CN107936498A - A kind of piston of automobile safety-key PBT and preparation method thereof - Google Patents
A kind of piston of automobile safety-key PBT and preparation method thereof Download PDFInfo
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- CN107936498A CN107936498A CN201711384012.9A CN201711384012A CN107936498A CN 107936498 A CN107936498 A CN 107936498A CN 201711384012 A CN201711384012 A CN 201711384012A CN 107936498 A CN107936498 A CN 107936498A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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Abstract
The invention discloses a kind of piston of automobile safety-key PBT, it is characterised in that counting material component in parts by weight includes：60 70 parts of PBT resin, 3 10 parts of low density polyethylene (LDPE), 25 37 parts of chopped glass fiber, 38 parts of toughness reinforcing compatilizer, 0.5 0.8 parts of PETS lubricants and 0.1 1.0 parts of antioxidant；Wherein, PBT resin is formed by component A PBT resin and B component PBT resin compounding, the inherent viscosity of component A PBT resin is 1 ± 0.015dl/g, and the inherent viscosity of B component is 0.8 ± 0.015dl/g, and the percentage by weight of component A PBT resin is 47~60% in PBT resin.Piston of automobile safety-key PBT alloy low-temperature flexibility, wear-resisting property and electrical performance indexes of the present invention meet piston of automobile safety-key performance requirement, and production cost is relatively low, can partly substitute PBT501 uses.
Description
Technical field
High molecular material PBT production technical fields of the present invention, and in particular to a kind of piston of automobile safety-key PBT and its system
Preparation Method.
Background technology
Modern advanced engine, its plunger designs is considerably complicated, has evolved into collection light-high-strength new material, possesses
The high technology content product of multinomial new technology and one, the part that piston is auto cost and technology is concentrated the most, piston conduct
The important part of automobile engine, has important influence to the overall performance of engine.The requirement on machining accuracy of piston is very high,
Weatherability, wearability particularly to material require also higher.It is general mainly with high-quality gray cast iron, spheroidal graphite cast-iron, alloy in the past
Based on the materials such as cast iron, and such a defect is complex process, it is necessary to very high by repeatedly processing, cost.In recent years, shut out with the U.S.
The PBT501 materials of nation are used for piston of automobile safety-key always, and are in trade monopoly status.PBT makes as piston safety-key
With in addition to needing to meet wearability and machining accuracy, it is also necessary to emphatically solve low temperature environment under material become fragile it is not applicable
Problem.
The content of the invention
It is an object of the present invention to overcome defect existing in the prior art, there is provided a kind of group partition inter-capacitive is good
Piston of automobile safety-key PBT.
To achieve the above object, the technical scheme is that：A kind of piston of automobile safety-key PBT, it is characterised in that
Meter material component in parts by weight includes：60-70 parts of PBT resin, 3-10 parts of low density polyethylene (LDPE), 25-37 parts be chopped
Glass, 3-8 parts of toughness reinforcing compatilizer, 0.5-0.8 parts of PETS lubricants and 0.1-1.0 parts of antioxidant；
Wherein, PBT resin is formed by component A PBT resin and B component PBT resin compounding, and the characteristic of component A PBT resin is glued
Spend for 1 ± 0.015dl/g, the inherent viscosity of B component is 0.8 ± 0.015dl/gdl/g, component A PBT resin in PBT resin
Percentage by weight is 47~60%.Further, the inherent viscosity of component A PBT resin is 1.0dl/g, B component PBT resin
Inherent viscosity 0.8dl/g, the weight ratio of compounding is 1:1.
Pure low viscosity PBT crystallization shrinkages are big, and dimensional stability is poor, is answered using medium viscosity PBT and low viscosity PBT
Match somebody with somebody, gained blending PBT material has higher Modulus Strength, and dimensional stability is improved.Low density polyethylene (LDPE) and toughness reinforcing phase
Hold the collective effect of agent, the processing performance and low-temperature flexibility of co-mixing system can be improved.
Preferable technical solution is that low density polyethylene (LDPE) is low for the branched chain type of average molecular weight 20000-35000 dalton
Density polyethylene.Low density polyethylene (LDPE) has good pliability at low temperature, with further preferred Narrow Molecular Weight Distribution
Low density polyethylene (LDPE) is compared, and the higher or relatively low low density polyethylene (LDPE) of molecular weight can make the mechanics such as tensile strength and bending elasticity
Performance has declined.
In order to make low density polyethylene (LDPE) and PBT preferably compatible, preferable technical solution is that the toughness reinforcing compatilizer is choosing
Autohemagglutination olefin-propylene esters of gallic acid-glycidyl methacrylate terpolymer, maleic anhydride grafted ethene octene copolymer
(POE), the more than one or at least two combinations in acrylic acid-grafted ethylene-octene block copolymer (OBC-G-AA).
Above-mentioned three kinds of copolymers serve not only as toughness reinforcing compatilizer, also the compatilizer as polyesters polyolefins mixing, promote compound PBT with it is low
The compatible combination of density polyethylene, the problem of improving the low impact strength under low-temperature condition and poor toughness.Preferable polyolefin-the third
Olefin(e) acid esters-glycidyl methacrylate terpolymer model EMA8900.
Preferable technical solution is, the antioxidant for Hinered phenols antioxidant and phosphite ester kind antioxidant compounding and
Into the percentage by weight of Hinered phenols antioxidant is 25-35% in antioxidant.Two kinds of antioxidant are applied in combination, and can improve material
Heat endurance and radiation resistance.
Preferable technical solution is a diameter of 7-10 μm of chopped glass fiber, and the length of chopped glass fiber is 3-6mm.Microcosmic knot
The chopped glass fiber of above-mentioned model fiber attrition and loss of strength in PBT material are small in structure, easy to process.
Preferable technical solution is that low density polyethylene (LDPE) is 1F7B low density polyethylene (LDPE)s or 1C7A low density polyethylene (LDPE)s.
Preferable technical solution is that toughness reinforcing compatilizer is by polyolefin-acrylates class-glycidyl methacrylate three
Membered copolymer and acrylic acid-grafted ethylene-octene block copolymer combinations form, wherein polyolefin-acrylates class-methyl-prop
The percentage by weight of olefin(e) acid ethylene oxidic ester terpolymer is 90~95%.Acrylic acid-grafted ethylene-octene block copolymer
The compatibility that OBC-G-AA and PBT is directly blended is poor, preferable with the compatibility of low density polyethylene (LDPE), with toughness reinforcing compatilizer polyene
Hydrocarbon-esters of acrylic acid-glycidyl methacrylate terpolymer EMA is added in PBT at the same time, has the effect of coordination plasticizing
Fruit, component compatibility is good, and the long side chain of octene helps to reduce the brittle-ductile transition point of material in OBC-G-AA, and intermingling material has
Higher impact strength, OBC-G-AA contents are excessive and polyolefin-acrylates class-glycidyl methacrylate ternary is total to
Copolymer content reduces, then can cause compatibility poor in material processing, influence the impact strength of blend alloy.
The method of acrylic acid-grafted ethylene-octene block copolymer is as described in CN102746468B.
Preferable technical solution is, acrylic acid-grafted ethylene-octene block copolymer by ethylene-octene block copolymer,
Acrylic acid, dibenzoyl peroxide, three (2,4- di-tert-butyl-phenyl) phosphite ester fusion-graftings obtain, wherein ethylene-octene
The hardness of block copolymer is 60-70, and the tensile strength of acrylic acid-grafted ethylene-octene block copolymer is not less than 5Mpa.
Further preferred acrylic acid-grafted ethylene-octene block copolymer can strengthen the wear resistance of PBT, specific optional model
For OBC Tao Shi INFUSE9500,9107,9,000 3 kind.
Another object of the present invention, which also resides in, provides a kind of preparation method of piston of automobile safety-key PBT, its feature exists
In comprising the following steps：
S1：Configuration raw material is formed according to above-mentioned piston of automobile safety-key PBT；
S2：Two steps charging method will be used raw material will be placed in double screw extruder to extrude, through cooling down, drying, pelletizing obtains
Piston of automobile safety-key PBT particles；
Chopped glass fiber is fed by the side feeding mouth of double screw extruder in S2, twin-screw extrusion when chopped glass fiber adds
The temperature of molten polymer is 250~260 DEG C in machine.270~320 DEG C of blending being different from described in CN105255149A is high
Temperature, the content of glass is smaller in above-mentioned formula, and blending temperature is excessive to cause that melt viscosity is too low, and frictional force is inadequate, screw rod with
The contact probability increase of glass, glass increased wear.
In order to further reduce glass abrasion probability, preferable technical solution is that screw speed is 300~400r/min,
Screw slenderness ratio is 44：1.
The advantages of the present invention are：
Piston of automobile safety-key of the present invention is modified with PBT raw materials while using low density polyethylene (LDPE) and toughness reinforcing compatilizer
PBT, while chopped glass fiber enhancing is added, gained PBT alloy low-temperature flexibility, wear-resisting property and electrical performance indexes meet automobile work
Safety-key performance requirement is filled in, production cost is relatively low, can partly substitute PBT501 uses.
Embodiment
With reference to embodiment, the embodiment of the present invention is further described.Following embodiments are only used for more
Add and clearly demonstrate technical scheme, and be not intended to limit the protection scope of the present invention and limit the scope of the invention.
Embodiment 1-3 (abbreviation S1-3, similarly hereinafter)
The piston of automobile safety-key of embodiment 1 forms meter in parts by weight with PBT raw materials and see the table below：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| PBT resin (part) | 60 | 70 | 65 |
| Low density polyethylene (LDPE) (part) | 10 | 3 | 5 |
| Chopped glass fiber (part) | 25 | 37 | 31 |
| Toughness reinforcing compatilizer (part) | 3 | 8 | 5 |
| PETS lubricants (part) | 0.8 | 0.5 | 0.65 |
| Antioxidant (part) | 0.1 | 1 | 0.6 |
PBT resin is formed by component A PBT resin and B component PBT resin compounding in embodiment 1-3, component A PBT resin
Inherent viscosity is 0.99dl/g, and the inherent viscosity of B component PBT resin is 0.79dl/g, the weight of component A PBT resin in PBT resin
It is 47% to measure percentage.
Embodiment 4-6
The raw material composition parts by weight of resin are with embodiment 3 in embodiment 4-6, difference lies in：
The inherent viscosity of component A PBT resin is 1.01dl/g in embodiment 4, and the inherent viscosity of B component PBT resin is
0.81dl/g, the percentage by weight of component A PBT resin is 60% in PBT resin.
The inherent viscosity of component A PBT resin is 1dl/g in embodiment 5, and the inherent viscosity of B component PBT resin is 0.8dl/
The weight ratio of g, component A PBT resin and B component PBT resin is 1:1.
The LD615 of the swallowization used in embodiment 1-5, toughness reinforcing compatilizer are connect using the common ethene-octene copolymers of PBT
Branch glycidyl methacrylate (POE-GMA).Antioxidant compounds for Hinered phenols antioxidant and phosphite ester kind antioxidant
Form, the percentage by weight of Hinered phenols antioxidant is 25-35% in antioxidant.A diameter of 10 μm of chopped glass fiber, be chopped glass
Fine length is 6-10mm.
The piston of automobile safety-key of embodiment 1-5 is comprised the following steps with the preparation method of PBT：
S1：Configure raw material；
S2：Two steps charging method will be used raw material will be placed in double screw extruder to extrude, through cooling down, drying, pelletizing obtains
Piston of automobile safety-key PBT particles；
Chopped glass fiber is fed by the side feeding mouth of double screw extruder in S2, twin-screw extrusion when chopped glass fiber adds
The temperature of molten polymer is 250~260 DEG C in machine.
Screw speed is 300~400r/min, screw slenderness ratio 44：1.- 2 area 210 of 1st area of screw extruder Temperature Distribution
DEG C, 260 DEG C of -4th area of 3rd area, 215 DEG C of -11st area of 5th area, 245 DEG C of head.
Embodiment 6-7
Embodiment 6 and 7 is respectively that low density polyethylene (LDPE) is low close for 1F7B difference lies in low density polyethylene (LDPE) with embodiment 5
Spend polyethylene, 1C7A low density polyethylene (LDPE)s.
Embodiment 8-12
Embodiment 8 is with embodiment 7 difference lies in toughness reinforcing compatilizer, and embodiment 8 is using maleic anhydride grafted ethene octene
Copolymer, embodiment 9 is using polyolefin-acrylates class-glycidyl methacrylate terpolymer, embodiment 10-
12 is embedding using polyolefin-acrylates class-glycidyl methacrylate terpolymer and acrylic acid-grafted ethylene-octene
Section copolymer in combination forms, wherein the weight hundred of polyolefin-acrylates class-glycidyl methacrylate terpolymer
Divide than being respectively 90%, 95%, 92%.Acrylic acid-grafted ethylene-octene block copolymer by ethylene-octene block copolymer,
Acrylic acid, dibenzoyl peroxide, three (2,4- di-tert-butyl-phenyl) phosphite ester fusion-graftings obtain, and wherein embodiment 10 is adopted
With OBC Tao Shi INFUSE9007, ethylene-octene block copolymer meets that hardness is 60-70 in embodiment 11 and 12, tensile strength
For the scope not less than 5Mpa, OBC Tao Shi INFUSE9500 and 9107 are respectively adopted.
The preparation method of acrylic acid-grafted ethylene-octene block copolymer is mixed including dispensing in embodiment 12, and mixing is situated between
Qualitative response and Screw Extrusion pelletizing step.Proportion scale：94 parts by weight of ethylene-octene block copolymer, 5 parts by weight of acrylic acid,
0.3 parts by weight of dibenzoyl peroxide, three (2,4- di-tert-butyl-phenyls) phosphite esters, 0.3 parts by weight；Double screw extruder material
Cylinder temperature is 143-148 DEG C of Ith area, II 150-155 DEG C of area, III 157-160 DEG C of area, IV 160-163 DEG C of area, V 158-161 DEG C of area,
Counter rotation twin screw extruder die head temperature is 155-158 DEG C, acrylic acid-grafted rate 1.2-1.4%.
Embodiment 13
Difference lies in a diameter of 7-10 μm of chopped glass fiber, the length of chopped glass fiber is 3-6mm to embodiment 13.
Comparative example (abbreviation D, similarly hereinafter)
Based on embodiment 1, comparative example 1 does not add low density polyethylene (LDPE) as plasticized modifier；
Based on embodiment 1, comparative example 2 and 3 uses the PBT of one-component, inherent viscosity 1dl/g, 0.8dl/g.
The detection of mechanical property is carried out to PBT alloy obtained by embodiment and comparative example：
Tensile strength is tested by ASTM D-638 standards.Batten size (mm)：165 (length) × 19 (end portion width) ×
3.05 (thickness), draw speed 50mm/min；
Notch impact strength is tested by ASTM D-256 standards.Specimen size (mm)：63.5×12.45×3.1；Lack
Mouthful residual thickness be 1.9mm, low temperature by sample when -40 DEG C of baking ovens placements 4 are small after test notch impact strength immediately.
Test result see the table below：
As can be seen from the above table, with the increase of low density polyethylene (LDPE) content in system, the notch impact strength under low temperature
Improved, show that low density polyethylene (LDPE) can improve the low-temperature flexibility of PBT material, on the other hand, the selection pair of toughness reinforcing compatilizer
Influenced substantially in the component compatibility of PBT alloy, the PBT alloy material finally obtained has excellent resistance to low temperature.
Sample obtained by embodiment 8-12 test with the relative friction coefficient of steel, the dynamic friction factor of embodiment 8-10
0.29 is all higher than with static friction factor, the dynamic friction factor of embodiment 11 and 12 is between 0.24~0.25.Above-mentioned as shown by data,
The further selection of acrylic acid-grafted ethylene-octene block copolymer contributes to the wear-resisting property of small elevation PBT alloy.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, some improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of piston of automobile safety-key PBT, it is characterised in that counting material component in parts by weight includes：60-70 parts
PBT resin, 3-10 parts of low density polyethylene (LDPE), 25-37 parts of chopped glass fiber, 3-8 parts of toughness reinforcing compatilizer, 0.5-0.8 parts
PETS lubricants and 0.1-1.0 parts of antioxidant；
Wherein, PBT resin is formed by component A PBT resin and B component PBT resin compounding, and the inherent viscosity of component A PBT resin is
1 ± 0.015dl/g, the inherent viscosity of B component are 0.8 ± 0.015dl/gdl/g, the weight of component A PBT resin in PBT resin
Percentage is 47~60%.
2. piston of automobile safety-key PBT according to claim 1, it is characterised in that low density polyethylene (LDPE) is average mark
The branched chain type low density polyethylene (LDPE) of son amount 20000-35000 dalton.
3. piston of automobile safety-key PBT according to claim 1 or 2, it is characterised in that the toughness reinforcing compatilizer is choosing
Autohemagglutination olefin-propylene esters of gallic acid-glycidyl methacrylate terpolymer, maleic anhydride grafted ethene octene copolymer
More than one or at least two combinations in thing, acrylic acid-grafted ethylene-octene block copolymer.
4. piston of automobile safety-key PBT according to claim 1 or 2, it is characterised in that the antioxidant is hindered phenol
Kind antioxidant and phosphite ester kind antioxidant compounding form, and the percentage by weight of Hinered phenols antioxidant is 25- in antioxidant
35%.
5. piston of automobile safety-key PBT according to claim 1, it is characterised in that a diameter of 7-10 μ of chopped glass fiber
M, the length of chopped glass fiber is 3-6mm.
6. piston of automobile safety-key PBT according to claim 2, it is characterised in that low density polyethylene (LDPE) is low for 1F7B
Density polyethylene or 1C7A low density polyethylene (LDPE)s.
7. piston of automobile safety-key PBT according to claim 3, it is characterised in that toughness reinforcing compatilizer is by polyolefin-the third
Olefin(e) acid esters-glycidyl methacrylate terpolymer and acrylic acid-grafted ethylene-octene block copolymer combinations and
Into, wherein the percentage by weight of polyolefin-acrylates class-glycidyl methacrylate terpolymer for 90~
95%.
8. piston of automobile safety-key PBT according to claim 7, it is characterised in that acrylic acid-grafted ethylene-octene is embedding
Section copolymer is by ethylene-octene block copolymer, acrylic acid, dibenzoyl peroxide, three (2,4- di-tert-butyl-phenyls) phosphorous
Acid esters fusion-grafting obtains, and the wherein hardness of ethylene-octene block copolymer is 60-70, acrylic acid-grafted ethylene-octene block
The tensile strength of copolymer is not less than 5Mpa.
9. a kind of preparation method of piston of automobile safety-key PBT, it is characterised in that comprise the following steps：
S1：Configuration raw material is formed according to the PBT of the piston of automobile safety-key described in any one in claim 1-8；
S2：Two steps charging method will be used raw material will be placed in double screw extruder to extrude, through cooling down, drying, pelletizing obtains automobile
Piston safety-key PBT particles；
Chopped glass fiber is fed by the side feeding mouth of double screw extruder in S2, when chopped glass fiber adds in double screw extruder
The temperature of molten polymer is 250~260 DEG C.
10. the preparation method of piston of automobile safety-key PBT according to claim 9, it is characterised in that screw speed is
300~400r/min, screw slenderness ratio 44：1.
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Cited By (5)
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| CN109233219A (en) * | 2018-08-22 | 2019-01-18 | 东莞市国亨塑胶科技有限公司 | A kind of push-button material and preparation method thereof for exempting from oiling |
| CN110669320A (en) * | 2019-08-26 | 2020-01-10 | 天津柯文实业股份有限公司 | Preparation method of high-impact-resistance high-low-temperature-resistance poly (p-xylylene glycol terephthalate) |
| CN111286166A (en) * | 2020-04-08 | 2020-06-16 | 广东圆融新材料有限公司 | Polybutylene terephthalate composition and preparation method thereof |
| CN111410823A (en) * | 2020-04-08 | 2020-07-14 | 广东圆融新材料有限公司 | Reinforced polybutylene terephthalate composition and preparation method thereof |
| CN116285237A (en) * | 2022-12-30 | 2023-06-23 | 金发科技股份有限公司 | A thin-wall flame-retardant PBT composition with high toughness and high fluidity, its preparation method and application |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233219A (en) * | 2018-08-22 | 2019-01-18 | 东莞市国亨塑胶科技有限公司 | A kind of push-button material and preparation method thereof for exempting from oiling |
| CN110669320A (en) * | 2019-08-26 | 2020-01-10 | 天津柯文实业股份有限公司 | Preparation method of high-impact-resistance high-low-temperature-resistance poly (p-xylylene glycol terephthalate) |
| CN111286166A (en) * | 2020-04-08 | 2020-06-16 | 广东圆融新材料有限公司 | Polybutylene terephthalate composition and preparation method thereof |
| CN111410823A (en) * | 2020-04-08 | 2020-07-14 | 广东圆融新材料有限公司 | Reinforced polybutylene terephthalate composition and preparation method thereof |
| CN116285237A (en) * | 2022-12-30 | 2023-06-23 | 金发科技股份有限公司 | A thin-wall flame-retardant PBT composition with high toughness and high fluidity, its preparation method and application |
| CN116285237B (en) * | 2022-12-30 | 2025-03-25 | 金发科技股份有限公司 | A thin-wall flame-retardant PBT composition with high toughness and high fluidity, and its preparation method and application |
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Application publication date: 20180420 |