of stick-slip phenomenon of the material is divided into ten grades: when RPN is 1-3, it is determined that the material has low risk of stick-slip noise; when RPN is 4-6, it is considered that the material has moderate risk of producing stick-slip noise; when RPN is 7-10, it is considered that the material has a greater probability of stick-slip noise under friction.

[0085] The mechanical properties, friction properties and noise test results of the relevant samples prepared according to the examples and comparative examples are shown in Tables 1-6.

[0086]

[0087]

[0088]

[0089] Table 1 shows the performance comparison of glass fiber reinforced PPS with wear resistance. The difference between Example 1 and Comparative Example 1 is mainly whether ethylene-octene-styrene-glycidyl methacrylate graft copolymer is used as wear resistance and noise reduction aid. From the results, the combination of GMA functional groups in ethylene-octene-styrene-glycidyl methacrylate graft copolymer and POE toughening and wear resistance is better than the glass fiber reinforced PPS system using only graphite. Not only is the strength not lost, but the notched impact strength is significantly improved, and more importantly, the wear resistance test data is better than that of graphite alone.

[0090] From the data of Example 2 and Comparative Examples 2 and 2' in Table 2, 10 parts of linear low density polyethylene-styrene graft copolymer BP-231, 10 parts of PTFE and no wear resistance and noise reduction aid were added to the glass fiber reinforced PA66 formulation system. From the basic mechanical property test data, the difference is not significant, and the notched impact performance of the system in Example 2 is slightly better, which can be explained by the good toughness of linear low density polyethylene, which can improve the impact performance of the entire material system. Although Comparative Example 2' has better tensile and bending performance, it has higher glass fiber content, but the impact performance is the lowest, and the tribology test is also the worst. In Comparative Example 2, an equal amount of PTFE is used to replace BP-231, which not only has no advantage in mechanical properties, but also is inferior to BP-231 in wear resistance. The main reason is that PTFE has no reinforcing effect and poor compatibility with the matrix, and the friction performance improvement effect is limited when the amount is insufficient. In Figure 2, the wear scar width of the friction sample of Example 2 (a) and Comparative Example 2 (b) and Comparative Example 2' (c) is shown. The advantages of the example are very obvious.

[0091] Table 3 shows the performance test results of carbon fiber reinforced PA6 of Example 3 and Comparative Example 3. The example selects low density polyethylene-styrene-maleic anhydride graft copolymer and molybdenum disulfide, which is obviously better than molybdenum disulfide alone in the comparative example in wear resistance. Not only that, but also because the graft copolymer contains reactive maleic anhydride functional groups, it can react with nylon and carbon fiber to improve the bonding force between carbon fiber and nylon matrix, and the low density polyethylene in the graft copolymer can have a synergistic toughening effect with the impact modifier.

[0092] In Table 4, different wear-resistant and noise-reducing solutions for polyformaldehyde are seen. Example 4 and Comparative Example 4 respectively add ethylene-vinyl acetate-styrene-acrylic acid graft copolymer, UHMWPE compounding solution, and PTFE and UHMWPE compounding solution. From the mechanical properties, the data gap is not large. In the example, due to the introduction of the multi-functional structure of ethylene-vinyl acetate-styrene-acrylic acid, there is a slight advantage in toughness, and the wear resistance is also slightly ahead of the PTFE and UHMWPE compounding form. More importantly, in the noise test results, it can be seen that the compounding solution of the example is significantly better than Comparative Example 4. Under the same test conditions, the RPN value of Example 4 is lower than that of Comparative Example 4. Comparative Example 4' does not use a compounding solution, but only adds ethylene-vinyl acetate-styrene-acrylic acid graft copolymer as a wear-resistant and noise-reducing additive. Except for the impact strength, the other mechanical properties are not as good as Example 4. In the wear and noise reduction test results, it also shows that its effect is slightly inferior to the compounding solution of Example 4.

[0093] Table 5 corresponds to the performance comparison of wear-resistant PC. In Example 5 and Comparative Example 5, the same attention is paid to whether the wear-resistant and noise-reducing additive of the application is used. After all the PC in Comparative Example 5 uses UHMWPE, the processing of PC is more difficult, the appearance of the prepared sample is also very poor, and the notched impact performance rapidly decreases, and the tribological performance is also general. Using the wear-resistant and noise-reducing additive of the application, not only the friction effect is excellent, but also the grafted GMA functional group can interact with the end group of PC, which can play the role of end-capping anti-hydrolysis and maintaining the mechanical properties of the material. In Comparative Example 5', only the ultra-high molecular weight polyethylene-styrene graft copolymer without a reactive functional group is used. Although the wear resistance performance is good, it also affects the impact performance and processing performance of PC. Without using the wear-resistant and noise-reducing additive containing GMA reactive functional group, there will be compatibility problems between it and PC, resulting in defects in the appearance and performance of the product, and greatly reducing the practicability.

[0094] Table 6 lists the effects of using different wear-resistant and noise-reducing additives in PC / ABS alloys. From the mechanical properties, Example 6 has better overall performance (balance of rigidity and toughness), while Comparative Example 6 has the best notched impact performance due to the use of ethylene-methyl acrylate-styrene-glycidyl methacrylate graft copolymer as the wear-resistant and noise-reducing additive, but the processing performance is general. This is because, on the one hand, ethylene-methyl acrylate has toughening effect, and on the other hand, the GMA content in the graft copolymer is too high, which will participate more in the reaction with PC, resulting in processing difficulty. Comparative Example 6' uses PTFE, not only the mechanical properties decrease significantly, but also the appearance of the product is poor. From the wear resistance and noise reduction effect, Example 6 uses a variety of wear-resistant additive compounding scheme, not only the wear resistance is outstanding, in the noise reduction effect, no matter how the conditions change, its RPN value is less than 3, in the low risk area; while using ethylene-methyl acrylate-styrene-glycidyl methacrylate graft copolymer system, the wear resistance performance is also good, but the noise reduction effect is general, the RPN value is basically in the medium risk area; Comparative Example 6' not only has unsatisfactory friction performance, but also has a high probability of generating stick-slip noise.

[0095] The specific embodiments of the present application are described above. It should be understood that the present application is not limited to the specific embodiments described above, and various modifications or changes can be made by those skilled in the art within the scope of the claims, which do not affect the essential content of the present application.

Claims

1. An environmentally friendly, wear-resistant, and noise-reducing engineering plastic composition, characterized in that, It comprises the following components: thermoplastic resin, wear-resistant and noise-reducing additive, wear-resistant aid, and processing aid; wherein the wear-resistant and noise-reducing additive is selected from at least one of polyolefin-styrene graft copolymer or polyolefin-styrene graft copolymer modified with reactive functional groups.

2. The environmentally friendly wear-resistant and noise-reducing engineering plastic composition according to claim 1, characterized in that, The thermoplastic resin is selected from one or more of nylon, polyoxymethylene, polyphenylene sulfide, polycarbonate, or their alloys; the environmentally friendly wear-resistant and noise-reducing engineering plastic composition further includes reinforcing fillers; the reinforcing fillers are selected from one or more of glass fiber, carbon fiber, or other inorganic minerals; the processing aids include at least one of antioxidants, lubricants, antibacterial agents, nucleating agents, antistatic agents, ultraviolet absorbers, colorants, compatibilizers, coupling agents, and impact modifiers; the wear-resistant aid is selected from one or more of UHMWPE, polysiloxane, molybdenum disulfide, graphite, and modified fatty acid esters.

3. The environmentally friendly wear-resistant and noise-reducing engineering plastic composition according to claim 2, characterized in that, The weight ratio of thermoplastic resin, reinforcing filler, wear-resistant and noise-reducing additive, wear-resistant agent and processing aid is 100:(0~60):(1~20):(0.1~10):(0.1~20).

4. The environmentally friendly wear-resistant and noise-reducing engineering plastic composition according to claim 1, characterized in that, The polyolefin-styrene graft copolymer is obtained by grafting styrene-based polymers onto the main chain of a substituted or unsubstituted polyolefin molecule; the polyolefin-styrene graft copolymer with reactive functional group modification is a graft copolymer incorporating reactive functional groups into a polyolefin-styrene graft copolymer.

5. The environmentally friendly wear-resistant and noise-reducing engineering plastic composition according to claim 4, characterized in that, In the polyolefin-styrene graft copolymer or the polyolefin-styrene graft copolymer modified with reactive functional groups, the polyolefin accounts for 50-95% by weight.

6. The environmentally friendly wear-resistant and noise-reducing engineering plastic composition according to claim 4, characterized in that, The polyolefin is selected from at least one of low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-high molecular weight polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, and other ethylene-α-olefin copolymers, ethylene-vinyl acetate copolymers, and ethylene-acrylate copolymers; the reactive functional group is selected from one or more of acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, dibutyl maleate, citric acid, itaconic acid, and glycidyl methacrylate groups.

7. The method for preparing the environmentally friendly wear-resistant and noise-reducing engineering plastic composition according to claim 1, characterized in that, It is prepared from thermoplastic resin, reinforcing filler, wear-resistant and noise-reducing additive, wear-resistant agent and processing aid.

8. The application of the environmentally friendly wear-resistant and noise-reducing engineering plastic composition according to claim 1 in the preparation of wear-resistant materials.

9. An environmentally friendly, wear-resistant, and noise-reducing plastic, characterized in that, It is prepared from the environmentally friendly wear-resistant and noise-reducing engineering plastic composition according to claim 1.

10. The application of the environmentally friendly wear-resistant and noise-reducing plastic of claim 9 in the preparation of polymer wear-resistant products.

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