CN112457655A - Vibration-damping wear-resistant material and preparation method and application thereof - Google Patents
Vibration-damping wear-resistant material and preparation method and application thereof Download PDFInfo
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- CN112457655A CN112457655A CN202011378911.XA CN202011378911A CN112457655A CN 112457655 A CN112457655 A CN 112457655A CN 202011378911 A CN202011378911 A CN 202011378911A CN 112457655 A CN112457655 A CN 112457655A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention provides a vibration-damping wear-resistant material and a preparation method and application thereof; the vibration-damping wear-resistant material is prepared from the following raw materials: 85 wt% -90 wt% of thermoplastic resin; 2-4 wt% of wear-resisting agent; 2 to 4 weight percent of dioctyl phthalate; 2-4 wt% of polytetrafluoroethylene; and the balance of auxiliary agent. Compared with the prior art, the vibration-damping wear-resistant material provided by the invention adopts specific content components, realizes better interaction, has vibration-damping and wear-resistant functions, can replace a metal rubber composite material to be used as a material for manufacturing an automobile vibration-damping system, and is suitable for working conditions such as vibration damping, friction resistance, corrosion resistance and the like on the basis of meeting the requirements on strength and rigidity; in addition, the product takes thermoplastic resin as a main raw material, has small dead weight and is convenient to recycle. Experimental results show that the self weight of the vibration-damping wear-resistant material is less than 100g, the tensile strength is greater than 15MPa, the elongation at break is greater than 20%, the Shore A hardness is 75-95, and the friction coefficient to 45# steel is less than 0.1.
Description
Technical Field
The invention relates to the technical field of automobile vibration reduction systems, in particular to a vibration reduction wear-resistant material and a preparation method and application thereof.
Background
According to relevant statistics, the largest global carbon emissions are from automotive emissions. With global resource shortage and climate warming, limiting carbon emission is an effective means for slowing down global exhaustion of petroleum energy and deterioration of natural ecological environment. Reducing the carbon emission of automobiles, prolonging the service life of parts and reducing the later maintenance cost are important subjects of the automobile industry in the future.
At present, automobiles use a large number of rubber metal vibration reduction systems to achieve the purposes of reducing vibration and supporting other parts. Taking a large commercial truck as an example, the truck largely uses shock absorbers such as a thrust rod, a stabilizer bar hanger rod, a rubber suspension, various bushings and the like. In order to bear a certain load, the traditional commercial truck mostly uses metal rubber composite materials to manufacture the product, namely the rubber metal composite damping sleeve.
The rubber metal composite damping sleeve is generally manufactured into two sections, a metal part is manufactured firstly, then the surface of the metal is treated, and then the rubber and the metal are vulcanized together through a mould; wherein the metal part provides product rigidity and strength and the rubber part provides a vibration damping function. The main problems with this system are: (1) the product is made of metal, so that the self weight is large, the corrosion resistance is poor, the light weight effect is poor, and the light weight advantage is not provided for the whole vehicle, so that the oil consumption of the whole vehicle is increased; (2) the condition that the transmission shaft is abraded by the metal material of the inner ring causes the service life of a product to be reduced, even the shaft is abraded, and the service life of the product or a system is reduced; (3) the rubber belongs to thermosetting materials, and can not be recycled after the whole life cycle of the product, thereby causing influence on the environment. In conclusion, the products have the problems of larger self weight, deviation of wear resistance, lower total service life, high and constant long-term oil consumption of the whole automobile and the like, which are similar to the current trend of light weight and maintenance-free of automobiles, and a large number of later quality claims and even serious quality accidents occur, thereby causing great troubles to the whole automobile factories.
Disclosure of Invention
In view of the above, the present invention provides a vibration-damping wear-resistant material, and a preparation method and an application thereof.
The invention provides a vibration-damping wear-resistant material which is prepared from the following raw materials:
85 wt% -90 wt% of thermoplastic resin;
2-4 wt% of wear-resisting agent;
2 to 4 weight percent of dioctyl phthalate;
2-4 wt% of polytetrafluoroethylene;
and the balance of auxiliary agent.
Preferably, the thermoplastic resin is selected from thermoplastic polyurethane, thermoplastic polyester, thermoplastic TPV or thermoplastic polyamide.
Preferably, the Shore A hardness of the thermoplastic resin is 70-100.
Preferably, the anti-wear agent is selected from one or more of aramid fiber, polyethylene fiber, polyester fiber, polyether, silicone powder, stearic acid, calcium stearate, oleic acid, oleamide, erucic acid and erucic acid amide.
Preferably, the auxiliary agent is selected from one or more of antioxidant, glass fiber, glass bead, basalt fiber, barium sulfate, calcium carbonate, quartz powder, wollastonite and talcum powder.
The invention also provides a preparation method of the vibration-damping wear-resistant material, which comprises the following steps:
a) and mixing the thermoplastic resin, the wear-resisting agent, the dioctyl phthalate, the polytetrafluoroethylene and the auxiliary agent, and compounding to obtain the vibration-damping wear-resisting material.
Preferably, the compounding process after the mixing in the step a) is performed by using a twin-screw extruder.
Preferably, the composite extrusion processing temperature is 180-240 ℃, the feeding speed is 30-65 rpm, and the extrusion speed is 30-50 m/min.
The invention also provides a wear-resistant vibration damping bushing which is integrally formed by the vibration damping and wear-resistant material in the modes of injection molding and die pressing;
or the like, or, alternatively,
the damping wear-resistant material is obtained by compounding an insert which is formed by injection molding and die pressing as an inner layer and thermoplastic resin as an outer layer;
the vibration-damping wear-resistant material is the vibration-damping wear-resistant material in the technical scheme.
Preferably, the tensile strength of the thermoplastic resin is more than 35MPa, the tear strength is 90N/mm-100N/mm, the elongation at break is 500% -700%, and the Shore A hardness is 70-100.
The invention provides a vibration-damping wear-resistant material and a preparation method and application thereof; the vibration-damping wear-resistant material is prepared from the following raw materials: 85 wt% -90 wt% of thermoplastic resin; 2-4 wt% of wear-resisting agent; 2 to 4 weight percent of dioctyl phthalate; 2-4 wt% of polytetrafluoroethylene; and the balance of auxiliary agent. Compared with the prior art, the vibration-damping wear-resistant material provided by the invention adopts specific content components, realizes better interaction, has vibration-damping and wear-resistant functions, can replace a metal rubber composite material to be used as a material for manufacturing an automobile vibration-damping system, and is suitable for working conditions such as vibration damping, friction resistance, corrosion resistance and the like on the basis of meeting the requirements on strength and rigidity; in addition, the product takes thermoplastic resin as a main raw material, has small dead weight and is convenient to recycle. Experimental results show that the self weight of the vibration-damping wear-resistant material is less than 100g, the tensile strength is greater than 15MPa, the elongation at break is greater than 20%, the Shore A hardness is 75-95, and the friction coefficient to 45# steel is less than 0.1.
In addition, the preparation method provided by the invention is simple and stable in process, easy in condition control, suitable for large-scale production and wide in application prospect.
Drawings
Fig. 1 is a schematic structural diagram of a wear-resistant damping bushing integrally formed from a damping wear-resistant material provided in embodiment 1 of the present invention;
fig. 2 is a schematic structural view of a wear-resistant vibration damping bush obtained by using a vibration-damping wear-resistant material provided in embodiment 4 of the present invention as an inner layer of the wear-resistant vibration damping bush.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a vibration-damping wear-resistant material which is prepared from the following raw materials:
85 wt% -90 wt% of thermoplastic resin;
2-4 wt% of wear-resisting agent;
2 to 4 weight percent of dioctyl phthalate;
2-4 wt% of polytetrafluoroethylene;
and the balance of auxiliary agent.
In the invention, the vibration-damping wear-resistant material comprises thermoplastic resin, a wear-resistant agent, dioctyl phthalate, polytetrafluoroethylene and an auxiliary agent, and preferably consists of the thermoplastic resin, the wear-resistant agent, the dioctyl phthalate, the polytetrafluoroethylene and the auxiliary agent.
In the present invention, the thermoplastic resin (thermoplastic elastomer) is preferably selected from thermoplastic polyurethane, thermoplastic polyester, thermoplastic TPV (a mixture of polyolefin and thermoplastic elastomer) or thermoplastic polyamide, more preferably thermoplastic polyurethane. The source of the thermoplastic resin is not particularly limited in the present invention, and commercially available products of the above thermoplastic polyurethane, thermoplastic polyester, thermoplastic TPV and thermoplastic polyamide (e.g., nylon 6, nylon 66, nylon 1010, nylon 1012, nylon 12) known to those skilled in the art may be used.
In the invention, the Shore A hardness of the thermoplastic resin is preferably 70-100, and more preferably 75-95.
In the present invention, the vibration-damping wear-resistant material comprises 85 wt% to 90 wt% of thermoplastic resin, preferably 90 wt%.
In the present invention, the anti-abrasion agent is preferably selected from one or more of aramid fiber, polyethylene fiber, polyester fiber, polyether, silicone powder, stearic acid, calcium stearate, oleic acid, oleamide, erucic acid, and erucic acid amide, and more preferably oleamide. The source of the anti-abrasion agent is not particularly limited in the present invention, and commercially available products of the above-mentioned aramid fiber, polyethylene fiber, polyester fiber, polyether, silicone powder, stearic acid, calcium stearate, oleic acid, oleamide, erucic acid, and erucamide, which are well known to those skilled in the art, may be used.
In the present invention, the vibration-damping wear-resistant material comprises 2 wt% to 4 wt% of a thermoplastic resin, preferably 3 wt%.
The sources of the dioctyl phthalate and the polytetrafluoroethylene are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the vibration-damping wear-resistant material comprises 2-4 wt% of dioctyl phthalate, and preferably 3 wt%.
In the invention, the vibration-damping wear-resistant material comprises 2-4 wt% of polytetrafluoroethylene, and preferably 3 wt%.
In the present invention, the auxiliary agent is preferably selected from one or more of an antioxidant, glass fiber, glass bead, basalt fiber, barium sulfate, calcium carbonate, quartz powder, wollastonite, and talc powder, and more preferably an antioxidant and/or wollastonite. The source of the auxiliary agent is not particularly limited in the present invention, and commercially available products of the above-mentioned antioxidant, glass fiber, glass bead, basalt fiber, barium sulfate, calcium carbonate, quartz powder, wollastonite, and talc, which are well known to those skilled in the art, may be used.
The vibration-damping wear-resistant material provided by the invention adopts components with specific contents, realizes better interaction, has vibration-damping and wear-resistant functions, can replace a metal rubber composite material to be used as a material for manufacturing an automobile vibration-damping system, and is suitable for working conditions such as vibration damping, friction resistance, corrosion resistance and the like on the basis of meeting the requirements on strength and rigidity; in addition, the product takes thermoplastic resin as a main raw material, has small dead weight and is convenient to recycle.
The invention also provides a preparation method of the vibration-damping wear-resistant material, which comprises the following steps:
a) and mixing the thermoplastic resin, the wear-resisting agent, the dioctyl phthalate, the polytetrafluoroethylene and the auxiliary agent, and compounding to obtain the vibration-damping wear-resisting material.
In the present invention, the thermoplastic resin, the wear-resistant agent, the dioctyl phthalate, the polytetrafluoroethylene and the auxiliary agent are the same as those in the above technical solution, and are not described herein again.
In the invention, the compounding process after mixing is preferably carried out by using a twin-screw extruder; on the basis, the composite extrusion processing temperature is preferably 180-240 ℃, and more preferably 190-225 ℃; the composite feeding speed is preferably 30rpm to 65rpm, and more preferably 35rpm to 50 rpm; the extrusion speed of the compounding is preferably 30m/min to 50m/min, and more preferably 40 m/min.
The preparation method provided by the invention has the advantages of simple and stable process, easily-controlled conditions, suitability for large-scale production and wide application prospect.
The invention also provides a wear-resistant vibration damping bushing which is integrally formed by the vibration damping and wear-resistant material in the modes of injection molding and die pressing;
or the like, or, alternatively,
the damping wear-resistant material is obtained by compounding an insert which is formed by injection molding and die pressing as an inner layer and thermoplastic resin as an outer layer;
the vibration-damping wear-resistant material is the vibration-damping wear-resistant material in the technical scheme.
In a preferred embodiment of the invention, the wear-resistant vibration damping bushing is integrally formed by vibration damping and wear-resistant materials through injection molding and die pressing; the vibration-damping wear-resistant material is the vibration-damping wear-resistant material in the technical scheme, and on the basis, the obtained wear-resistant vibration-damping bushing has vibration-damping and wear-resistant functions.
In another preferred embodiment of the invention, the wear-resistant damping bushing is obtained by compounding an insert, which is formed by injection molding and die pressing of a damping and wear-resistant material, as an inner layer and thermoplastic resin as an outer layer; the vibration-damping wear-resistant material is the vibration-damping wear-resistant material in the technical scheme and has vibration-damping and wear-resistant functions; the thermoplastic resin is the thermoplastic resin in the technical scheme and has a vibration damping function.
In the invention, the tensile strength of the thermoplastic resin is preferably more than 35MPa, the tearing strength is preferably 90N/mm-100N/mm, more preferably 95N/mm, the breaking elongation is preferably 500-700%, more preferably 600%, and the Shore A hardness is preferably 70-100, more preferably 75-95.
In the present invention, the preferable process of compounding the inner layer and the outer layer is specifically:
and placing the insert formed by the vibration-damping wear-resistant material in a mould, and coating thermoplastic resin on the periphery of the insert by an injection molding mode to form a vibration-damping functional layer to obtain a composite product, namely the wear-resistant vibration-damping bushing.
The wear-resistant vibration damping bush provided by the invention can replace a large amount of rubber-metal composite vibration damping sleeves used in the field of automobiles to be applied to an automobile vibration damping system, and has the advantages of small self weight and better wear resistance; the composite bushing for the automobile has the advantages that the composite bushing for the automobile is light, the service life of a product is prolonged, the later maintenance of the product is reduced, the quality of the product is ensured, the quality risk is avoided, and quality accidents are avoided, so that the composite bushing has wide application prospect and great market value.
The invention provides a vibration-damping wear-resistant material and a preparation method and application thereof; the vibration-damping wear-resistant material is prepared from the following raw materials: 85 wt% -90 wt% of thermoplastic resin; 2-4 wt% of wear-resisting agent; 2 to 4 weight percent of dioctyl phthalate; 2-4 wt% of polytetrafluoroethylene; and the balance of auxiliary agent. Compared with the prior art, the vibration-damping wear-resistant material provided by the invention adopts specific content components, realizes better interaction, has vibration-damping and wear-resistant functions, can replace a metal rubber composite material to be used as a material for manufacturing an automobile vibration-damping system, and is suitable for working conditions such as vibration damping, friction resistance, corrosion resistance and the like on the basis of meeting the requirements on strength and rigidity; in addition, the product takes thermoplastic resin as a main raw material, has small dead weight and is convenient to recycle. Experimental results show that the self weight of the vibration-damping wear-resistant material is less than 100g, the tensile strength is greater than 15MPa, the elongation at break is greater than 20%, the Shore A hardness is 75-95, and the friction coefficient to 45# steel is less than 0.1.
In addition, the preparation method provided by the invention is simple and stable in process, easy in condition control, suitable for large-scale production and wide in application prospect.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples and comparative examples of the present invention are commercially available; wherein the tensile strength of the thermoplastic polyurethane is more than 35MPa, the tearing strength is 95N/mm, the elongation at break is 600%, and the Shore A hardness is 75-95.
Example 1
(1) The raw material ratio is as follows:
thermoplastic polyurethane (shore a hardness 85): 90% by mass; oleic acid amide: 3 percent of mass; dioctyl phthalate: 3 percent of mass; polytetrafluoroethylene: 3 percent of mass; antioxidant: 1 percent by mass.
(2) The preparation method comprises the following steps:
compounding the raw materials into a composite material by a double-screw extruder according to the proportion requirement; the specific conditions and parameters are as follows:
extrusion processing temperature: 190 ℃; feeding speed: 35 rpm; extrusion speed: 40 m/min;
obtaining a vibration-damping wear-resistant material; and integrally forming the vibration-damping wear-resistant material in an injection molding and die pressing mode to obtain the wear-resistant vibration-damping bushing shown in the figure 1.
Through detection, the basic properties of the vibration-damping wear-resistant material provided by the embodiment 1 of the invention are as follows:
the self weight is 82g, the tensile strength is 25MPa, the elongation at break is more than 300 percent, the Shore A hardness is 85 percent, and the friction coefficient to 45# steel is 0.02.
Example 2
(1) The raw material ratio is as follows:
thermoplastic polyurethane (shore a hardness of 75): 90% by mass; oleic acid amide: 3 percent of mass; dioctyl phthalate: 3 percent of mass; polytetrafluoroethylene: 3 percent of mass; antioxidant: 1 percent by mass.
(2) The preparation method comprises the following steps:
compounding the raw materials into a composite material by a double-screw extruder according to the proportion requirement; the specific conditions and parameters are as follows:
extrusion processing temperature: 190 ℃; feeding speed: 35 rpm; extrusion speed: 40 m/min;
obtaining the vibration-damping wear-resistant material.
Through detection, the basic properties of the vibration-damping wear-resistant material provided by the embodiment 2 of the invention are as follows:
the self weight is 83g, the tensile strength is 35MPa, the elongation at break is more than 200%, the Shore A hardness is 75, and the friction coefficient to 45# steel is 0.05.
Example 3
(1) The raw material ratio is as follows:
thermoplastic polyurethane (shore a hardness 95): 90% by mass; oleic acid amide: 3 percent of mass; dioctyl phthalate: 3 percent of mass; polytetrafluoroethylene: 3 percent of mass; antioxidant: 1 percent by mass.
(2) The preparation method comprises the following steps:
compounding the raw materials into a composite material by a double-screw extruder according to the proportion requirement; the specific conditions and parameters are as follows:
extrusion processing temperature: 190 ℃; feeding speed: 35 rpm; extrusion speed: 40 m/min;
obtaining the vibration-damping wear-resistant material.
Through detection, the basic properties of the vibration-damping wear-resistant material provided by the embodiment 3 of the invention are as follows:
the self weight is 82g, the tensile strength is 16MPa, the elongation at break is more than 200%, the Shore A hardness is 95, and the friction coefficient to 45# steel is 0.04.
Comparative example 1
(1) The raw material ratio is as follows:
thermoplastic polyurethane (shore a hardness 85): 96 percent by mass; oleic acid amide: 1% by mass; dioctyl phthalate: 1% by mass; polytetrafluoroethylene: 1% by mass; antioxidant: 1 percent by mass.
(2) The preparation method comprises the following steps:
compounding the raw materials into a composite material by a double-screw extruder according to the proportion requirement; the specific conditions and parameters are as follows:
extrusion processing temperature: 190 ℃; feeding speed: 35 rpm; extrusion speed: 40 m/min.
The basic properties of the composite material provided in comparative example 1 were examined as follows:
the self weight is 82g, the tensile strength is 11MPa, the elongation at break is more than 100%, the Shore A hardness is 85, and the friction coefficient to 45# steel is 0.5.
Compared with the vibration-damping wear-resistant materials provided by the embodiments 1-3 of the invention, the friction coefficient of the composite material provided by the comparative example 1 to the 45# steel is obviously increased, and the technical requirements of vibration damping and low friction cannot be met.
Comparative example 2
(1) The raw material ratio is as follows:
thermoplastic polyurethane (shore a hardness 85): 84% by mass; oleic acid amide: 5 percent of mass; dioctyl phthalate: 5 percent of mass; polytetrafluoroethylene: 5 percent of mass; antioxidant: 1 percent by mass.
(2) The preparation method comprises the following steps:
compounding the raw materials into a composite material by a double-screw extruder according to the proportion requirement; the specific conditions and parameters are as follows:
extrusion processing temperature: 190 ℃; feeding speed: 35 rpm; extrusion speed: 40 m/min;
obtaining the vibration-damping wear-resistant material.
The basic properties of the vibration-damping wear-resistant material provided by the comparative example 2 are detected as follows:
the self weight is 82g, the tensile strength is 7MPa, the elongation at break is less than 80%, the Shore A hardness is 80, and the friction coefficient to 45# steel is 0.2.
Compared with the vibration-damping wear-resistant materials provided by the embodiments 1-3 of the invention and the composite material provided by the comparative example 1, the composite material provided by the comparative example 2 has improved friction coefficient compared with the comparative example 1 for the 45# steel, but the friction coefficient is still lower than that of the embodiments 1-3 of the invention, the vibration-damping performance is obviously reduced, and the technical requirements of vibration damping and low friction cannot be met.
Example 4
(1) The raw material ratio is as follows:
abrasion resistant nylon PA6 (shore a hardness 85): 90% by mass; oleic acid amide: 3 percent of mass; dioctyl phthalate: 3 percent of mass; polytetrafluoroethylene: 3 percent of mass; antioxidant: 1 percent by mass.
(2) The preparation method comprises the following steps:
compounding the raw materials into a composite material by a double-screw extruder according to the proportion requirement; the specific conditions and parameters are as follows:
extrusion processing temperature: 225 ℃; feeding speed: 50 rpm; extrusion speed: 40 m/min;
obtaining the vibration-damping wear-resistant material.
Through detection, the basic properties of the vibration-damping wear-resistant material provided by the embodiment 4 of the invention are as follows:
the self weight is 95g, the tensile strength is 68MPa, the bending strength is more than 130MPa, the elongation at break is more than 20%, the Shore A hardness is 85%, and the friction coefficient to 45# steel is 0.09.
The vibration-damping and wear-resistant material provided by the embodiment 4 is molded into an insert in an injection molding and die pressing mode and used as an inner layer (a wear-resistant functional layer) of a wear-resistant vibration-damping bushing; placing the wear-resistant damping bushing in a mold, and coating thermoplastic polyurethane (the tensile strength is more than 35MPa, the tear strength is 95N/mm, the elongation at break is 600%, and the Shore A hardness is 75-95) on the periphery of the wear-resistant damping bushing in an injection molding mode to form a damping functional layer, so that the wear-resistant damping bushing shown in the figure 2 is obtained.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The vibration-damping wear-resistant material is prepared from the following raw materials:
85 wt% -90 wt% of thermoplastic resin;
2-4 wt% of wear-resisting agent;
2 to 4 weight percent of dioctyl phthalate;
2-4 wt% of polytetrafluoroethylene;
and the balance of auxiliary agent.
2. The vibration damping, wear resistant material of claim 1 wherein the thermoplastic resin is selected from thermoplastic polyurethane, thermoplastic polyester, thermoplastic TPV or thermoplastic polyamide.
3. The vibration damping and wear resistant material according to claim 1, wherein the Shore A hardness of the thermoplastic resin is 70-100.
4. The vibration damping and wear resistant material of claim 1 wherein the wear resistant agent is selected from one or more of aramid fiber, polyethylene fiber, polyester fiber, polyether, silicone powder, stearic acid, calcium stearate, oleic acid, oleamide, erucic acid, and erucamide.
5. The vibration damping and wear resistant material of claim 1 wherein the auxiliary agent is selected from one or more of antioxidants, glass fibers, glass beads, basalt fibers, barium sulfate, calcium carbonate, quartz powder, wollastonite, and talc.
6. A method for preparing the vibration-damping wear-resistant material as claimed in any one of claims 1 to 5, comprising the following steps:
a) and mixing the thermoplastic resin, the wear-resisting agent, the dioctyl phthalate, the polytetrafluoroethylene and the auxiliary agent, and compounding to obtain the vibration-damping wear-resisting material.
7. The method as claimed in claim 6, wherein the compounding after the mixing in the step a) is performed using a twin screw extruder.
8. The preparation method of claim 7, wherein the composite extrusion processing temperature is 180 ℃ to 240 ℃, the feeding speed is 30rpm to 65rpm, and the extrusion speed is 30m/min to 50 m/min.
9. A wear-resistant damping bushing is integrally formed by damping and wear-resistant materials in an injection molding and mould pressing mode;
or the like, or, alternatively,
the damping wear-resistant material is obtained by compounding an insert which is formed by injection molding and die pressing as an inner layer and thermoplastic resin as an outer layer;
the vibration-damping wear-resistant material is the vibration-damping wear-resistant material as claimed in any one of claims 1 to 5.
10. A wear resistant vibration damping bushing according to claim 9, characterized in that the thermoplastic resin has a tensile strength of more than 35MPa, a tear strength of 90-100N/mm, an elongation at break of 500-700%, and a shore a hardness of 70-100.
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Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009299026A (en) * | 2008-05-15 | 2009-12-24 | Dainichiseika Color & Chem Mfg Co Ltd | Thermoplastic polyurethane resin composition |
CN103374220A (en) * | 2012-04-24 | 2013-10-30 | 上海杰事杰新材料(集团)股份有限公司 | Natural fiber-reinforced polyurethane elastomer composite material and preparation method thereof |
CN103483801A (en) * | 2013-09-27 | 2014-01-01 | 安徽科聚新材料有限公司 | Thermoplastic polyurethane composite material and preparation method thereof |
CN104629243A (en) * | 2015-02-09 | 2015-05-20 | 银禧工程塑料(东莞)有限公司 | High-shock-absorbance wear-resistant thermoplastic elastomer and preparation method thereof |
CN105778469A (en) * | 2016-03-28 | 2016-07-20 | 王社兵 | Anti-aging and anti-twisting wind power cable |
CN107725601A (en) * | 2017-07-10 | 2018-02-23 | 北华大学 | A kind of preparation method of double-decker polyurethane composite bearing |
CN108001013A (en) * | 2016-10-28 | 2018-05-08 | 苏州正源建信建材科技有限公司 | A kind of preparation method of the elastic TPU coiled material floors of environment-protecting and non-poisonous evil |
CN108623987A (en) * | 2018-05-17 | 2018-10-09 | 株洲时代新材料科技股份有限公司 | A kind of auxiliary guide wheels wear part and preparation method |
CN108795016A (en) * | 2018-05-17 | 2018-11-13 | 株洲时代新材料科技股份有限公司 | A kind of modified thermoplastic material and preparation method |
CN108869549A (en) * | 2018-04-11 | 2018-11-23 | 启东海大聚龙新材料科技有限公司 | A kind of multi-layer wear-resistant material and the preparation method and application thereof |
CN109096733A (en) * | 2018-05-21 | 2018-12-28 | 南京宜凯瑞新材料有限公司 | A kind of wear-resistant thermoplastic polyurethane elastomer processing method |
WO2019143200A1 (en) * | 2018-01-18 | 2019-07-25 | 주식회사 엘지하우시스 | Thermoplastic polyurethane composition for powder slush molding, preparation method therefor, and automotive interior skin material manufactured using same |
CN110953411A (en) * | 2019-12-13 | 2020-04-03 | 青岛盛高石油装备有限责任公司 | Wear-resistant high-pressure-resistant non-metal composite flexible pipe for mining and preparation method and application thereof |
CN111087806A (en) * | 2019-12-27 | 2020-05-01 | 株洲时代工程塑料科技有限责任公司 | High-strength wear-resistant nylon composite material and preparation method thereof |
CN111560158A (en) * | 2020-05-21 | 2020-08-21 | 上海金山锦湖日丽塑料有限公司 | Low-warpage wear-resistant conductive PBT (polybutylene terephthalate) composite material and preparation method thereof |
-
2020
- 2020-11-30 CN CN202011378911.XA patent/CN112457655A/en active Pending
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009299026A (en) * | 2008-05-15 | 2009-12-24 | Dainichiseika Color & Chem Mfg Co Ltd | Thermoplastic polyurethane resin composition |
CN103374220A (en) * | 2012-04-24 | 2013-10-30 | 上海杰事杰新材料(集团)股份有限公司 | Natural fiber-reinforced polyurethane elastomer composite material and preparation method thereof |
CN103483801A (en) * | 2013-09-27 | 2014-01-01 | 安徽科聚新材料有限公司 | Thermoplastic polyurethane composite material and preparation method thereof |
CN104629243A (en) * | 2015-02-09 | 2015-05-20 | 银禧工程塑料(东莞)有限公司 | High-shock-absorbance wear-resistant thermoplastic elastomer and preparation method thereof |
CN105778469A (en) * | 2016-03-28 | 2016-07-20 | 王社兵 | Anti-aging and anti-twisting wind power cable |
CN108001013A (en) * | 2016-10-28 | 2018-05-08 | 苏州正源建信建材科技有限公司 | A kind of preparation method of the elastic TPU coiled material floors of environment-protecting and non-poisonous evil |
CN107725601A (en) * | 2017-07-10 | 2018-02-23 | 北华大学 | A kind of preparation method of double-decker polyurethane composite bearing |
WO2019143200A1 (en) * | 2018-01-18 | 2019-07-25 | 주식회사 엘지하우시스 | Thermoplastic polyurethane composition for powder slush molding, preparation method therefor, and automotive interior skin material manufactured using same |
CN108869549A (en) * | 2018-04-11 | 2018-11-23 | 启东海大聚龙新材料科技有限公司 | A kind of multi-layer wear-resistant material and the preparation method and application thereof |
CN108623987A (en) * | 2018-05-17 | 2018-10-09 | 株洲时代新材料科技股份有限公司 | A kind of auxiliary guide wheels wear part and preparation method |
CN108795016A (en) * | 2018-05-17 | 2018-11-13 | 株洲时代新材料科技股份有限公司 | A kind of modified thermoplastic material and preparation method |
CN109096733A (en) * | 2018-05-21 | 2018-12-28 | 南京宜凯瑞新材料有限公司 | A kind of wear-resistant thermoplastic polyurethane elastomer processing method |
CN110953411A (en) * | 2019-12-13 | 2020-04-03 | 青岛盛高石油装备有限责任公司 | Wear-resistant high-pressure-resistant non-metal composite flexible pipe for mining and preparation method and application thereof |
CN111087806A (en) * | 2019-12-27 | 2020-05-01 | 株洲时代工程塑料科技有限责任公司 | High-strength wear-resistant nylon composite material and preparation method thereof |
CN111560158A (en) * | 2020-05-21 | 2020-08-21 | 上海金山锦湖日丽塑料有限公司 | Low-warpage wear-resistant conductive PBT (polybutylene terephthalate) composite material and preparation method thereof |
Non-Patent Citations (3)
Title |
---|
XIAO, S: "Effect of molecular weight on scratch and abrasive wear behaviors of thermoplastic polyurethane elastomers", 《POLYMER》 * |
周杉鸿等: "热塑性弹性体材料在汽车轻量化研究中的应用", 《江苏科技信息》 * |
王中发: "《机械设计》", 31 July 1998, 北京理工大学出版社 * |
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