CN113024989A - Modified polyformaldehyde, automobile accelerator pedal bushing and preparation method - Google Patents

Modified polyformaldehyde, automobile accelerator pedal bushing and preparation method Download PDF

Info

Publication number
CN113024989A
CN113024989A CN202110294342.9A CN202110294342A CN113024989A CN 113024989 A CN113024989 A CN 113024989A CN 202110294342 A CN202110294342 A CN 202110294342A CN 113024989 A CN113024989 A CN 113024989A
Authority
CN
China
Prior art keywords
percent
polyformaldehyde
modified
antioxidant
heat stabilizer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110294342.9A
Other languages
Chinese (zh)
Other versions
CN113024989B (en
Inventor
郝文奇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aiways Automobile Shanghai Co Ltd
Original Assignee
Aiways Automobile Shanghai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aiways Automobile Shanghai Co Ltd filed Critical Aiways Automobile Shanghai Co Ltd
Priority to CN202110294342.9A priority Critical patent/CN113024989B/en
Publication of CN113024989A publication Critical patent/CN113024989A/en
Application granted granted Critical
Publication of CN113024989B publication Critical patent/CN113024989B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2359/00—Characterised by the use of polyacetals containing polyoxymethylene sequences only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

The invention discloses a modified polyformaldehyde, an automobile accelerator pedal bushing and a preparation method thereof, and relates to the field of high polymer materials. The composite material comprises the following raw materials in percentage by weight: 88.5 to 96.5 percent of polyformaldehyde, 0.1 to 9.5 percent of flexibilizer, 0.1 to 9 percent of reinforcing agent, 0.1 to 1 percent of antioxidant and 0.1 to 0.5 percent of heat stabilizer. The polyformaldehyde with high toughness, high rigidity and high wear resistance provided by the invention is compounded with a toughening agent, a reinforcing agent, an antioxidant, a heat stabilizer and polyformaldehyde, so that the polyformaldehyde is reinforced, toughened and wear resistant. The polyformaldehyde with high toughness, high rigidity and high wear resistance can be used for producing automobile accelerator pedal shaft sleeves.

Description

Modified polyformaldehyde, automobile accelerator pedal bushing and preparation method
Technical Field
The invention relates to the field of high polymer materials, in particular to a modified polyformaldehyde, an automobile accelerator pedal bushing and a preparation method thereof.
Background
Polyoxymethylene (POM) is widely used in automobile accelerator pedal bushings due to its high wear resistance, and with the improvement of automobile performance, higher requirements are put forward on toughness, rigidity and wear resistance of the accelerator pedal bushing. At present, the most common method for toughening type POM is to add an elastomer, so that the impact toughness of the POM can be greatly improved, but the rigidity of the toughened POM system is reduced; the most common method for enhancing the POM is to mix the POM with long glass fibers, which can greatly improve the rigidity of the POM, but the method cannot greatly improve the impact toughness of the POM. In addition, the two modification methods in the prior art can not effectively improve the wear resistance of the POM while improving any performance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a modified polyformaldehyde, an automobile accelerator pedal bushing and a preparation method thereof so as to solve the technical problems.
The invention is realized by the following steps:
the invention provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 88.5 to 96.5 percent of polyformaldehyde, 0.1 to 9.5 percent of flexibilizer, 0.1 to 9 percent of reinforcing agent, 0.1 to 1 percent of antioxidant and 0.1 to 0.5 percent of heat stabilizer.
The invention provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 88.5 to 96 percent of polyformaldehyde, 2 to 8 percent of flexibilizer, 2 to 8 percent of reinforcing agent, 0.1 to 1 percent of antioxidant and 0.1 to 0.5 percent of heat stabilizer;
preferably, the material comprises the following raw materials in percentage by weight: 88.5 percent of polyformaldehyde, 4 percent of flexibilizer, 6 percent of reinforcing agent, 1 percent of antioxidant and 0.5 percent of heat stabilizer.
In a preferred embodiment of the present invention, the toughening agent is zirconia.
In a preferred embodiment of the present invention, the reinforcing agent is chopped carbon fibers; the chopped carbon fibers are T700-grade carbon fibers.
In a preferred embodiment of the present invention, the antioxidant is at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and phenyl tris (2, 4-di-tert-butyl) phosphite.
In a preferred embodiment of the present invention, the heat stabilizer is n-octadecyl beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
preferably, the polyoxymethylene is polyoxymethylene M90.
The invention provides a preparation method of modified paraformaldehyde, which comprises the following steps: mixing polyformaldehyde, toughening agent, reinforcing agent, antioxidant and heat stabilizer in proportion, and extruding and molding after mixing.
In the preferred embodiment of the present invention, the preparation method comprises melt-extruding the mixed materials at 170-180 ℃ by using a torque rheometer, and then injection-molding the extruded master batch at 170-180 ℃ and 55-60MPa by using an injection molding machine.
The modified polyformaldehyde is applied to preparation of an automobile accelerator pedal bushing.
The invention provides an automobile accelerator pedal bushing which is prepared from the modified polyformaldehyde or the modified polyformaldehyde prepared by the preparation method.
The invention has the following beneficial effects:
the invention provides a modified polyformaldehyde, which is compounded with a toughening agent, a reinforcing agent, an antioxidant, a heat stabilizer and polyformaldehyde, so that the polyformaldehyde is reinforced, toughened and wear-resistant. The modified polyformaldehyde can be used for producing automobile accelerator pedal shaft sleeves.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
The invention provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 88.5 to 96.5 percent of polyformaldehyde, 0.1 to 9.5 percent of flexibilizer, 0.1 to 9 percent of reinforcing agent, 0.1 to 1 percent of antioxidant and 0.1 to 0.5 percent of heat stabilizer.
The toughening agent plays a role in improving the toughness of the polyformaldehyde. The reinforcing agent acts to increase the stiffness of the material. Antioxidants and heat stabilizers to improve the durability of polyoxymethylene.
The invention provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 88.5 to 96 percent of polyformaldehyde, 2 to 8 percent of flexibilizer, 2 to 8 percent of reinforcing agent, 0.1 to 1 percent of antioxidant and 0.1 to 0.5 percent of heat stabilizer;
alternatively, the content of the polyoxymethylene may be 89%, 90%, 91%, 92%, 93%, 94%, 95% or 96%.
Optionally, the content of the above toughening agent may be 2%, 3%, 4%, 5%, 6%, 7% or 8%.
Optionally, the enhancer may be present in an amount of 2%, 3%, 4%, 5%, 6%, 7% or 8%.
Alternatively, the antioxidant may be present in an amount of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%.
Optionally, the heat stabilizer may be present in an amount of 0.1%, 0.2%, 0.3%, 0.4% or 0.5%.
In other embodiments, the actual content of each raw material may be adaptively adjusted within the content range provided by the present invention, and is not limited to the specific content values listed above.
Preferably, the material comprises the following raw materials in percentage by weight: 88.5 percent of polyformaldehyde, 4 percent of flexibilizer, 6 percent of reinforcing agent, 1 percent of antioxidant and 0.5 percent of heat stabilizer.
The inventor finds that the accelerator pedal shaft sleeve prepared by the following raw materials has the best comprehensive mechanical property and the lowest friction coefficient (namely, the toughness is high, the rigidity is high, and the wear resistance is better) when the raw materials are as follows: 88.5 percent of polyformaldehyde, 4 percent of flexibilizer, 6 percent of reinforcing agent, 1 percent of antioxidant and 0.5 percent of heat stabilizer.
In a preferred embodiment of the present invention, the toughening agent is zirconium oxide (ZrO)2) Or a core-shell polymer.
The mechanism of zirconia toughening is as follows: the expansion accompanying the volume at the time of the phase transition of zirconia is utilized to generate a process of shielding the propagation of cracks or counteracting the residual stress. The smaller the particle size of the tetragonal zirconia grains, the better the toughening effect.
The core-shell polymer refers to a particulate polymer with an inner core and an outer shell compounded by a plurality of macromolecule enriching layers respectively.
In a preferred embodiment of the present invention, the reinforcing agent is chopped carbon fibers. The chopped carbon fiber is formed by chopping carbon fiber filaments by a fiber cutter.
In a preferred embodiment of the present invention, the antioxidant is at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and phenyl tris (2, 4-di-tert-butyl) phosphite.
In a preferred embodiment of the present invention, the heat stabilizer is n-octadecyl beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
preferably, the polyoxymethylene is polyoxymethylene M90.
The invention provides a preparation method of modified paraformaldehyde, which comprises the following steps: mixing polyformaldehyde, toughening agent, reinforcing agent, antioxidant and heat stabilizer in proportion, and extruding and molding after mixing.
In the preferred embodiment of the present invention, the preparation method comprises melt-extruding the mixed materials at 170-180 ℃ by using a torque rheometer, and then injection-molding the extruded master batch at 170-180 ℃ and 55-60MPa by using an injection molding machine.
The modified polyformaldehyde is applied to preparation of an automobile accelerator pedal bushing.
The invention provides an automobile accelerator pedal bushing which is prepared from the modified polyformaldehyde or the modified polyformaldehyde prepared by the preparation method.
Optionally, the modified polyoxymethylene may also be used in the field of producing handlebar grips and the like, and is not limited to the automotive accelerator pedal bushing described above.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 88.5 percent of polyformaldehyde, 4 percent of zirconia, 6 percent of chopped carbon fiber, 1 percent of one or a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri (2, 4-di-tert-butyl) phenyl phosphite as an antioxidant and 0.5 percent of heat stabilizer beta (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate.
The polyformaldehyde in the embodiment is POM/M90 of Yunnan chemical products Co., Ltd, the toughening agent zirconia is purchased from Bohuas nanometer technology (Ningbo) Co., Ltd, and the reinforcing agent chopped carbon fiber is purchased from Xiangsheng carbon fiber technology Co., Ltd in salt cities.
The method for producing the automobile accelerator pedal bush by using the modified polyformaldehyde raw material comprises the following steps: putting polyformaldehyde, zirconia, chopped carbon fibers, an antioxidant and a heat stabilizer into a high-speed mixer, uniformly mixing for 20 minutes, then melting and extruding the mixed materials at 180 ℃ by using a torque rheometer, and carrying out injection molding on the extruded master batch at 180 ℃ and 60MPa by using an injection molding machine.
In other embodiments, the modified polyoxymethylene may be prepared by the above-described preparation method.
Example 2
The embodiment provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 88.5 percent of polyformaldehyde, 2 percent of zirconia, 8 percent of chopped carbon fiber, 1 percent of one or a mixture of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri (2, 4-di-tert-butyl) phenyl phosphite as an antioxidant and 0.5 percent of heat stabilizer beta (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate.
The polyformaldehyde in the embodiment is POM/M90 of Yunnan chemical products Co., Ltd, the toughening agent zirconia is purchased from Bohuas nanometer technology (Ningbo) Co., Ltd, and the reinforcing agent chopped carbon fiber is purchased from Xiangsheng carbon fiber technology Co., Ltd in salt cities.
The method for producing the automobile accelerator pedal bush by using the modified polyformaldehyde raw material comprises the following steps: putting polyformaldehyde, zirconia, chopped carbon fibers, an antioxidant and a heat stabilizer into a high-speed mixer, uniformly mixing for 20 minutes, then melting and extruding the mixed materials at 180 ℃ by using a torque rheometer, and carrying out injection molding on the extruded master batch at 180 ℃ and 60MPa by using an injection molding machine.
In other embodiments, the modified polyoxymethylene may be prepared by the above-described preparation method.
Example 3
The embodiment provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 88.5% of polyformaldehyde, 6% of zirconia, 4% of chopped carbon fiber, 1% of antioxidant and 0.5% of heat stabilizer.
The polyformaldehyde in the embodiment is POM/M90 of Yunnan chemical products Co., Ltd, the toughening agent zirconia is purchased from Bohuas nanometer technology (Ningbo) Co., Ltd, and the reinforcing agent chopped carbon fiber is purchased from Xiangsheng carbon fiber technology Co., Ltd in salt cities.
The method for producing the automobile accelerator pedal bush by using the modified polyformaldehyde raw material comprises the following steps: putting polyformaldehyde, zirconia, chopped carbon fibers, an antioxidant and a heat stabilizer into a high-speed mixer, uniformly mixing for 20 minutes, then melting and extruding the mixed materials at 180 ℃ by using a torque rheometer, and carrying out injection molding on the extruded master batch at 180 ℃ and 60MPa by using an injection molding machine.
In other embodiments, the modified polyoxymethylene may be prepared by the above-described preparation method.
Example 4
The embodiment provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 88.5% of polyformaldehyde, 8% of zirconia, 2% of chopped carbon fiber, 1% of antioxidant and 0.5% of heat stabilizer.
The polyformaldehyde in the embodiment is POM/M90 of Yunnan chemical products Co., Ltd, the toughening agent zirconia is purchased from Bohuas nanometer technology (Ningbo) Co., Ltd, and the reinforcing agent chopped carbon fiber is purchased from Xiangsheng carbon fiber technology Co., Ltd in salt cities.
The method for producing the automobile accelerator pedal bush by using the modified polyformaldehyde raw material comprises the following steps: putting polyformaldehyde, zirconia, chopped carbon fibers, an antioxidant and a heat stabilizer into a high-speed mixer, uniformly mixing for 20 minutes, then melting and extruding the mixed materials at 180 ℃ by using a torque rheometer, and carrying out injection molding on the extruded master batch at 180 ℃ and 60MPa by using an injection molding machine.
In other embodiments, the modified polyoxymethylene may be prepared by the above-described preparation method.
Example 5
The embodiment provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 88.5% of polyformaldehyde, 9% of zirconia, 1% of chopped carbon fiber, 1% of antioxidant and 0.5% of heat stabilizer.
The polyformaldehyde in the embodiment is POM/M90 of Yunnan chemical products Co., Ltd, the toughening agent zirconia is purchased from Bohuas nanometer technology (Ningbo) Co., Ltd, and the reinforcing agent chopped carbon fiber is purchased from Xiangsheng carbon fiber technology Co., Ltd in salt cities.
The method for producing the automobile accelerator pedal bush by using the modified polyformaldehyde raw material comprises the following steps: putting polyformaldehyde, zirconia, chopped carbon fibers, an antioxidant and a heat stabilizer into a high-speed mixer, uniformly mixing for 20 minutes, then melting and extruding the mixed materials at 180 ℃ by using a torque rheometer, and carrying out injection molding on the extruded master batch at 180 ℃ and 60MPa by using an injection molding machine.
In other embodiments, the modified polyoxymethylene may be prepared by the above-described preparation method.
Example 6
The embodiment provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 90% of polyformaldehyde, 4% of zirconia, 4.5% of chopped carbon fibers, 1% of antioxidant and 0.5% of heat stabilizer.
The polyformaldehyde in the embodiment is POM/M90 of Yunnan chemical products Co., Ltd, the toughening agent zirconia is purchased from Bohuas nanometer technology (Ningbo) Co., Ltd, and the reinforcing agent chopped carbon fiber is purchased from Xiangsheng carbon fiber technology Co., Ltd in salt cities.
The method for producing the automobile accelerator pedal bush by using the modified polyformaldehyde raw material comprises the following steps: putting polyformaldehyde, zirconia, chopped carbon fibers, an antioxidant and a heat stabilizer into a high-speed mixer, uniformly mixing for 20 minutes, then melting and extruding the mixed materials at 180 ℃ by using a torque rheometer, and carrying out injection molding on the extruded master batch at 180 ℃ and 60MPa by using an injection molding machine.
In other embodiments, the modified polyoxymethylene may be prepared by the above-described preparation method.
Example 7
The embodiment provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 95% of polyformaldehyde, 1% of zirconia, 2.5% of chopped carbon fibers, 1% of antioxidant and 0.5% of heat stabilizer.
The polyformaldehyde in the embodiment is POM/M90 of Yunnan chemical products Co., Ltd, the toughening agent zirconia is purchased from Bohuas nanometer technology (Ningbo) Co., Ltd, and the reinforcing agent chopped carbon fiber is purchased from Xiangsheng carbon fiber technology Co., Ltd in salt cities.
The method for producing the automobile accelerator pedal bush by using the modified polyformaldehyde raw material comprises the following steps: putting polyformaldehyde, zirconia, chopped carbon fibers, an antioxidant and a heat stabilizer into a high-speed mixer, uniformly mixing for 20 minutes, then melting and extruding the mixed materials at 180 ℃ by using a torque rheometer, and carrying out injection molding on the extruded master batch at 180 ℃ and 60MPa by using an injection molding machine.
In other embodiments, the modified polyoxymethylene may be prepared by the above-described preparation method.
Example 8
The embodiment provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 92.5% of polyformaldehyde, 3% of zirconia, 3% of chopped carbon fibers, 1% of antioxidant and 0.5% of heat stabilizer.
The polyformaldehyde in the embodiment is POM/M90 of Yunnan chemical products Co., Ltd, the toughening agent zirconia is purchased from Bohuas nanometer technology (Ningbo) Co., Ltd, and the reinforcing agent chopped carbon fiber is purchased from Xiangsheng carbon fiber technology Co., Ltd in salt cities.
The method for producing the automobile accelerator pedal bush by using the modified polyformaldehyde raw material comprises the following steps: putting polyformaldehyde, zirconia, chopped carbon fibers, an antioxidant and a heat stabilizer into a high-speed mixer, uniformly mixing for 20 minutes, then melting and extruding the mixed materials at 180 ℃ by using a torque rheometer, and carrying out injection molding on the extruded master batch at 180 ℃ and 60MPa by using an injection molding machine.
In other embodiments, the modified polyoxymethylene may be prepared by the above-described preparation method.
Example 9
The embodiment provides a modified polyformaldehyde, which comprises the following raw materials in percentage by weight: 96.5% of polyformaldehyde, 1% of zirconia, 1% of chopped carbon fiber, 0.5% of antioxidant and 1% of heat stabilizer.
The polyformaldehyde in the embodiment is POM/M90 of Yunnan chemical products Co., Ltd, the toughening agent zirconia is purchased from Bohuas nanometer technology (Ningbo) Co., Ltd, and the reinforcing agent chopped carbon fiber is purchased from Xiangsheng carbon fiber technology Co., Ltd in salt cities.
The method for producing the automobile accelerator pedal bush by using the modified polyformaldehyde raw material comprises the following steps: putting polyformaldehyde, zirconia, chopped carbon fibers, an antioxidant and a heat stabilizer into a high-speed mixer, uniformly mixing for 20 minutes, then melting and extruding the mixed materials at 180 ℃ by using a torque rheometer, and carrying out injection molding on the extruded master batch at 180 ℃ and 60MPa by using an injection molding machine.
In other embodiments, the modified polyoxymethylene may be prepared by the above-described preparation method.
Comparative example 1
Compared with the example 1, the difference is only that the modified polyformaldehyde has different raw material contents, and comprises the following raw materials in percentage by weight: 88.5% of polyformaldehyde, 0% of zirconia, 10% of chopped carbon fiber, 1% of antioxidant and 0.5% of heat stabilizer.
Comparative example 2
Compared with the example 1, the difference is only that the modified polyformaldehyde has different raw material contents, and comprises the following raw materials in percentage by weight: 88.5% of polyformaldehyde, 10% of zirconia, 0% of chopped carbon fiber, 1% of antioxidant and 0.5% of heat stabilizer.
Comparative example 3
Compared with the example 1, the difference is only that the modified polyformaldehyde has different raw material contents, and comprises the following raw materials in percentage by weight: 98.5% of polyformaldehyde, 0% of zirconia, 0% of chopped carbon fiber, 1% of antioxidant and 0.5% of heat stabilizer.
Comparative example 4
Compared with the example 1, the difference is that the modified polyformaldehyde adopts the raw materials with different long glass fiber contents, and the raw materials comprise the following raw materials in percentage by weight: 88.5% of polyformaldehyde, 4% of zirconia, 6% of long glass fiber, 1% of antioxidant and 0.5% of heat stabilizer.
Experimental example 1
The automobile accelerator pedal bushings produced in examples 1 to 2,5,8 to 9 and comparative examples 1 to 4 were tested for tensile strength, flexural modulus, impact strength and coefficient of friction, respectively. The raw material compositions of the examples and comparative examples are shown in table 1, and the mechanical properties of the automobile accelerator pedal bushing are shown in table 2.
Table 1 composition of raw materials for each example and comparative example.
Figure BDA0002983597400000121
Table 2 mechanical properties of accelerator pedal sleeve.
Figure BDA0002983597400000122
It should be noted that the methods for testing tensile strength, bending modulus, notched impact strength and friction coefficient by testing the sample bars are as follows:
(1) the tensile strength was measured by the method specified in GB/T1040.2 at a test speed of 5 mm/min.
(2) The bending strength and the bending modulus are tested by the method specified in GB/T9341, the testing speed is 2mm/min, and the span is 64 mm.
(3) Notched impact strength was tested using the method specified in GB/T1043.1.
(4) The coefficient of friction was measured using the method specified in ISO 8295.
As can be seen from table 2, in example 1, when the polyoxymethylene content was 88.5%, the zirconia content was 4%, the chopped carbon fiber content was 6%, the antioxidant content was 1%, and the heat stabilizer content was 0.5%, the resultant accelerator pedal bushing had the best overall mechanical properties and the lowest friction coefficient.
Example 1 tensile strength was increased by 54.7%, flexural strength was increased by 37.1%, flexural modulus by 43.2%, notched impact strength by 66.7%, and coefficient of friction was reduced by 43.3% over comparative example 3 pure polyoxymethylene version.
Compared with the accelerator pedal shaft sleeves of comparative examples 1 and 2, the accelerator pedal shaft sleeves produced by the examples have obviously improved bending strength, bending modulus and notched impact strength.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The modified polyformaldehyde is characterized by comprising the following raw materials in percentage by weight: 88.5 to 96.5 percent of polyformaldehyde, 0.1 to 9.5 percent of flexibilizer, 0.1 to 9 percent of reinforcing agent, 0.1 to 1 percent of antioxidant and 0.1 to 0.5 percent of heat stabilizer.
2. The modified polyoxymethylene of claim 1, comprising the following raw materials in weight percent: 88.5 to 96 percent of polyformaldehyde, 2 to 8 percent of flexibilizer, 2 to 8 percent of reinforcing agent, 0.1 to 1 percent of antioxidant and 0.1 to 0.5 percent of heat stabilizer;
preferably, the material comprises the following raw materials in percentage by weight: 88.5 percent of polyformaldehyde, 4 percent of flexibilizer, 6 percent of reinforcing agent, 1 percent of antioxidant and 0.5 percent of heat stabilizer.
3. The modified polyoxymethylene of claim 1 or 2, wherein the toughening agent is zirconia.
4. The modified polyoxymethylene of claim 1 or 2, wherein the reinforcing agent is chopped carbon fiber; preferably, the chopped carbon fibers are T700-grade carbon fibers.
5. The modified polyoxymethylene of claim 1 or 2, wherein the antioxidant is at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and phenyl tris (2, 4-di-tert-butyl) phosphite.
6. The modified polyoxymethylene of claim 1 or 2, wherein the heat stabilizer is n-octadecyl β (3,5 di-tert-butyl 4 hydroxyphenyl) propionate;
preferably, the polyoxymethylene is polyoxymethylene M90.
7. A process for the preparation of the modified paraformaldehyde according to any one of claims 1-6, wherein the process comprises: mixing polyformaldehyde, toughening agent, reinforcing agent, antioxidant and heat stabilizer in proportion, and extruding and molding after mixing.
8. The method as claimed in claim 7, wherein the method comprises melt-extruding the mixed material at 170-180 ℃ by a torque rheometer and then injection-molding the extruded master batch at 170-180 ℃ under 55-60MPa by an injection molding machine.
9. Use of the modified polyoxymethylene according to any one of claims 1 to 6 or the modified polyoxymethylene obtained by the production process according to any one of claims 7 to 8 for producing a bushing for an accelerator pedal of an automobile.
10. An automobile accelerator pedal bushing, characterized in that it is made of the modified polyoxymethylene of any one of claims 1 to 6 or the modified polyoxymethylene obtained by the production method of any one of claims 7 to 8.
CN202110294342.9A 2021-03-19 2021-03-19 Modified polyformaldehyde, automobile accelerator pedal bushing and preparation method Active CN113024989B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110294342.9A CN113024989B (en) 2021-03-19 2021-03-19 Modified polyformaldehyde, automobile accelerator pedal bushing and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110294342.9A CN113024989B (en) 2021-03-19 2021-03-19 Modified polyformaldehyde, automobile accelerator pedal bushing and preparation method

Publications (2)

Publication Number Publication Date
CN113024989A true CN113024989A (en) 2021-06-25
CN113024989B CN113024989B (en) 2022-12-27

Family

ID=76471551

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110294342.9A Active CN113024989B (en) 2021-03-19 2021-03-19 Modified polyformaldehyde, automobile accelerator pedal bushing and preparation method

Country Status (1)

Country Link
CN (1) CN113024989B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2172169A1 (en) * 2008-10-01 2010-04-07 Coltene Whaledent AG Dental post
CN102161812A (en) * 2011-05-30 2011-08-24 连云港鹰游碳塑材料有限责任公司 Carbon-fiber-reinforced wear-resistant polyformaldehyde gear and preparation method thereof
US20160083499A1 (en) * 2013-04-18 2016-03-24 Basf Se Polyoxymethylene copolymers and thermoplastic pom composition
CN105690807A (en) * 2016-02-06 2016-06-22 陕西科技大学 Preparation method and application of carbon fiber reinforced polymer-based composite
CN110903671A (en) * 2019-11-20 2020-03-24 天津渤化永利化工股份有限公司 Polyformaldehyde-based wood-plastic composite material and preparation method thereof
CN112280238A (en) * 2020-11-05 2021-01-29 青岛聚合利安工程技术有限公司 Preparation method of enhanced high-thermal-stability polyacetal composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2172169A1 (en) * 2008-10-01 2010-04-07 Coltene Whaledent AG Dental post
CN102161812A (en) * 2011-05-30 2011-08-24 连云港鹰游碳塑材料有限责任公司 Carbon-fiber-reinforced wear-resistant polyformaldehyde gear and preparation method thereof
US20160083499A1 (en) * 2013-04-18 2016-03-24 Basf Se Polyoxymethylene copolymers and thermoplastic pom composition
CN105690807A (en) * 2016-02-06 2016-06-22 陕西科技大学 Preparation method and application of carbon fiber reinforced polymer-based composite
CN110903671A (en) * 2019-11-20 2020-03-24 天津渤化永利化工股份有限公司 Polyformaldehyde-based wood-plastic composite material and preparation method thereof
CN112280238A (en) * 2020-11-05 2021-01-29 青岛聚合利安工程技术有限公司 Preparation method of enhanced high-thermal-stability polyacetal composition

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
HOSSEIN SALAVATI，等: "Preparation and characterization of polyphosphotungstate/ZrO 2 nanocomposite and their sonocatalytic and photocatalytic activity under UV light illumination", 《ULTRASONICS SONOCHEMISTRY》 *
汪瑾，等: "纳米Zr02／POM复合材料机械性能和摩擦磨损性能的研究", 《2006全国摩擦学学术会议论文集（三）》 *
洪凯，等: "碳纤维含量对聚甲醛自润滑材料力学和摩擦磨损性能的影响", 《化工新型材料》 *
温变英: "《高分子材料与加工》", 31 March 2011, 中国轻工业出版社 *

Also Published As

Publication number Publication date
CN113024989B (en) 2022-12-27

Similar Documents

Publication Publication Date Title
CN109679205B (en) High-strength anti-warping polyolefin composite material and preparation method thereof
CN105504489A (en) Alkali-free glass fiber reinforcing modified polypropylene composite material and preparing method thereof
CN108164821B (en) Long glass fiber reinforced polypropylene composite material with high fluidity, high apparent property and low VOC (volatile organic compounds) and preparation method thereof
CN101875759B (en) Reinforced polyethylene glycol terephthalate-modified material and preparation method thereof
CN101205362A (en) Warpage-resistant composite reinforced nylon 66 composition
CN104387663A (en) Long glass fiber reinforced polypropylene composite material as well as preparation method and application thereof
CN102516662A (en) Polypropylene composite material with high strength and high heat resistance and its preparation method
CN113462141A (en) High-toughness low-floating-fiber-reinforced PC/PBT alloy material and preparation method thereof
JPH0423863A (en) Highly strong polyamide resin composition and its preparation thereof
CN101880432B (en) Polyhydric graft ethylene-octene copolymer and preparation method thereof
CN112574558A (en) Anti-floating fiber type glass fiber reinforced bio-based nylon material and preparation method thereof
CN111117185A (en) High-impact-resistance glass fiber reinforced PC/ABS alloy material and preparation method thereof
CN105131592A (en) High-content glass fiber reinforced polyamide 66 composite material and preparing method
CN110655710B (en) Scratch-resistant impact-resistant polypropylene material and preparation method thereof
CN113024989B (en) Modified polyformaldehyde, automobile accelerator pedal bushing and preparation method
CN114149651A (en) Long glass fiber reinforced polypropylene material with low odor, low floating fiber and thermal aging resistance and preparation process thereof
CN102321327A (en) Multi-grafted phenylethylene-ethylene-butylene copolymer and preparation method thereof
CN101445654B (en) Material of filling and glass fibre reinforced nylon 6 and preparation method thereof
KR102463416B1 (en) Polyamide complex composition reinforced with glass fiber and carbon fiber
CN1765990A (en) Nylon 6 composition useable for car engine hood and its preparation method
CN114044999B (en) Low-fiber-floating glass fiber reinforced ABS composition and preparation method and application thereof
CN111138756A (en) Long glass fiber reinforced polypropylene composite material for automobile storage battery bracket and preparation method thereof
CN104610717A (en) Glass fiber reinforced nylon 66 composite
CN112876775B (en) High-wear-resistance polypropylene material and preparation method thereof
CN109161180B (en) High-apparent-performance glass fiber reinforced PC/PBT alloy automobile windscreen wiper material and preparation thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
PP01 Preservation of patent right
PP01 Preservation of patent right

Effective date of registration: 20230131

Granted publication date: 20221227

PD01 Discharge of preservation of patent
PD01 Discharge of preservation of patent

Date of cancellation: 20240108

Granted publication date: 20221227

PP01 Preservation of patent right
PP01 Preservation of patent right

Effective date of registration: 20240227

Granted publication date: 20221227