CN105542376B - Thermoplastic elastomehc sex camplex and preparation method thereof and the application in preparing automobile bottom backplate - Google Patents
Thermoplastic elastomehc sex camplex and preparation method thereof and the application in preparing automobile bottom backplate Download PDFInfo
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- CN105542376B CN105542376B CN201510846826.4A CN201510846826A CN105542376B CN 105542376 B CN105542376 B CN 105542376B CN 201510846826 A CN201510846826 A CN 201510846826A CN 105542376 B CN105542376 B CN 105542376B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- 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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- 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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- C08L2207/04—Thermoplastic elastomer
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Abstract
Application the invention discloses a kind of thermoplastic elastomehc sex camplex and preparation method thereof and in preparing automobile bottom backplate, is made of the raw material of following weight percent：Matrix resin 10~50%；Filling oil 15~50%；Thermoplastic elastomer (TPE) 20~60%；Mineral filler 0~20%；Bond reinforcing agent 2~15%；Special addition agent 0~5%；Processing aid 0~5%；Stabilizer 0.1~5%.The preparation method of the present invention has the advantages that easy to operate, strong operability, is suitable for industrialized production.The thermoplastic elastomehc sex camplex of the present invention can be separately formed, also post forming can be carried out with polypropylene material, with good lower temperature resistance, high temperature resistant compressibility, excellent mechanical property and with the good cementitiousness of polypropylene, it can be used for preparing automobile bottom backplate, the automobile bottom backplate elastic recovery is good, product is smooth, and the loss of long term high temperature ageing properties is small.
Description
Technical field
The present invention relates to thermoplastic elastomer (TPE) fields, and in particular to a kind of thermoplastic elastomehc sex camplex and preparation method thereof and
Application in preparing automobile bottom backplate.
Background technology
Sealing material is widely used in building and the fields such as automobile, can be with the intrusion of rain-proof and anti-wind noise, can be with
Play the role of damping, dust-proof, improvement comfort.In conventional art, generally polyvinyl chloride (PVC) material is used to be used as sealing material
Material, but PVC material at low temperature harden by feel, and contains some toxicity additives and plasticizer in PVC material, may exudation or
Gasification, can interfere biological endocrine, can also increase carcinogenic risk, incinerate PVC rubbish and will produce carcinogenic bioxin and pollute big
Gas, there are environmental issues.And in the past few years, the application of the molding mode of quadric injection mould it is more universal, in the car very much
Product is all molded using this kind of mode, especially most widely used plastics variety-polypropylene in the car, using this kind of mode
Molding product is especially prominent, such as guiding gutter, bottom backplate, seat backplate etc..And polyvinyl chloride due to compatibility the problem of, can not
It gains ground in this aspect.
The sealing element that part is directly molded using polyethylene, low-temperature flexibility is good, but low temperature (- 40 degrees Celsius with
Under) lower part product size can change, subsequent assembly is caused to perplex.Using ethylene propylene diene rubber heat cure, although
Various aspects of performance is excellent, but its whole Productive statistics is big, complex process, and production cost is excessive.The two can not equally be applied
With in polypropylene post forming purposes.
Thermoplastic sulfurized rubber (TPV) various aspects of performance is excellent, can carry out post forming with polypropylene material.But it is whole
Productive statistics are big, complex process, unit price is higher.
The Chinese invention patent application that application publication number is CN 101845195A (application No. is 201010166515.0) is public
A kind of wear-resistant thermoplastic elastomer and preparation method thereof is opened, which includes the original of following mass percent
Material：It is matrix resin 10%~80%, filling oil 0~42%, masterbatch 10%~60%, thermoplastic resin 0~20%, mineral-filled
Agent 0~30%, coupling agent 0~1.5%, processing aid 0.1~2%, stabilizer 0.1%~2%, wherein the masterbatch is by such as
The raw material of lower weight percent is made：It is vector resin 50%~80%, compatilizer 0~30%, anti-wear agent 5%~20%, inorganic
Nano-particle 4%~25%：The matrix resin is selected from Styrene-Butadiene-Styrene Block Copolymer, hydrogenation of benzene second
One or both of alkene-butadiene-styrene block copolymer；The filling oil is more than 200 DEG C of saturation selected from flash-point
Linear paraffin oil, flash-point are more than 200 DEG C of one or both of naphthenic oil：The thermoplastic resin be selected from polypropylene,
One kind in polyethylene, polystyrene or at least two, the mineral filler are selected from talcum powder, calcium carbonate, kaolin, cloud
One kind in female powder, wollastonite or at least two.Although it is wear-resisting that the technical solution solves thermoplastic elastomer (TPE) to a certain extent
Property difference problem, obtained a kind of wear-resisting thermoplastic elastic material, but its high temperature resistant lower temperature resistance is poor.
For the present invention by carrying out thermoplasticity elastomer material preferably with cooperation, it is excellent to be prepared for various aspects of performance, raw
Production input is low, simple for process, the lower composition for thermoplastic elastomer of unit price, and the composition is successfully applied to automobile bottom shield
Panel products.
Invention content
The present invention provides a kind of thermoplastic elastomehc sex camplex and preparation method thereof and answering in preparing automobile bottom backplate
With the thermoplastic elastomehc sex camplex can be separately formed, also can carry out post forming with polypropylene material, have good resistance to
Low temperature properties, high temperature resistant compressibility, excellent mechanical property and with the good cementitiousness of polypropylene.
A kind of thermoplastic elastomehc sex camplex, is made of the raw material of following weight percent：
The present invention carries out rational proportion by thermoplastic elastomer (TPE), matrix resin kind, auxiliary agent type, and to it, fully
It waves to take off and obtains thermoplastic elastomehc sex camplex (i.e. automobile bottom backplate thermoplastic elastomer (TPE)), size is steady under high/low temperature condition
It is fixed, there is preferable lower temperature resistance and heat-resisting quantity, post forming can be carried out with polypropylene product, it is current to be protected in automobile bottom
Plate has a vast market foreground and application value.
In order to obtain better invention effect, below as the preferred of the present invention：
The thermoplastic elastomehc sex camplex, is made of the raw material of following weight percent：
Mineral filler particle can further carry out dimensionally stable, and (i.e. automobile bottom protects obtained thermoplastic elastomehc sex camplex
Plate thermoplastic elastomer (TPE)) its performance has certain promotion, it is seen that and mineral filler can promote the thermoplastic elastic of the present invention
Complex has better lower temperature resistance and heat-resisting quantity, preferably can carry out post forming with polypropylene product.
Still more preferably, the thermoplastic elastomehc sex camplex, is made of the raw material of following weight percent：
The increase of special addition agent can play synergistic effect with other compositions, increase substantially thermoplastic elastomehc of the present invention
The performance of sex camplex.
The matrix resin is polypropylene.Polypropylene can specifically select the PP 1304E3 that Exxon Mobil produces, platform modeling
PP 3015, the PP 1120 of Ningbo production, K4818, GM1600E of oil of SPC production, the PP of Y2600T, South Korea SK production
R380Y, PP R370Y, it is one or more in the commercial product of the trades mark such as K7025, K4535, K1085 of platform.Matrix resin
It can be specifically chosen according to actual needs.
The filling oil is in saturated straight chain alkane oil of the flash-point more than 200 DEG C, naphthenic oil of the flash-point more than 200 DEG C
One or two, thermal stability is good.The 150 of specific optional U.S.'s sun-stone (SUNPAR) production of filling oil, the double dragons of South Korea
150SN, the 250SN of production, the PW-90 of Japanese light extraction (Idemitsu) production, the KN4020 of Kelamayi production, Hebei Science Court
It is one or more in the commercial product such as KP6025, KP6030 of production.
The thermoplastic elastomer (TPE) is selected from styrenic elastomer, ethylene propylene diene rubber (EPDM), ethylene-octene copolymerization
One kind or at least two in object elastomer (POE), thermoplastic vulcanizates (TPV).Benzene second can be selected in styrenic elastomer
The block copolymer (SEBS) that alkene (S)-ethylene (E)/butylene (B)-styrene (S) is constituted, styrene (S)-ethylene (E)/propylene
(P) block copolymer (SEPS) that-styrene (S) is constituted, styrene (S)-ethylene (E)/ethylene (E)/propylene (P)-styrene
(S) block copolymer (SEEPS) constituted；SEBS specifically selection section can rise SEBS 6151, SEBS that (KRATON) is produced
1633, SEBS 1654, SEBS 1650, SEBS MD6944, platform rubber share SEBS6151, SEBS6159, Yueyang petrochemical iy produced
It is one or more in the commercial product such as SEBS 602, SEBS 503；SEPS can specifically select Kuraray (Kuraray)
2005,2007；SEEPS can specifically select the 4055,4077,4099 of Kuraray (Kuraray)；Ethylene propylene diene rubber can be selected specifically
It is one or more in the commercial product such as EPDM 3062EM, EPDM 3072EM, the EPDM 3090E produced with Mitsui Chemicals；Second
Alkene-octene copolymer elastomer can specifically select POE 0203, the POE 0201 that Exxon Mobil produces；Dow production
It is one or more in the commercial product such as POE9807, POE9817；Thermoplastic vulcanizates can specifically select santoprene
(Santoprene) TPV 101-84, TPV 101-80, TPV201-64, TPV201-35, TPV201-55, TPV8211-55
It is one or more in equal commercial product.
The mineral filler is one in talcum powder, calcium carbonate, kaolin, mica powder, wollastonite, nanometer illiteracy support soil
Kind is two or more (including two kinds).Domestic production producer can be selected such as：Guilin city, Jiangsu is vertical to be reached, the sub- safe, Liao Ninghai in Dalian
City, Zhejiang Feng Hong Deng Duo companies product.
The special addition agent is one or both of initiator, chain extender etc..Preferably, the special addition agent
For the mixture of initiator and chain extender, mass ratio 1:1, the initiator is bis 25 vulcanizing agent, above-mentioned initiation
Agent and chain extender can generate synergistic effect, can increase substantially the performance of thermoplastic elastomehc sex camplex of the present invention.Special type helps
Agent can be selected specifically such as bis 25 vulcanizing agent (initiator), CHEM CORD CM-3020 (chain extender), CelymerTMMDA (chain extensions
Agent), CelymerTMThe products such as 2160 (chain extenders), Hiplamide HP101 (chain extender).
The bonding reinforcing agent agent is one or more of propylene-based copolymer, terpene resin, Petropols
(including two kinds).For example, the Vistamax6202 of Exxon Mobil Corporation, the limited public affairs of Zhejiang Henghe oil shares can be selected specifically
At least one of the trades mark such as C5 hydrogenated petroleum resins of department commercial product.
The processing aid is aliphatic acid, fatty acid salt, fatty acid amide, polyethylene wax, polytetrafluoroethylene (PTFE), silicone
One or more of substance (including two kinds).For example, stearic acid, calcium stearate, zinc stearate, silicon can be selected specifically
At least one in the commercial product such as ketone powder, silicone master batch, organically-modified silicone, erucyl amide, oleamide, polytetrafluoroethylene (PTFE)
Kind.Preferably, the processing aid is oleamide, content is 0.1%~1%.
The stabilizer is the stabilizer of functional compounds containing benzophenone (i.e. benzophenone stabilizer), hindered phenol
One or more of class stabilizer, phosphite-type stabilisers, hindered amines stabilizer (including two kinds).For example, can
At least one in the trades mark commercial product such as specific UV-53l, 1010,168,1076,1024 for selecting Ciba Specialty Chemicals' product
Kind.
The present invention also provides a kind of preparation methods of thermoplastic elastomehc sex camplex, have easy to operate, strong operability, fit
In the industrialized production the advantages of.
The preparation method of the thermoplastic elastomehc sex camplex, includes the following steps：
Thermoplastic elastomer (TPE) and filling oil are sufficiently mixed uniformly, oil to be filled adds after being blotted completely by thermoplastic elastomer (TPE)
Enter matrix resin, add mineral filler, is added in whipping process and bonds reinforcing agent and special addition agent, added processing and help
Agent and stabilizer are sent into extruding pelletization in double screw extruder, are waved by hot air circulation de- (in granulation process after mixing
Using double vacuum suctions, vacuum pressure is maintained at 0.08MPA, and the product pellet after granulation carries out 4 hours in hot blast baking oven
Ventilation cycle), final obtained thermoplastic elastomehc sex camplex (i.e. automobile bottom backplate thermoplastic elastomer (TPE)).
As preferred：
The rotating speed of the double screw extruder is 200 revs/min~900 revs/min.
Each section of extruder temperature of the double screw extruder is 160 DEG C~240 DEG C, and the temperature of each section of screw rod can be identical
It can also be different.
Equipment commonly used in the art can be selected in the double screw extruder.
Thermoplastic elastomehc sex camplex prepared by the present invention, which can be separately formed, also can
With polypropylene material carry out post forming, have good lower temperature resistance, high temperature resistant compressibility, excellent mechanical property and with
The good cementitiousness of polypropylene, can be used for preparing automobile bottom backplate, and the automobile bottom backplate elastic recovery is good, and product is smooth, long
Phase high temperature ageing performance loss is small.
Compared with prior art, the invention has the advantages that：
The present invention can according to actual needs, polyvinyl resin that matrix resin can select low-temperature flexibility good, resistance to height
It is one or more in the good acrylic resin of temperature, it can specifically be adjusted according to the use environment of the rubber seal product of preparation
It is whole, the thermoplastic elastics such as SEBS, EPDM, POE, TPV (thermoplastic vulcanizates) of high-low temperature resistant and good stability of the dimension are added
Body is as modifying agent, and by talcum powder, the mineral fillers such as nano imvite particle further carries out dimensionally stable, and is added viscous
Reinforcing agent, special addition agent, processing aid, stabilizer etc. are tied, by having obtained automobile bottom backplate heat to the improvement of blending formula
Thermoplastic elastomer material so that automobile bottom backplate with thermoplastic elastic material there is more excellent performance, the material to have
Preferable ageing-resistant and excellent mechanical property.
The preparation method of automobile bottom backplate thermoplastic elastic material of the present invention, preparation manipulation is simple, controllability is good,
Production cost is low, is easy to industrialized production, and is not related to the use of chemical solvent in entire material modification production process, to environment
Influence small, halogen-free environmental, while the automobile bottom backplate prepares the leftover pieces of product with thermoplastic elastic material and also repeatable makes
With with preferable economic benefit and environmental benefit.Automobile bottom backplate thermoplastic elastomer (TPE) prepared by the present invention with it is similar
Product is compared, cheap, can with polypropylene matrix carry out post forming, product obtained can be widely used in automobile,
The fields such as building, household electrical appliances, such as prepare car storage box gasket, the Related products such as seat backplate, have a vast market foreground with
Higher application value.
Specific implementation mode
Embodiment 1
Using the raw material of following weight：
Filling oily (SUNPAR 150) is added in thermoplastic elastomer (TPE) (SEBS 6151) and is sufficiently mixed uniformly, waits filling out
It is oil-filled blotted completely by thermoplastic elastomer (TPE) after, matrix resin (PP R370Y) and mineral filler (1250 mesh carbonic acid is added
Calcium), it is added in whipping process and bonds reinforcing agent (Vistamax 6202) and special addition agent (initiator and chain extender) processing,
Then processing aid and 2Kg compound stabilizers is added, material after mixing in feeder feeding double screw extruder by cutting
It cuts, be kneaded, each screw temperature set of double screw extruder is at 220 DEG C~230 DEG C, 20 hertz of feeding frequency, engine speed 600
Rev/min.It is followed through double vacuum extractions (vacuum pressure is maintained at 0.08MPA), head extrusion, tie rod, air-cooled, pelletizing, hot blast
It is packed after ring drying in 4 hours, automobile bottom backplate is made with thermoplastic elastomer (TPE) (particle).
The automobile bottom backplate prepared to embodiment 1 is tested for the property as follows with thermoplastic elastomer (TPE), test side
Method and the results detailed in Table 1.
Table 1
Automobile bottom backplate thermoplastic elastomer (TPE) particle prepared by embodiment 1 obtains after 240 degrees Celsius of lower post formings
To automobile bottom guard plate material, the sealing element elastic recovery is good, and product is smooth, and the loss of long term high temperature ageing properties is small.
Embodiment 2
Filling oily (SUNPAR 150) is added in thermoplastic elastomer (TPE) (SEBS 6151) and is sufficiently mixed uniformly, waits filling out
It is oil-filled blotted completely by thermoplastic elastomer (TPE) after, matrix resin (PP R370Y) and mineral filler (1250 mesh carbonic acid is added
Calcium), it is added in whipping process and bonds reinforcing agent (Vistamax 6202) processing, processing aid (erucyl amide) is then added
With 2Kg compound stabilizers, material after mixing is sent into shearing in double screw extruder by feeder, is kneaded, and twin-screw squeezes
Go out each screw temperature set of machine at 220 DEG C~230 DEG C, 20 hertz of feeding frequency, 600 revs/min of engine speed.It is taken out through double vacuum
It is packed after proposing (vacuum pressure is maintained at 0.08MPA), head extrusion, tie rod, air-cooled, pelletizing, hot blast cycle drying in 4 hours,
Automobile bottom backplate is made with thermoplastic elastomer (TPE) (particle).
The automobile bottom backplate prepared to embodiment 2 is tested for the property as follows with thermoplastic elastomer (TPE), test side
Method and the results detailed in Table 2.
Table 2
Automobile bottom backplate thermoplastic elastomer (TPE) particle prepared by embodiment 2 obtains after 240 degrees Celsius of lower post formings
To automobile bottom guard plate material, the sealing element elastic recovery is good, and product is smooth, and the loss of long term high temperature ageing properties is small.
Compared with Example 2, embodiment 1 uses special addition agent (initiator and chain extender) to embodiment 1, and embodiment 2 does not have
There is use, other all sames, automobile bottom backplate thermoplastic elastomer (TPE) performance prepared by embodiment 1 will be significantly better than embodiment 2,
This is because when initiator and chain extender are used in conjunction in embodiment 1, synergistic effect is produced so that automobile bottom shield of the invention
Plate has more excellent performance with thermoplastic elastomer (TPE) performance.
Embodiment 3
Other than using the raw material of following weight, automobile bottom backplate thermoplastic elastomer (TPE) prepares other operations with real
Example 1 is applied, automobile bottom backplate thermoplastic elastomer (TPE) is made.
Embodiment 4
In addition to the raw material using following weight, each screw temperature set of double screw extruder is except 240 DEG C, automobile bottom shield
Automobile bottom backplate thermoplastic elastomer (TPE) is made with embodiment 1 in other operations prepared by plate thermoplastic elastomer (TPE).
Automobile bottom backplate heat prepared by the automobile bottom backplate thermoplastic elastomer (TPE) and embodiment 4 prepared to embodiment 3
Thermoplastic elastic is tested for the property as follows respectively, test method and the results detailed in Table 3.
Table 3
Automobile bottom backplate thermoplastic elastomer (TPE) particle prepared by embodiment 3 obtains after 240 degrees Celsius of lower post formings
To automobile bottom guard plate material, the sealing element elastic recovery is good, and product is smooth, and the loss of long term high temperature ageing properties is small.
Automobile bottom backplate thermoplastic elastomer (TPE) particle prepared by embodiment 4 obtains after 240 degrees Celsius of lower post formings
To automobile bottom guard plate material, the sealing element elastic recovery is good, and product is smooth, and the loss of long term high temperature ageing properties is small.
Claims (1)
1. a kind of thermoplastic elastomehc sex camplex being used to prepare automobile bottom backplate, which is characterized in that by following weight percent
Raw material is made：
Preparation method includes the following steps：
SUNPAR 150 is added in SEBS 6151 and is sufficiently mixed uniformly, oil to be filled is blotted completely by thermoplastic elastomer (TPE)
Afterwards, PP R370Y and 1250 mesh calcium carbonate are added, be added in whipping process Vistamax 6202, bis 25 vulcanizing agent and
CHEM CORD CM-3020 processing, is then added oleamide and 2Kg by UV-53l, the compound stabilizers of 1010,168 compositions,
Material after mixing is sent into shearing in double screw extruder by feeder, is kneaded, and each extruder temperature of double screw extruder is set
It is scheduled on 220 DEG C~230 DEG C, 20 hertz of feeding frequency, 600 revs/min of engine speed；It is maintained at 0.08MPA's through vacuum pressure
Double vacuum extractions, head extrusion, tie rod, air-cooled, pelletizing, hot blast are packed after recycling drying in 4 hours, and automobile bottom backplate is made and uses
Thermoplastic elastomehc sex camplex.
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| CN106084808B (en) * | 2016-06-22 | 2019-01-22 | 广东波斯科技股份有限公司 | A kind of scratch-resistant thermoplastic elastic material and preparation method thereof |
| CN112778676B (en) * | 2020-12-30 | 2023-02-21 | 金发科技股份有限公司 | TPV material formed by secondary coating with PA substrate and preparation method and application thereof |
| CN114736482A (en) * | 2022-03-09 | 2022-07-12 | 金发科技股份有限公司 | Thermoplastic elastomer composite material and preparation and application thereof |
| CN116144135A (en) * | 2022-12-28 | 2023-05-23 | 佩尔哲汽车内饰系统(太仓)有限公司 | Thermoplastic elastomer material and preparation method thereof |
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| WO2010077881A2 (en) * | 2008-12-15 | 2010-07-08 | Exxonmobil Chemical Patents Inc. | Thermoplastic polyolefin in-reactor blends and molded articles therefrom |
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| CN102276897A (en) * | 2011-06-29 | 2011-12-14 | 广州市聚赛龙工程塑料有限公司 | Polyethylene/nylon alloy composite material and preparation method thereof |
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