CN113024989B - Modified polyformaldehyde, automobile accelerator pedal bushing and preparation method - Google Patents
Modified polyformaldehyde, automobile accelerator pedal bushing and preparation method Download PDFInfo
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- CN113024989B CN113024989B CN202110294342.9A CN202110294342A CN113024989B CN 113024989 B CN113024989 B CN 113024989B CN 202110294342 A CN202110294342 A CN 202110294342A CN 113024989 B CN113024989 B CN 113024989B
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- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 43
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 42
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 28
- 239000012745 toughening agent Substances 0.000 claims abstract description 19
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 50
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 49
- 239000004917 carbon fiber Substances 0.000 claims description 49
- -1 polyoxymethylene Polymers 0.000 claims description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 30
- 238000001746 injection moulding Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 72
- 238000005516 engineering process Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical group [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
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- 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
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 the above, the present 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 [ beta- (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 a preferred embodiment of the present invention, the above preparation method comprises melt-extruding the mixed materials at 170-180 deg.C by using a torque rheometer, and then injection-molding the extruded master batch at 170-180 deg.C 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 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 polyoxymethylene may be contained in an amount of 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 in which an inner core and an outer shell are respectively compounded by a plurality of macromolecule-enriched layers.
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 [ beta- (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: proportionally mixing polyformaldehyde, toughening agent, reinforcing agent, antioxidant and heat stabilizer, and extruding for molding.
In a preferred embodiment of the present invention, the above preparation method comprises melt-extruding the mixed materials at 170-180 deg.C by using a torque rheometer, and then injection-molding the extruded master batch at 170-180 deg.C 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.
Alternatively, the modified polyformaldehyde may be used in the production of handlebar gloves, and is not limited to the automobile accelerator pedal bushing.
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 carried out according to 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 fibers, 1% of antioxidant and 0.5% of heat stabilizer.
The polyformaldehyde in the embodiment is POM/M90 of Yunnan Yuntanhua chemical Co., ltd, the toughening agent zirconia is purchased from Bohuas nanometer technology (Ningbo) Ltd, and the reinforcing agent chopped carbon fiber is purchased from Xiangsheng carbon fiber technology 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 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 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 bushing 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 bushing 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 bushing 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 bushing 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 the raw materials comprise 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 the raw materials comprise 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.
Table 2 mechanical properties of accelerator pedal sleeve.
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 5mm/min.
(2) The flexural strength and flexural modulus were measured by the method specified in GB/T9341 at a speed of 2mm/min over a span of 64mm.
(3) The notched impact strength was tested by 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, when the polyoxymethylene content of example 1 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: 88.5-93% of polyformaldehyde, 4-8% of flexibilizer, 2-7% of reinforcing agent, 0.1-1% of antioxidant and 0.1-0.5% of heat stabilizer;
the toughening agent is zirconium oxide; the reinforcing agent is chopped carbon fibers.
2. The modified polyoxymethylene of claim 1, comprising the following raw materials in weight percent: 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, wherein said chopped carbon fiber is a T700 grade carbon fiber.
4. The modified polyoxymethylene of claim 1 or 2, wherein the antioxidant is at least one of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and phenyl tris (2, 4-di-tert-butyl) phosphite.
5. The modified polyoxymethylene of claim 1 or 2, wherein the heat stabilizer is n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
6. The modified polyoxymethylene of claim 1 or 2, wherein 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: proportionally mixing polyformaldehyde, toughening agent, reinforcing agent, antioxidant and heat stabilizer, and extruding for molding.
8. The method of claim 7, wherein the method comprises melt-extruding the mixed materials at 170-180 ℃ using a torque rheometer, and then injection molding the extruded masterbatch at 170-180 ℃ and 55-60MPa using 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.
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