CN108203536A - Thermoplastic polyester elastomer composition and manufacture the method for secondary spring with it - Google Patents
Thermoplastic polyester elastomer composition and manufacture the method for secondary spring with it Download PDFInfo
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- CN108203536A CN108203536A CN201611183138.5A CN201611183138A CN108203536A CN 108203536 A CN108203536 A CN 108203536A CN 201611183138 A CN201611183138 A CN 201611183138A CN 108203536 A CN108203536 A CN 108203536A
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- polyester elastomer
- elastomer composition
- secondary spring
- hard segment
- thermoplastic polyester
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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
- C08K3/34—Silicon-containing compounds
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Abstract
The invention discloses a kind of thermoplastic polyester elastomer compositions, including pet copolyester block copolymer and auxiliary agent, the block copolymer includes hard segment and soft chain segment, the hard segment derives the repetitive unit formed by least one aklylene glycol and at least one aromatic binary carboxylic acid and forms, and the soft chain segment is derived by polycaprolactone diols to be formed.The invention also discloses the methods that carrier secondary spring is manufactured with above-mentioned polyester elastomer composition.The present invention is by improving the composition of thermoplastic polyester elastomer composition, physical property of the thermoplastic polyester elastomer under high temperature and low temperature environment is improved, the secondary spring manufactured with the thermoplastic polyester elastomer can preferably meet the rigors such as high dynamic load, low compression set, durability and the comfort of carrier.
Description
Technical field
The present invention relates to Material Field, more particularly to a kind of thermoplastic polyester elastomer composition and by the thermoplastic
Property polyester elastomer composition for carrier secondary spring manufacturing method.
Background technology
Thermoplastic polyester elastomer is also known as lactoprene, is that one kind contains polyphenyl dioctyl phthalate alkyl diol ester hard section and fat
The line-type block polymer of adoption ester or polyester soft segment.Thermoplastic polyester elastomer has both the excellent elasticity of rubber and thermoplasticity modeling
The workability of material, and its structural strength is high, creep resistant is good, resilience is excellent, anti-impact and resist bending are tired, wear-resisting, ruler
Very little stabilization has flexibility in low temperature, can also keep good performance at high temperature.Therefore with thermoplastic polyester elastomer system
Standby product may be used as bearing the high-strength damping element of dynamic fatigue, such as the bumper and absorbing shock element of the automobile vehicles and
Bridge Seismic block etc..
The Breakage Mechanism of commercial vehicle secondary spring is to lead to material self-heating since alternating bending deforms, at this time
Temperature reduce the physical characteristic of material, generate local crackle or product gross distortion.Therefore, the auxiliary of excellent in te pins of durability
Materials for springs must have the property that physical characteristic does not also reduce even in a high temperature environment.Need that there is firm crosslinking thus
The higher-dimension structure of the polyester molecule chain of structure.However, it uses with trade markIt is auxiliary made from this polyester elastomer sold
Helping spring, (cross sectional shape is as shown in Figure 1, ingredient mainly includes three kinds：Dimethyl terephthalate (DMT), polyethylene glycol (such as poly- four
Methylene ether ethylene glycol, poly- ethyleneether ethylene glycol or polytrimethylene ether ethylene glycol etc.), short-chain diol (such as butanediol, second two
Alcohol)), carrying out Plumb load experiment, (experimental condition is：20kN~200kN, cycle frequency 1Hz；It is required that it is that product does not damage
Bad, when permanent deformation is no more than 25%), cycle occurs as soon as serious cracking phenomena less than 10,000 times, can not meet the outstanding of commercial vehicle
Hang the requirement of shock mitigation system.
From the structure of secondary spring, meat thickness is especially big, and most thickness is 56mm, and most thin is 10mm, and volume is also very big, about
For 1000cm3, the block of size needed for using continuous extrusion, then cutting again is relatively suitble to be processed or using casting
Technique is made, i.e., fills mold with melted material, is then cooled down while pressure is applied.However both processing method systems
There is phenomena such as big of damaging or be permanently deformed when carrying out load fatigue test in the secondary spring obtained.In addition, using common note
It is also feasible that molding process, which is processed, but its production efficiency is very low, and being molded each secondary spring needs thirty or forty minute,
If improve efficiency, it is necessary to put into more machines and manpower, also increase processing cost in this way.
Invention content
One of the technical problem to be solved in the present invention is to provide a kind of thermoplastic polyester elastomer composition, it is in high temperature ring
There is good physical characteristic under border.
In order to solve the above technical problems, the thermoplastic polyester elastomer composition of the present invention, is total to including polyester-polyester block
Polymers and auxiliary agent, the block copolymer include hard segment and soft chain segment, the hard segment by least one aklylene glycol and
At least one aromatic binary carboxylic acid derives the repetitive unit to be formed and forms, and the soft chain segment derives shape by polycaprolactone diols
Into.
The auxiliary agent includes nucleating agent, heat stabilizer and antioxidant, the nucleating agent preferably talc powder, and additive amount is
1.5~2.5wt%.Such nucleating agent can preferably control the dispersibility of nucleating agent particle and its be distributed in the elastomer
Uniformity improves the crystallization rate of elastomer, and decisive role is played to the consistency and reproducibility of subsequent forming processing.Consider
Stay longer in the melt is needed during secondary spring is manufactured, therefore a effective amount of thermostabilization can be added to elastomer
Agent and antioxidant, heat stabilizer and antioxidant additive amount are generally respectively 0.5~1.5wt%.
The weight ratio of the hard segment and soft chain segment is 50:50~70:30, preferably 65:35.This ratio synthesis gathers
Ester elastomer has elasticity, intensity and cryogenic property, and can also meet the Static stiffness requirement of secondary spring well well.
The aklylene glycol be ethylene glycol, propylene glycol or butanediol, the aromatic binary carboxylic acid be phthalic acid, institute
State hard segment by one kind in polyethylene terephthalate, polytrimethylene phthalate, polybutylene terephthalate or
A variety of compositions.It is described hard when the aklylene glycol is 1,4-butanediol, and the aromatic binary carboxylic acid is terephthalic acid (TPA)
Segment is made of mutual-phenenyl two acid bromide two alcohol ester as repetitive unit, and the number-average molecular weight of hard segment is 10000~40000, excellent
It is selected as 30000.
The polycaprolactone diols is by 6-caprolactone and low molecular weight diols (such as ethylene glycol, butanediol and new penta 2
Alcohol etc.) it is formed through ring-opening polymerisation, number-average molecular weight is for 5000~20000 (if the number-average molecular weight of polycaprolactone diols is less than
5000, then block can be poor；If higher than 20000, the compatibility of hard segment and soft chain segment can reduce, obtained thermoplasticity
The mechanical strength of polyester elastomer can be poor), preferred number average molecular weight 10000.
Melt index of the thermoplastic polyester elastomer composition under 230 DEG C of temperature, 2.16kg mass for 0.5~
10g/10min, preferably 0.5~1.5g/10min.The elastomer of this melt index is relatively suitble in multistation injection (mo(u)lding) machine
Upper molding, obtained secondary spring have better performance.
The preferable hardness of the thermoplastic polyester elastomer composition is shore D50~D60.
The second technical problem to be solved by the present invention is to provide a kind of manufacturing method of carrier secondary spring.
In order to solve the above technical problems, the carrier secondary spring of the present invention, is combined using above-mentioned polyester elastomer
Object is made by multistation injection (mo(u)lding) machine and hot runner plastic injection mould injection moulding.
The multistation injection (mo(u)lding) machine includes a mobile ejecting device, 2 or more locked mode stations and ejecting mechanism.
Since in the forming process of secondary spring, cooling occupies the 80% of total molding time, and therefore, mobile ejecting device can made
Injection pressurize is carried out to other molds in product cooling procedure, can thus greatly improve processing efficiency, reduces equipment and manpower
Input.
The present invention is derived by improving the composition of thermoplastic polyester elastomer by hard polyester segments and polycaprolactone diols
Soft chain segment collectively form polyester elastomer, and hard segment and soft even section form the cross-linked structure of higher-dimension, ensure that material in height
Physical characteristic does not reduce, and improve the stability and processing efficiency of product under mild low temperature environment, with the auxiliary bullet of its making
Spring can preferably meet the harshness such as high dynamic load, low compression set, durability and comfort of carrier will
It asks, while can also be effectively reduced the processing cost of secondary spring.
Description of the drawings
Fig. 1 is the schematic shapes of commercial vehicle secondary spring.Wherein, (A) figure is the front view of secondary spring；(B)
Figure is the vertical view of secondary spring.
Fig. 2 is the bearingtest schematic diagram of secondary spring.
Specific embodiment
There is more specific understanding for technology contents, feature and effect to the present invention, in conjunction with specific embodiment, to this hair
It is bright to be further described in detail.These embodiments are interpreted as the guarantor for being merely to illustrate the present invention rather than the limitation present invention
Protect range.After the content of the invention recorded has been read, those skilled in the art can make the present invention various changes or repair
Change, these equivalence changes and modification equally fall into the scope of the claims in the present invention.
Embodiment 1
By 100 parts by weight of poly terephthalic acid diol ester with number-average molecular weight 30000 and with number-average molecular weight
10000 33.3 parts of polycaprolactone glycol mixing, is stirred 1 hour under 230~245 DEG C of temperature, 130Pa pressure, treat resin into
It after transparence, takes out, cooling obtains polyester-polyester block copolymer (i.e. thermoplastic polyester elastomer).
At a temperature of 225~235 DEG C, on the twin screw extruder by above-mentioned polyester-polyester block copolymer and thermostabilization
Agent, antioxidant, nucleating agent carry out melt blending, and quenching is granulated in water.The nucleating agent is talcum powder, and additive amount is poly-
The 2wt% of ester elastomer composition.The additive amount of the heat stabilizer and antioxidant is respectively polyester elastomer composition
1wt%.
By six station injection (mo(u)lding) machines and hot runner plastic injection mould, using the processing conditions shown in table 1, manufacture such as Fig. 1
Shown secondary spring.The forming process of secondary spring is consistent with common moulding, including storing, injection, pressurize, cooling,
The processes such as demoulding, in this process, cooling occupy the 80% of molding time.
Table 1
Molding secondary spring product is immediately placed in constant temperature oven, is made annealing treatment.Annealing temperature is 120
DEG C, annealing time is 4~5h, it is then allowed voluntarily to be cooled to room temperature in baking oven, taking-up is tested for the property.
Embodiment 2
As different from Example 1, number-average molecular weight 10000 is substituted using the polycaprolactone glycol of number-average molecular weight 5000
Polycaprolactone glycol, other are the same as embodiment 1.
Embodiment 3
As different from Example 1, number-average molecular weight is substituted using the polycaprolactone glycol of number-average molecular weight 20000
10000 polycaprolactone glycol, other are the same as embodiment 1.
Embodiment 4 (comparative example)
As different from Example 1, multistation injection (mo(u)lding) machine is substituted using the single screw extrusion machine of 45mm, squeezed out as schemed
Then the bar of cross sectional shape shown in 1 carries out cutting into secondary spring as required again.Other are the same as embodiment 1.
Embodiment 5 (comparative example)
As different from Example 1, without using nucleating agent.Other are the same as embodiment 1.
Embodiment 6 (comparative example)
It usesThe polyester elastomer manufacture secondary spring of the model 5556 of sale, processing conditions with table 1, into
Annealing conditions after type are the same as embodiment 1.
7 secondary spring performance test of embodiment
With the evaluation of the sheet form obtained in above example carries out tensile strength with polyester elastomer sample, fracture is prolonged
Rate, tearing strength and compression set test are stretched, the sample for evaluation of the secondary spring in addition manufactured using above example is carried out
High/low temperature static compress is tested and the durability test of identical compression travel.Wherein, tensile strength, fracture elongation standard correspond to
In ASTM D412.Tearing strength test standard corresponds to ASTM D2262.
Static compress set (Cs%) test method is：Φ 15mm × 10mm test blocks are taken out from test piece, it is former to measure test piece
Beginning height h0With spacer height h2.40%, the aging 22hr in 70 DEG C of baker of test piece height are compressed, places 2hr again at room temperature
Release measures height h after aging1.Calculation formula is as follows：
Cs%=(h0-h1)/(h0-h2) × 100%.
Static compression properties test method is：With the speed precompressed sample 3 times of 50mm/min to 200KN, then with sample
The original height 82mm of product is zero, and the 4th is compressed to 200KN at the same rate, records power-displacement curve and a certain position
Such as the bearing capacity of 18mm；Then after being preheated 3 hours in 100 DEG C of environment, it is compressed to 200KN at the same rate, record power-
The bearing capacity of displacement curve and a certain position 18mm.
Dynamic fatigue test method is：Measure product original height h0, along product short transverse using compression travel as 0-
18mm (the original height 82mm of sample be zero), the frequency of 1HZ, cycle 100,000 times, survey height h after product fatigue1, Yi Jidong
The variation of the bearing capacity of peak position before and after state fatigue.Calculation formula is as follows：
△ L=h0-h1
Each test result is as shown in table 2.
Table 2
As can be seen from Table 2, the secondary spring manufactured using the method for the present invention, under 100 DEG C of high temperature, static bearing capacity can be with
Maintain more than 80% bearing capacity at normal temperatures, variation of the bearing capacity compared to the bearing capacity under room temperature under dynamic fatigue exists
20% hereinafter, illustrating the secondary spring of the present invention there is physical characteristic under high temperature atmosphere to reduce dynamic characteristic small, under high load capacity
With the advantages of durability is good, damping characteristic is small.
Claims (9)
1. a kind of thermoplastic polyester elastomer composition, which is characterized in that including polyester-polyester block copolymer and auxiliary agent, institute
It states block copolymer and includes hard segment and soft chain segment, the hard segment is by least one aklylene glycol and at least one aromatic series
Dicarboxylic acids derives the repetitive unit to be formed and forms, and the soft chain segment is derived by polycaprolactone diols to be formed.
2. polyester elastomer composition according to claim 1, which is characterized in that it is steady that the auxiliary agent includes nucleating agent, heat
Determine agent and antioxidant, the additive amount of the nucleating agent is 1.5~2.5wt%, the addition of the heat stabilizer and antioxidant
Amount is respectively 0.5~1.5wt%.
3. polyester elastomer composition according to claim 1, which is characterized in that the weight of the hard segment and soft chain segment
Than being 50:50~70:30.
4. polyester elastomer composition according to claim 3, which is characterized in that the weight of the hard segment and soft chain segment
Than being 65:35.
5. polyester elastomer composition according to claim 1, which is characterized in that the aklylene glycol for ethylene glycol,
Propylene glycol or butanediol, the aromatic binary carboxylic acid are phthalic acid, and the hard segment is by polyethylene terephthalate, poly-
One or more compositions in benzene dicarboxylic acid trimethylene glycol ester, polybutylene terephthalate.
6. polyester elastomer composition according to claim 5, which is characterized in that the aklylene glycol is Isosorbide-5-Nitrae-fourth two
Alcohol, the aromatic binary carboxylic acid are terephthalic acid (TPA), and the hard segment is by mutual-phenenyl two acid bromide two alcohol ester as repetitive unit
It forms, number-average molecular weight is 10000~40000.
7. polyester elastomer composition according to claim 1, which is characterized in that the polycaprolactone diols by ε-oneself
Lactone and low molecular weight diols are formed through ring-opening polymerisation, and number-average molecular weight is 5000~20000.
It is 8. special using the method for the polyester elastomer composition manufacture carrier secondary spring described in claim 1~7
Sign is, the secondary spring is injection moulded by multistation injection (mo(u)lding) machine and injection mold.
9. according to the method described in claim 8, it is characterized in that, the multistation injection (mo(u)lding) machine is penetrated including a movable type
Go out device, 2 or more locked mode stations and ejecting mechanism.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611183138.5A CN108203536A (en) | 2016-12-20 | 2016-12-20 | Thermoplastic polyester elastomer composition and manufacture the method for secondary spring with it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611183138.5A CN108203536A (en) | 2016-12-20 | 2016-12-20 | Thermoplastic polyester elastomer composition and manufacture the method for secondary spring with it |
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| CN108203536A true CN108203536A (en) | 2018-06-26 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1806134A (en) * | 2003-06-11 | 2006-07-19 | 帝斯曼知识产权资产管理有限公司 | Process for making a compression spring member from copolyetherester |
| CN101230184A (en) * | 2008-02-01 | 2008-07-30 | 北京市化学工业研究院 | Polyester elastomer composition and method of making the same |
| CN103804857A (en) * | 2012-11-15 | 2014-05-21 | 上海凯众材料科技股份有限公司 | Thermoplastic polyester elastomer composition and application thereof |
| CN105694009A (en) * | 2014-11-25 | 2016-06-22 | 上海凯众材料科技股份有限公司 | Zirconium/cerium-montmorillonite composite catalyst, and preparation method for polyester glycol |
-
2016
- 2016-12-20 CN CN201611183138.5A patent/CN108203536A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1806134A (en) * | 2003-06-11 | 2006-07-19 | 帝斯曼知识产权资产管理有限公司 | Process for making a compression spring member from copolyetherester |
| CN101230184A (en) * | 2008-02-01 | 2008-07-30 | 北京市化学工业研究院 | Polyester elastomer composition and method of making the same |
| CN103804857A (en) * | 2012-11-15 | 2014-05-21 | 上海凯众材料科技股份有限公司 | Thermoplastic polyester elastomer composition and application thereof |
| CN105694009A (en) * | 2014-11-25 | 2016-06-22 | 上海凯众材料科技股份有限公司 | Zirconium/cerium-montmorillonite composite catalyst, and preparation method for polyester glycol |
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