CN110669325A - Automobile guide ball pin formed by PET polyester modified by nano-alumina particles - Google Patents
Automobile guide ball pin formed by PET polyester modified by nano-alumina particles Download PDFInfo
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- CN110669325A CN110669325A CN201910934047.8A CN201910934047A CN110669325A CN 110669325 A CN110669325 A CN 110669325A CN 201910934047 A CN201910934047 A CN 201910934047A CN 110669325 A CN110669325 A CN 110669325A
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/011—Nanostructured additives
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
Discloses an automobile guide ball pin, which is made of a material formed by melt blending of polycarbonate, ethylene-methacrylate copolymer and PET polyester; the PET polyester is obtained by blending and modifying common PET polyester and nano-grade alumina particles. The automobile guide ball pin not only has higher impact strength, but also has higher elongation at break; the related technical indexes can fully meet the performance requirements of the automobile guide ball pin.
Description
Technical Field
The invention belongs to the field of automobile materials; relates to a material for a guide ball pin of an automobile; and more particularly, to an automobile guide ball pin formed by PET polyester modified by nano-alumina particles.
Background
The guide ball pin is an important part on the automobile and is used for controlling the steering of the automobile. Long-time, the structure of direction ball round pin is comparatively complicated, needs the form fit through ball seat and cylindrical casing just can rotate, and operation and equipment convenience are poor, have improved the processing cost of car to a certain extent. In addition, the structure is complex, so that the guide ball pin is worn seriously under long-term tensile and pressure load bearing, the service life is short, and the reliability requirement of long-term use is difficult to meet.
The inventor uses PET polyester as synthetic resin to form a small ball seat in Chinese utility model CN200820165818, and replaces the original steel wire small ball. The material has better elasticity, has larger matching surface, increases the friction surface, plays a role in compensating the abrasion of the product, and has excellent rotation performance and tensile pressure.
However, the use of PET polyester as a material for ball seats of guide ball pins for automobiles has disadvantages of low notched impact strength and low elongation at break.
To ameliorate these technical deficiencies, polycarbonate has further been alloyed with PET polyester. By virtue of the advantages of the amorphous polycarbonate polymer, the alloy formed by the amorphous polycarbonate polymer has excellent impact resistance and dimensional stability. Zengbanlu et al (polymer materials science and engineering, 1991, 110-.
Because PET polyester is a crystalline polymer and polycarbonate is an amorphous polymer, a simple blending system formed by the PET polyester and the polycarbonate is easy to generate phase separation, the bonding force of a two-phase interface is poor, and the notch impact strength is difficult to improve.
Therefore, the automobile guide ball pin formed by PET polyester modified by nano-alumina particles is urgently needed to be further researched on the basis of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the automobile guide ball pin formed by the PET polyester modified by the nano-alumina particles, which has higher notch impact strength and higher elongation at break.
In order to achieve the aim, the invention provides an automobile guide ball pin which is made of a material formed by melt blending of polycarbonate, ethylene-methacrylate copolymer and PET polyester; the PET polyester is characterized by being obtained by blending and modifying common PET polyester and nano-scale alumina particles.
In the present invention, the nano-scale means a particle size range having an average particle size of 1 to 1000 nm. Preferably, nanoscale means a particle size range having an average particle size of 10 to 900 nm; more preferably, nanoscale means a particle size range having an average particle size of 50 to 700 nm; and, most preferably, nanoscale means a particle size range having an average particle size of 100-500 nm.
In a particular embodiment, the nanoscale alumina is selected from alumina powders having an average particle size of 320 nm.
The automobile guide ball pin is characterized in that the weight ratio of the polycarbonate to the ethylene-methacrylate copolymer to the PET polyester is (60-80): (0.5-6): (40-20).
Preferably, the weight ratio of the polycarbonate, the ethylene-methacrylate copolymer and the PET polyester is (65-75): (1-5): (40-25); more preferably, the weight ratio of the polycarbonate, the ethylene-methacrylate copolymer, and the PET polyester is (60-75): (1.5-4): (40-25); and, most preferably, the weight ratio of the polycarbonate, the ethylene-methacrylate copolymer, and the PET polyester is (60-70): (2-3): (40-30).
In a specific embodiment, the weight ratio of the polycarbonate, the ethylene-methacrylate copolymer, and the PET polyester is 65: 2.5: 35.
the automobile guide ball pin provided by the invention has the advantages that the number average molecular weight Mn of the polycarbonate is 14000-30000 daltons.
Preferably, the number average molecular weight Mn of the polycarbonate is 16000 and 28000 daltons; more preferably, the number average molecular weight Mn of the polycarbonate is 18000 and 26000 daltons; and, most preferably, the number average molecular weight Mn of the polycarbonate is 20000-.
In a specific embodiment, the polycarbonate has a number average molecular weight Mn of 22000 daltons.
The automobile guide ball pin provided by the invention has the advantages that the number average molecular weight Mn of the PET polyester is 30000-46000 daltons.
Preferably, the number average molecular weight Mn of the PET polyester is 32000-44000 dalton; more preferably, the number average molecular weight Mn of the PET polyester is 34000 and 42000 daltons; and, most preferably, the number average molecular weight Mn of the PET polyester is 36000-40000 Dalton.
In a particular embodiment, the PET polyester has a number average molecular weight Mn of 38500 daltons.
The automobile guide ball pin is characterized in that the nanoscale alumina particles are further modified by glycidyl methacrylate.
In a specific embodiment, the glycidyl methacrylate is obtained from Shandong Yukang chemical Co., Ltd, and has a purity of 99.9%.
The automobile guide ball pin provided by the invention has the advantages that the grafting ratio of glycidyl methacrylate of the nano-scale alumina particles is 8.0-18.0%.
Preferably, the grafting ratio of the glycidyl methacrylate of the nano-scale alumina particles is 9.0-17.0%; more preferably, the nano-scale alumina particles have a glycidyl methacrylate grafting ratio of 10.0 to 16.0%; and, most preferably, the nano-sized alumina particles have a glycidyl methacrylate grafting ratio of 11.3 to 15.4%.
In a specific embodiment, the nano-sized alumina particles have a glycidyl methacrylate grafting ratio of 13.8%.
The automobile guide ball pin according to the invention, wherein the grafting ratio is obtained from TGA data.
According to the automobile guide ball pin, the nanoscale alumina particles are obtained by reacting nanoscale alumina powder with a silane coupling agent and then polymerizing the nanoscale alumina powder with glycidyl methacrylate.
The automobile guide ball pin according to the present invention, wherein the silane coupling agent is a silane coupling agent having a polymerizable group.
Preferably, the polymerizable group is selected from the group consisting of vinyl, ethynyl, epoxy, and (meth) acryloxy; more preferably, the polymerizable group is selected from vinyl and (meth) acryloxy; and, most preferably, the polymerizable group is selected from (meth) acryloxy groups.
In a specific embodiment, the silane coupling agent is a silane coupling agent having a methacryloxypropyl group.
In a more specific embodiment, the silane coupling agent is selected from the group consisting of KH-570, 99.8% purity; purchased from Nanjing to the front chemical Co.
The automobile guide ball pin provided by the invention is characterized in that the weight ratio of the nanoscale alumina powder to the silane coupling agent to the glycidyl methacrylate is 10: (3-9): (4-15).
Preferably, the weight ratio of the nanoscale alumina powder, the silane coupling agent and the glycidyl methacrylate is 10: (3-8): (5-14); more preferably, the weight ratio of the nanoscale alumina powder, the silane coupling agent and the glycidyl methacrylate is 10: (4-7): (5-13); and, most preferably, the weight ratio of the nanoscale alumina powder, the silane coupling agent, and the glycidyl methacrylate is 10: (4-6): (6-12).
In a specific embodiment, the weight ratio of the nanoscale alumina powder, the silane coupling agent, and the glycidyl methacrylate is 10: 5: 10.
the automobile guide ball pin provided by the invention is characterized in that the weight ratio of the nanoscale alumina particles to the PET polyester is 1: (2-8).
Preferably, the weight ratio of the nano-alumina particles to the PET polyester is 1: (3-7); more preferably, the weight ratio of the nano-alumina particles to the PET polyester is 1: (3.5-6.5); and, most preferably, the weight ratio of the nano-sized alumina particles to the PET polyester is 1: (4-6).
In a specific embodiment, the weight ratio of the nano-alumina particles to the PET polyester is 1: 5.
the automobile guide ball pin provided by the invention is characterized in that the melt index of the ethylene-methacrylate copolymer is 1-10g/10 min; the methacrylate content is 8-40 wt%.
Preferably, the ethylene-methacrylate copolymer has a melt index of 2 to 9g/10 min; the methacrylate content is 14-36 wt%; more preferably, the ethylene-methacrylate copolymer has a melt index of 3 to 8g/10 min; the methacrylate content is 18-32 wt%; and, most preferably, the ethylene methacrylate copolymer has a melt index of 4 to 7g/10 min; the methacrylate content is 22-28 wt%.
In a specific embodiment, the ethylene methacrylate copolymer has a melt index of 6g/10 min; the methacrylate content was 24% by weight.
Advantageously, the material of the automotive guide ball pin according to the invention is formed by melt blending in a twin-screw extruder.
The inventor finds that the alloy material obtained by using the modified PET polyester obtained by modifying nano-alumina particles, the ethylene-methacrylate copolymer and the polycarbonate has high impact strength and high elongation at break. Without wishing to be bound by any theory, the modified nanoscale alumina particles used in the invention not only play a role in improving the toughness of the material of the ball seat of the automobile guide ball, but also promote the compatibility with a resin system through the reactivity of methacryloxypropyl on the surface of alumina, and have a synergistic effect with an ethylene-methacrylate copolymer, so that the notch impact strength and the elongation at break of the material of the ball seat of the automobile guide ball are further improved.
Compared with the prior art, the invention has the following beneficial technical effects:
i) the automobile guide ball pin has excellent notch impact strength and elongation at break, and the notch impact strength is more than or equal to 50KJ × m-2And the elongation at break is more than or equal to 130 percent; so that the performance requirement of the ball seat for the automobile guide ball pin can be fully met.
ii) the method of the invention is simple and easy to implement, easy to popularize and has higher practical value.
Detailed Description
In a specific embodiment of the present invention, the notched impact strength test was performed according to astm d256-2018 standard, the impact energy was 2.8J, and the average was taken for 5 test samples.
The elongation at break test was performed according to ASTM D638-2014, the tensile rate was 10mm/min, the test temperature was room temperature, and the average value was taken for 5 test samples.
The TGA test was carried out using a Q500 thermogravimetric analyzer of TA, with a temperature rise rate of 10 degrees/min from room temperature to 700 degrees under a nitrogen atmosphere.
The grafting rate of the modified nanoscale alumina was obtained from the TGA data.
Example 1:
10g of nano-sized alumina powder (average particle size: 320nm) and 5g of silane coupling agent KH570 were ultrasonically dispersed in toluene, reacted with stirring at 120 ℃ for 4 hours in a nitrogen atmosphere, and then cooled to room temperature. 8g of glycidyl methacrylate dissolved in toluene and a few drops of AIBN were added and the reaction was stirred at 80 ℃ for 2 hours under a nitrogen atmosphere. After centrifugal drying, acetone extraction is used for removing unreacted coupling agent and residual toluene solvent, finally drying is carried out, modified nanometer alumina particles are obtained, and the grafting rate of glycidyl methacrylate obtained by TGA data is 13.8 wt%.
Preheating 8g of modified nano-alumina particles at 90 ℃, adding the modified nano-alumina particles into 40g of PET polyester preheated and melted at 90 ℃, and stirring the PET polyester under vacuum for 2.5h to ensure that the modified PET polyester is uniformly mixed with the PET polyester, wherein the number average molecular weight Mn of the PET polyester is 38500 daltons.
65g of polycarbonate (number average molecular weight Mn is 22000 dalton), 2.5g of ethylene-methacrylate copolymer (melt index is 6g/10 min; methacrylate content is 24 wt%) and 35g of modified PET polyester are mixed uniformly, and then added into a double-screw extruder to be extruded and granulated, wherein the extrusion processing temperature is controlled between 240 +/-2 ℃, and the screw rotation speed is 400 rpm. Then, the extruded and cut granules are dried at 120 ℃ and prepared into samples.
Example 2:
10g of nano-sized alumina powder (average particle size: 320nm) and 6g of silane coupling agent KH570 were ultrasonically dispersed in toluene, reacted with stirring at 130 ℃ for 6 hours in a nitrogen atmosphere, and then cooled to room temperature. 12g of glycidyl methacrylate dissolved in toluene and a few drops of AIBN were added and the reaction was stirred at 80 ℃ for 2 hours under a nitrogen atmosphere. After centrifugal drying, acetone extraction is used for removing unreacted coupling agent and residual toluene solvent, finally drying is carried out, modified nanometer alumina particles are obtained, and the grafting rate of glycidyl methacrylate obtained by TGA data is 15.4 wt%.
Preheating 10g of modified nano-alumina particles at 90 ℃, adding the particles into 40g of PET polyester preheated and melted at 90 ℃, and stirring the PET polyester under vacuum for 3 hours to uniformly mix the modified nano-alumina particles and the PET polyester, wherein the number average molecular weight Mn of the PET polyester is 38500 daltons.
70g of polycarbonate (the number average molecular weight Mn is 22000 dalton), 3g of ethylene-methacrylate copolymer (the melt index is 6g/10 min; the methacrylate content is 24 wt%) and 30g of modified PET polyester are mixed uniformly, and then the mixture is added into a double-screw extruder to be extruded and granulated, wherein the extrusion processing temperature is controlled between 230 +/-2 ℃, and the screw rotating speed is 600 rpm. Then, the extruded and cut granules are dried at 110 ℃ and prepared into samples.
Example 3:
10g of nano-sized alumina powder (average particle size: 320nm) and 4g of silane coupling agent KH570 were ultrasonically dispersed in toluene, reacted with stirring at 125 ℃ for 3 hours in a nitrogen atmosphere, and then cooled to room temperature. 6g of glycidyl methacrylate dissolved in toluene and a few drops of AIBN were added and the reaction was stirred at 80 ℃ for 2 hours under a nitrogen atmosphere. After centrifugal drying, acetone extraction is used for removing unreacted coupling agent and residual toluene solvent, finally drying is carried out, modified nanometer alumina particles are obtained, and the grafting rate of glycidyl methacrylate obtained by TGA data is 11.3 wt%.
Preheating 7g of modified nano-alumina particles at 90 ℃, adding the particles into 42g of PET polyester preheated and melted at 90 ℃, and stirring the PET polyester under vacuum for 4 hours to uniformly mix the modified nano-alumina particles and the PET polyester, wherein the number average molecular weight Mn of the PET polyester is 38500 daltons.
60g of polycarbonate (the number average molecular weight Mn is 22000 dalton), 2g of ethylene-methacrylate copolymer (the melt index is 6g/10 min; the methacrylate content is 24 wt%) and 40g of modified PET polyester are mixed uniformly, and then the mixture is added into a double-screw extruder to be extruded and granulated, wherein the extrusion processing temperature is controlled between 250 +/-2 ℃, and the screw rotating speed is 600 rpm. The extruded and cut pellets were then dried at 130 ℃ and prepared into samples.
Comparative example 1:
the remaining conditions were the same as in example 1, but unmodified nanosize alumina powder was used directly.
Comparative example 2:
the same procedure as in example 1 was repeated except that 10g of nanosized alumina powder (average particle diameter: 320nm), 1g of silane coupling agent KH570 and 2g of glycidyl methacrylate were used to obtain modified nanosized alumina particles having a glycidyl methacrylate graft ratio of 6.9 wt%.
Comparative example 3:
the same procedure as in example 1 was repeated except that 10g of nano-alumina (average particle diameter: 320nm), 0.5g of KH570 as a silane coupling agent, and 1g of glycidyl methacrylate were used to obtain modified nano-alumina particles having a glycidyl methacrylate graft ratio of 3.7 wt%.
The notched impact strength and elongation at break of the test specimens of examples 1-3 and comparative examples 1-3 according to the test methods described above are shown in Table 1 with the results associated therewith:
TABLE 1
As can be seen from Table 1, the materials obtained by blending and modifying the modified PET polyester obtained by using the modified nano-alumina particles of examples 1 to 3 of the present invention, the ethylene-methacrylate copolymer and the polycarbonate not only have high impact strength, but also have high elongation at break. Correlation index (notch impact strength is more than or equal to 50KJ m)-2And the elongation at break is more than or equal to 130 percent) so that the performance requirements of the automobile guide ball pin can be fully met.
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 shall fall within the protection scope of the present invention.
Claims (11)
1. An automobile guide ball pin is made of a material formed by melt blending of polycarbonate, ethylene-methacrylate copolymer and PET polyester; the PET polyester is characterized by being obtained by blending and modifying common PET polyester and nano-scale alumina particles.
2. The automotive guide ball pin of claim 1, wherein the weight ratio of the polycarbonate, the ethylene-methacrylate copolymer, and the PET polyester is (60-80): (0.5-6): (40-20).
3. The ball guide pin of claim 1, wherein the number average molecular weight Mn of the PET polyester is 30000 and 46000 daltons.
4. The automobile guide ball pin of claim 1, wherein the nano-sized alumina particles are further modified from glycidyl methacrylate.
5. The automobile guide ball pin of claim 1, wherein the nano-sized alumina particles have a glycidyl methacrylate grafting ratio of 8.0-18.0%.
6. The automobile guide ball pin of claim 1, wherein the nano-sized alumina particles have a glycidyl methacrylate grafting ratio of 11.3 to 15.4%.
7. The automobile guide ball pin of claim 1, wherein the nano-sized alumina particles are obtained by reacting nano-sized alumina powder with a silane coupling agent and then polymerizing with glycidyl methacrylate.
8. The automotive guide ball pin of claim 7, wherein the weight ratio of the nanoscale alumina powder, silane coupling agent, and glycidyl methacrylate is 10: (3-9): (4-15).
9. The automotive guide ball pin of claim 7, wherein the silane coupling agent is a silane coupling agent having a methacryloxypropyl group.
10. The automobile guide ball pin of claim 1, wherein the weight ratio of the nano-sized alumina particles to the PET polyester is 1: (2-8).
11. The automotive guide ball pin of claim 1, wherein the ethylene-methacrylate copolymer has a melt index of 1-10g/10 min; the methacrylate content is 8-40 wt%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201280156Y (en) * | 2008-10-16 | 2009-07-29 | 沈百庆 | Guide ball-pin assembly |
| CN102061076A (en) * | 2010-12-10 | 2011-05-18 | 深圳市富恒塑胶新材料有限公司 | Super-tough PC (polycarbonate)/PBT (Polybutylece Terephthalate)/PET (Polyethylene Glycol Terephthalate) alloy and preparation method thereof |
| CN104693764A (en) * | 2013-12-10 | 2015-06-10 | 青岛同创节能环保工程有限公司 | Nano-particle filled and reinforced PC/PET alloy |
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2019
- 2019-09-29 CN CN201910934047.8A patent/CN110669325B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201280156Y (en) * | 2008-10-16 | 2009-07-29 | 沈百庆 | Guide ball-pin assembly |
| CN102061076A (en) * | 2010-12-10 | 2011-05-18 | 深圳市富恒塑胶新材料有限公司 | Super-tough PC (polycarbonate)/PBT (Polybutylece Terephthalate)/PET (Polyethylene Glycol Terephthalate) alloy and preparation method thereof |
| CN104693764A (en) * | 2013-12-10 | 2015-06-10 | 青岛同创节能环保工程有限公司 | Nano-particle filled and reinforced PC/PET alloy |
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| 孙贵生等: "纳米二氧化硅表面改性及辐射引发接枝GMA的研究", 《辐射研究与辐射工艺学报》 * |
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Denomination of invention: Automobile guide ball pin formed by PET polyester modified by nano alumina particles Effective date of registration: 20220107 Granted publication date: 20211026 Pledgee: Zhejiang Shaoxing Ruifeng Rural Commercial Bank Co.,Ltd. Keyan sub branch Pledgor: SOMIC AUTOMOTIVE COMPONENTS Co.,Ltd. Registration number: Y2022330000023 |
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