CN114163816A - Wear-resistant reinforced PPS composition and preparation method and application thereof - Google Patents
Wear-resistant reinforced PPS composition and preparation method and application thereof Download PDFInfo
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- CN114163816A CN114163816A CN202111675677.1A CN202111675677A CN114163816A CN 114163816 A CN114163816 A CN 114163816A CN 202111675677 A CN202111675677 A CN 202111675677A CN 114163816 A CN114163816 A CN 114163816A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- 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
- C08K2201/00—Specific properties of additives
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses an abrasion-resistant reinforced PPS composition, and a preparation method and application thereof. The reinforced PPS composition comprises the following components in parts by weight: 45-70 parts of PPS, 10-30 parts of chopped carbon fibers, 5-15 parts of PTFE, 5-10 parts of graphite and 5-10 parts of carbon powder; the graphite is a mixture of graphite with a first particle size and graphite with a second particle size, the D50 particle size of the graphite with the first particle size is 40-80 mu m, and the D50 particle size of the graphite with the second particle size is 10-15 mu m; the surfaces of the chopped carbon fibers and the carbon powder are coated with a surface treatment agent. Through the synergistic effect of graphite, polytetrafluoroethylene, chopped carbon fiber and carbon powder, the wear resistance of the PPS material is greatly improved, the friction loss and the friction coefficient are reduced, and the original high rigidity and high strength are maintained.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a wear-resistant reinforced PPS composition and a preparation method and application thereof.
Background
Polyphenylene Sulfide (PPS) has a structure in which benzene rings and sulfur atoms alternate with each other, and is imparted with good wear resistance and rigidity due to its specific structure, and is widely used for manufacturing parts such as seal rings, bearings, gears, and the like in automobiles. For precision and high-end applications, such as automobile bearing supports, aircraft landing gears, rotorcraft operating panels, etc., PPS materials are also required to have lower friction loss, lower coefficient, and higher rigidity.
The carbon fiber reinforced PPS can greatly improve the wear resistance and rigidity of the PPS, and the polytetrafluoroethylene is also a common wear-resistant auxiliary agent. The prior art discloses a carbon fiber reinforced PPS wear-resistant material, which comprises PPS, carbon fibers, polytetrafluoroethylene and the like. However, the poor compatibility of PPS with polytetrafluoroethylene causes the deterioration of the rigidity of PPS.
In addition, the prior art reports a high-wear-resistance polyphenylene sulfide material which comprises components such as PPS, polyamide and carbon fiber. Although the friction loss of the PPS material is improved to a certain extent by adding the polyamide, the friction coefficient of the PPS material is not obviously reduced.
Accordingly, there is a need to develop an abrasion resistant reinforced PPS composition having extremely low friction loss, coefficient of friction, and maintaining good stiffness.
Disclosure of Invention
The PPS composition greatly improves the wear resistance of a PPS material, reduces friction loss and friction coefficient and keeps original high rigidity and high strength through the synergistic effect of graphite, polytetrafluoroethylene, chopped carbon fibers and carbon powder.
It is another object of the present invention to provide a process for the preparation of the above-described reinforced PPS composition.
It is another object of the present invention to provide the use of the above-described reinforced PPS composition in the preparation of highly rigid, wear resistant PPS articles.
In order to solve the technical problems, the invention adopts the technical scheme that:
an abrasion-resistant reinforced PPS composition comprises the following components in parts by weight:
45-70 Parts of Polyphenylene Sulfide (PPS),
10-30 parts of short-cut carbon fiber,
5-15 parts of Polytetrafluoroethylene (PTFE),
5-10 parts of graphite,
5-10 parts of carbon powder;
the graphite is a mixture of graphite with a first particle size and graphite with a second particle size, the D50 particle size of the graphite with the first particle size is 40-80 mu m, and the D50 particle size of the graphite with the second particle size is 10-15 mu m;
the surfaces of the chopped carbon fibers and the carbon powder are coated with a surface treatment agent.
The reinforced PPS composition greatly improves the wear resistance of the PPS material, reduces the friction loss and the friction coefficient and keeps the original high rigidity and high strength through the synergistic effect of the graphite, the polytetrafluoroethylene, the chopped carbon fibers and the carbon powder.
The graphite in the reinforced PPS composition is a mixture of a larger particle size and a smaller particle size, wherein the graphite with the smaller particle size is easy to migrate to the surface of a material in the extrusion process, so that the wear resistance of the reinforced PPS composition is obviously enhanced; along with the increase of the abrasion loss of the material, the graphite with small particle size is more easily lost in the friction process, and at the moment, the graphite with larger particle size further plays a role in improving the wear resistance, so that the reinforced PPS composition keeps extremely low friction loss and has lasting and excellent friction performance.
The surfaces of the chopped carbon fibers and the carbon powder are coated with the surface treatment agent, the surface treatment agent has better interface bonding force to PTFE, and the performance reduction caused by the addition of the PTFE can be compensated.
Preferably, the surface treating agent is one or more of a polyurethane type surface treating agent, an epoxy resin surface treating agent and a polyamide surface treating agent.
More preferably, the surface treatment agent is a polyurethane-type surface treatment agent.
Optionally, the polyurethane-type surface treatment agent is one or more of a polymer of 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol and bis (isocyanatomethyl) benzene, a polyurethane resin (type 7160) or a polyurethane resin (type 7110J 3).
The CAS number of the polyurethane resin (7160 type) is 67700-43-0; the CAS number of the polyurethane resin (7110J3 type) is: 68227-93-0.
Preferably, the surface treatment agent coated on the surface of the chopped carbon fiber accounts for 0.5-2 wt% of the weight of the chopped carbon fiber; the surface treating agent coated on the carbon powder accounts for 0.5-2 wt% of the weight of the carbon powder.
Preferably, the chopped carbon fibers have an average length of 100 to 400 μm in the reinforced PPS composition.
More preferably, the chopped carbon fibers have an average length of 200 to 390 μm in the reinforced PPS composition.
When the chopped carbon fibers are in a proper length range, the mechanical property and the wear resistance of the reinforced PPS composition are better.
Preferably, the length of the raw material of the chopped carbon fiber is 3-12 mm.
The carbon powder is cylindrical particles obtained by grinding and screening carbon fibers.
Preferably, the average particle size of the carbon powder is 20 to 100 μm.
More preferably, the average particle size of the carbon powder is 25 to 50 μm.
The chopped carbon fibers are used as a main stress acceptor, and the material reinforcing effect is more obvious. The carbon powder has smaller average particle size and larger specific surface area, is more easily infiltrated by a resin matrix, and has more obvious improvement on the wear resistance of the reinforced PPS composition.
Preferably, the melt flow rate of the PPS under the conditions of 316 ℃ and 5kg is 100-1800 g/10 min.
More preferably, the melt flow rate of the PPS is 200-500 g/10min at 316 ℃ and 5 kg.
The melt flow rate of PPS is measured according to ISO1133-2011 standard method.
Preferably, the mass ratio of the first particle size graphite to the second particle size graphite in the graphite is (0.5-2): 1.
the invention also provides a preparation method of the reinforced PPS composition, which comprises the following steps:
PPS, PTFE, graphite and carbon powder are mixed and then added into a main feeding port of an extruder, chopped carbon fibers are added into a side feeding port of the extruder, and the mixture is subjected to melt mixing and extrusion granulation to obtain the reinforced PPS composition.
Preferably, the extruder is a twin screw extruder.
Preferably, the temperature of a screw cylinder of the extruder is 200-320 ℃, the rotating speed is 100-800 rpm, and the length-diameter ratio of a screw is 28: 1-64: 1.
Preferably, the temperatures of the screw barrel 1-12 zones of the double-screw extruder are 200-220 ℃, 240-260 ℃, 280-300 ℃, 300-300 ℃ and 300-320 ℃.
The invention also protects the application of the reinforced PPS composition in preparing high-rigidity wear-resistant PPS products.
The rigid wear-resistant PPS part can be an automobile bearing bracket, an airplane landing gear or a rotorcraft operation panel.
Compared with the prior art, the invention has the beneficial effects that:
the wear-resistant reinforced PPS composition is developed, and the wear resistance of the PPS material is greatly improved, the friction loss and the friction coefficient are reduced, and the original high rigidity and high strength are maintained through the synergistic effect of the graphite, the polytetrafluoroethylene, the chopped carbon fibers and the carbon powder.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The raw materials in the examples and comparative examples are all commercially available;
reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Examples 1 to 20
Examples 1 to 20 each provide a PPS composition having the component contents shown in table 1, and the preparation method is as follows:
mixing PPS, PTFE, graphite and carbon powder according to the table 1, adding the mixture into a main feeding port of a double-screw extruder, adding chopped carbon fibers into a side feeding port of the double-screw extruder, and carrying out melt mixing, extrusion and granulation to obtain a PPS composition; wherein the length-diameter ratio of the screws of the double-screw extruder is 48: 1, the screw rotating speed of a screw barrel 1-12 area of a double-screw extruder is 500 rpm;
the temperatures of the barrel sections 1 to 12 of the twin-screw extruder are 200 to 220 ℃, 240 to 260 ℃, 280 to 300 ℃ and 300 to 320 ℃, respectively.
TABLE 1 component content (parts by weight) of PPS compositions of examples 1 to 20
Comparative examples 1 to 7
Comparative examples 1 to 7 each provide a PPS composition having the component contents shown in table 2, and the preparation method is as follows:
mixing the components except the chopped carbon fibers according to the table 2, adding the mixture into a main feeding port of a double-screw extruder, adding the chopped carbon fibers into a side feeding port of the double-screw extruder, and carrying out melt mixing, extrusion and granulation to obtain the PPS composition; wherein the length-diameter ratio of the screws of the double-screw extruder is 48: 1;
the screw rotating speed of a screw barrel 1-12 area of the double-screw extruder is 500 rpm;
the temperatures of the barrel sections 1 to 12 of the twin-screw extruder are 200 to 220 ℃, 240 to 260 ℃, 280 to 300 ℃ and 300 to 320 ℃, respectively.
TABLE 2 component contents (parts by weight) of PPS compositions of comparative examples 1 to 7
Performance testing
The reinforced PPS compositions prepared in the above examples and comparative examples were tested for their performance by the following specific methods:
friction loss: the test was carried out according to the standard ASTM D3702-2019 method, with the following test equipment: the TABER/5135 type friction loss tester has the following test conditions: single-arm load: 500 g; the type of the grinding wheel: h-18; speed: 72 r/min; the number of rubs: 25000 times;
coefficient of dynamic friction: the test was carried out according to the method of standard ASTM D1894-2014, with the test equipment: the 500N-zwickl friction coefficient meter has the following test conditions: during testing, the direction force FN applied to the slide block is 2N, the speed is 100mm/min, and the testing stroke is 60 mm;
modulus of elasticity: the test was carried out according to the method of standard ISO 527-2-2012, with the following test equipment: the universal electronic testing machine has the following testing conditions: the gauge length is 50mm, and the stretching speed is 1 mm/min;
average length of carbon fiber: burning the reinforced PPS composition at 900 ℃ for 60min under the protection of nitrogen, standing and cooling to 23 ℃, collecting residues, dispersing the residues by using a solution, observing the retention length value of the fiber by using a microscope, and calculating to obtain the average length of the carbon fiber.
The test results of examples 1 to 20 are shown in Table 3, and the test results of comparative examples 1 to 7 are shown in Table 4.
TABLE 3 test results of examples 1 to 20
According to the test results in Table 3, the reinforced PPS compositions prepared in the examples of the invention have the friction loss less than or equal to 3.0 per thousand, the dynamic friction coefficient less than or equal to 0.31 and excellent friction resistance; the elastic modulus is more than or equal to 7500MPa, the rigidity of the material is good, and the strength is high.
In examples 1, 4, 5, 8 and 9, when the surface treatment agent of the chopped carbon fibers and the carbon powder is a polyurethane-based surface treatment agent, the reinforced PPS composition is more excellent in friction resistance and higher in rigidity.
From the test results of examples 1 to 3 and examples 1, 6 and 7, the average length of the chopped carbon fibers in the reinforced PPS composition is preferably 100 to 300 μm, and the average particle size of the carbon powder is preferably 20 to 50 μm.
From the embodiment 1 and the embodiment 13 to 15, the melt flow rate of PPS is preferably 100 to 1800g/10min at 316 ℃ and 5 kg; more preferably 200 to 500g/10 min.
In the graphite obtained in examples 1 and 16 to 18, the mass ratio of the graphite having the first particle size to the graphite having the second particle size is (0.5 to 2): at 1, the coefficient of dynamic friction is relatively lower and the modulus of elasticity is higher.
TABLE 4 test results for comparative examples 1 to 7
According to the test results in Table 4, in comparative example 1 in which graphite having a larger particle size and graphite having a smaller particle size were not compounded but only graphite having a particle size of 30 μm of D50 was added, the PPS composition obtained had a large frictional loss and poor rigidity, and had an elastic modulus of only 6920 MPa.
In comparative example 2, graphite with the particle size of D50 being 100 μm and 3 μm is used for compounding, so that the effect of improving the wear resistance cannot be effectively realized, and the friction loss and the dynamic friction coefficient of the PPS composition are high.
In comparative example 3, the graphite with the D50 particle size of 40-80 μm is not contained, and in comparative example 4, the graphite with the D50 particle size of 10-15 μm is not contained, so that the wear resistance of the PPS composition is poor.
The carbon fiber in comparative example 5 was not coated with the surface treatment agent, and the carbon powder in comparative example 6 was not coated with the surface treatment agent, so that the compatibility of PTFE with other components was poor, and the obtained PSS composition was poor in comprehensive properties.
In comparative example 6, the carbon powder was not contained, and although the chopped carbon fibers could play a part of the reinforcing role, the wear resistance of the PSS composition could not meet the actual wear resistance requirements.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. An abrasion-resistant reinforced PPS composition is characterized by comprising the following components in parts by weight:
45-70 parts of PPS, 10-30 parts of chopped carbon fibers, 5-15 parts of PTFE, 5-10 parts of graphite and 5-10 parts of carbon powder;
the graphite is a mixture of graphite with a first particle size and graphite with a second particle size, the D50 particle size of the graphite with the first particle size is 40-80 mu m, and the D50 particle size of the graphite with the second particle size is 10-15 mu m;
the surfaces of the chopped carbon fibers and the carbon powder are coated with a surface treatment agent.
2. The reinforced PPS composition as recited in claim 1, wherein said surface treatment agent is one or more of a polyurethane-type surface treatment agent, an epoxy resin surface treatment agent, or a polyamide surface treatment agent.
3. The enhanced PPS composition of claim 2 wherein said surface treatment agent is a polyurethane-type surface treatment agent.
4. The reinforced PPS composition of claim 1 wherein the chopped carbon fibers have an average length of 100 to 400 μm in the reinforced PPS composition.
5. The reinforced PPS composition as recited in claim 1, wherein the carbon powder has an average particle size of 20 to 100 μm.
6. The reinforced PPS composition as recited in claim 1, wherein the ratio of the first particle size graphite to the second particle size graphite in the graphite is (0.5-2): 1.
7. the reinforced PPS composition of claim 1 wherein the PPS has a melt flow rate of 100 to 1800g/10min at 316 ℃ and 5 kg.
8. The reinforced PPS composition of claim 7 wherein the PPS has a melt flow rate of 200 to 500g/10min at 316 ℃ and 5 kg.
9. A method of preparing an enhanced PPS composition according to any of claims 1 to 8 comprising the steps of:
PPS, PTFE, graphite and carbon powder are mixed and then added into a main feeding port of an extruder, chopped carbon fibers are added into a side feeding port of the extruder, and the mixture is subjected to melt mixing and extrusion granulation to obtain the reinforced PPS composition.
10. Use of the reinforced PPS composition according to any of claims 1 to 8 for the preparation of a highly rigid, wear resistant PPS article.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0711088A (en) * | 1993-06-25 | 1995-01-13 | Asahi Glass Co Ltd | Polytetrafluoroethylene composition |
| JPH08311338A (en) * | 1995-05-18 | 1996-11-26 | Ntn Corp | Heat-resistant, lubricating resin composition |
| JP2003213063A (en) * | 2002-01-29 | 2003-07-30 | Mitsubishi Cable Ind Ltd | Seal composition and seal using the same and used for rotary shaft |
| CN106084778A (en) * | 2016-06-29 | 2016-11-09 | 广州市聚赛龙工程塑料股份有限公司 | A kind of heat conduction wear-resisting high-strength degree polyphenyl thioether composite material and preparation method thereof |
| CN111117248A (en) * | 2019-12-31 | 2020-05-08 | 苏州纳磐新材料科技有限公司 | Carbon fiber reinforced PPS wear-resistant material and preparation method thereof |
| WO2020114419A1 (en) * | 2018-12-04 | 2020-06-11 | 大金氟化工（中国）有限公司 | Preparation method for polytetrafluoroethylene composition, polytetrafluoroethylene composition, forming product, conductive pipe, heat conduction film, and substrate ccl |
| CN111574833A (en) * | 2020-05-17 | 2020-08-25 | 上海交通大学 | High-wear-resistance polyphenylene sulfide/regenerated carbon fiber composite material and preparation thereof |
-
2021
- 2021-12-31 CN CN202111675677.1A patent/CN114163816B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0711088A (en) * | 1993-06-25 | 1995-01-13 | Asahi Glass Co Ltd | Polytetrafluoroethylene composition |
| JPH08311338A (en) * | 1995-05-18 | 1996-11-26 | Ntn Corp | Heat-resistant, lubricating resin composition |
| JP2003213063A (en) * | 2002-01-29 | 2003-07-30 | Mitsubishi Cable Ind Ltd | Seal composition and seal using the same and used for rotary shaft |
| CN106084778A (en) * | 2016-06-29 | 2016-11-09 | 广州市聚赛龙工程塑料股份有限公司 | A kind of heat conduction wear-resisting high-strength degree polyphenyl thioether composite material and preparation method thereof |
| WO2020114419A1 (en) * | 2018-12-04 | 2020-06-11 | 大金氟化工（中国）有限公司 | Preparation method for polytetrafluoroethylene composition, polytetrafluoroethylene composition, forming product, conductive pipe, heat conduction film, and substrate ccl |
| CN111117248A (en) * | 2019-12-31 | 2020-05-08 | 苏州纳磐新材料科技有限公司 | Carbon fiber reinforced PPS wear-resistant material and preparation method thereof |
| CN111574833A (en) * | 2020-05-17 | 2020-08-25 | 上海交通大学 | High-wear-resistance polyphenylene sulfide/regenerated carbon fiber composite material and preparation thereof |
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