CN109749327A - A kind of lightweight, wear-resisting, automobile low noise ASA composite material and preparation method thereof - Google Patents
A kind of lightweight, wear-resisting, automobile low noise ASA composite material and preparation method thereof Download PDFInfo
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- CN109749327A CN109749327A CN201811623432.2A CN201811623432A CN109749327A CN 109749327 A CN109749327 A CN 109749327A CN 201811623432 A CN201811623432 A CN 201811623432A CN 109749327 A CN109749327 A CN 109749327A
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Abstract
The invention discloses a kind of lightweights, wear-resisting, automobile low noise ASA composite material and preparation method thereof, and the raw material based on following weight percent is formulated: acrylonitritrile-styrene resin 35%~80%；Acrylicstyrene-acrylate graft copolymers 10%~60%；Polyamide 10%~30%；Compatilizer 2%~8%；Hollow glass micropearl 1%~25%: coupling agent: 0.3%~5%；Antioxidant 0.2%~1%；Light stabilizer 0.2%~2%.The present invention is by adding polyamide in acrylonitritrile-styrene resin, acrylicstyrene-acrylate graft copolymers resin, making the ASA composite material of preparation has the effect of wear-resisting and self-lubricating, hollow glass micropearl is added in formula simultaneously, the intensity of ASA can not only be enhanced, also reduce the density of enhancing ASA, achieve the purpose that lightweight and loss of weight, in the special hollow structure synergistic effect with self-lubricating function and hollow glass micropearl, make the ASA composite material of preparation that there is certain anti-acoustic capability.
Description
Technical field
The present invention relates to a kind of ASA resin composite material, specially a kind of lightweight, wear-resisting, automobile low noise ASA is compound
Material and preparation method thereof belongs to polymer modification and processing technique field.
Background technique
ASA resin also becomes AAS resin, it be by acrylonitrile (A), what styrene (S) and acrylate (A) copolymerization obtained
A kind of ternary graft copolymer, AS is one kind by acrylonitrile (A) and a kind of styrene copolymerized obtained bipolymer, due to this
Unlike yet forming a new double bond after polymerizing butadiene in ABS in two kinds of polymer, it is oxidized easily, therefore they are opposite
There is higher weatherability in ABS, by modification appropriate, be able to take it is long-term be exposed to the sun, mechanical property does not occur substantially
It reduces, so auto vendor is by ASA material directly as exposed inner and outer decorative parts.However ASA is easy in being used as automobile interior decoration
Abnormal sound is generated, which results in the complaint of consumer, lot of domestic and foreign mainstream main engine plants all start to produce low noise material dense
Thick interest, therefore develop the low noise material inexorable trend that necessarily automobile-used modification is expected in the future.Polyamide is a kind of engineering
Plastics, it not only has excellent mechanical performance, and corrosion resistance also has good wearability, self-lubricating property.
Lightweight is the topic and research direction of automotive material invariability because the lightweight of automobile be automobile especially
New-energy automobile can increase course continuation mileage, shortening braking distance and promote the means of starting speed, be even more the effective of energy-saving and emission-reduction
Mode can contribute meagre strength also for " blue sky defended war ", therefore as to mould Dai Gang, low-density, fretting map etc. technology always
It is the core technology that material quotient keeps material advance.Relative to glass and glass microballoon, hollow glass is added in modified plastics
Glass microballoon not only has the function of enhancing, also has the effect of loss of weight, while its hollow special construction makes material have drop
The effect made an uproar.The present invention is by acrylonitritrile-styrene resin, acrylicstyrene-acrylate graft copolymers tree
Polyamide and hollow glass micropearl are added in rouge, in polyamide and hollow glass with self-lubricating, wear-resisting functions
Under the synergistic effect of microballon, a kind of novel low-noise wearable ASA composite material is prepared, while realizing light-weighted effect
Fruit.
Summary of the invention
The purpose of the present invention is to provide lightweights, wear-resisting, automobile low noise ASA composite material, to solve the prior art
The above problem.
The purpose of the present invention is mainly achieved through the following technical solutions:
A kind of lightweight, wear-resisting, automobile low noise ASA composite material, the raw material based on following weight percent
It is formulated:
The melt flow rate (MFR) of the acrylonitritrile-styrene resin is in 10~60g/10min, test condition are as follows: 220
℃×10kg。
Acrylicstyrene-acrylate graft copolymers acrylic rubber content by weight percentage
40%~80%.
The polyamide is PA6, and relative viscosity index is 2.0~4.0.
The compatilizer is styrene-maleic anhydride copolymer (SMA).
The partial size of the hollow glass micropearl is 5~40 microns；
The coupling agent is amino silicane coupling agent；
The antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 1010 and antioxidant 619F compound, antioxygen
One of agent 1076 and antioxidant 619F compound.
The light stabilizer is one or more of hindered amine light stabilizer.
A kind of lightweight, wear-resisting, automobile low noise ASA composite material, it is characterised in that: the steps include:
(1) acrylonitritrile-styrene resin, acrylicstyrene-acrylate graft copolymers and polyamide are existed
8 hours dry or more at 100 DEG C~120 DEG C, compatilizer is 2~4 hours dry at 70 DEG C -100 DEG C；
(2) by the acrylic ester grafted copolymerization of acrylonitritrile-styrene resin, acrylicstyrene-after drying process
Object, polyamide, compatilizer, 1/3 part of hollow glass micropearl, coupling agent, antioxidant, light stabilizer are put into high speed after weighing in proportion
In mixing machine, stirred 5~10 minutes under room temperature；
(3) it is put into after mixing well each component in the main spout of double screw extruder；Again by other 2/3 part of sky
Heart glass microballoon is divided into two equal parts, is added in main barrel from two side spouts respectively, screw diameter 35mm, draw ratio L/D
=36, machine barrel Discrete control temperature, 190~220 DEG C of an area, two 220~240 DEG C of areas, three 230~245 DEG C of areas, four areas 220~
240℃.Engine speed is 350 revs/min, this is obtained after the processes such as melting extrusion, sink cooling, drying process, pelletizing
A kind of lightweight, wear-resisting, the automobile low noise ASA composite material of invention.
In step (2), the double screw extruder is bilateral feed screw extruder, and one of side spout is located at
At 1/5~3/5 position of discharge port, another side spout is located at the position apart from discharge port 3/5~4/5.
Compared with the prior art, the advantages of the present invention are as follows the following aspects for the technology:
1, the present invention is by acrylonitritrile-styrene resin, acrylicstyrene-acrylate graft copolymers tree
Polyamide is added in rouge, and the ASA composite material of preparation is made to have the effect of wear-resisting and self-lubricating；
2, inventive formulation is added to hollow glass micropearl, can not only enhance the intensity of ASA, also reduces enhancing ASA's
Density achievees the purpose that lightweight and loss of weight；
3, make in the present invention in the special hollow structure of the polyamide of self-lubricating function and hollow glass micropearl synergistic effect
The ASA composite material that must be prepared has certain anti-acoustic capability；
4, the present invention selects the mode of bilateral feeding to add hollow glass micropearl, reduces screw rod to hollow glass micropearl molten
Melt coextrusion to destroy in the process, while the dispersibility of glass microballoon in the substrate can also be improved, so that the material property of preparation
More preferably, more stable；
5, lightweight proposed by the present invention, wear-resisting, automobile low noise ASA composite material preparation, production cost is low, easily
In mass production.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
In embodiment and comparative example composite-material formula, two kinds of acrylonitritrile-styrene resin be respectively DN89 and
DN59 is the production of Ben Ling company, and wherein the melting means of DN89 is 10~20g/10min, and DN59 melting means is 10~20g/10min (220
℃×10min).Acrylonitrile-styrene-acrylic ester graft copolymer is the 960A product of U.S. GE company production, wherein glue
Content is 60%, and polyamide is that the M2000 that Mei Da Co., Ltd provides, relative viscosity 2.0 are newly understood in Guangzhou.Compatilizer is city
The styrene-maleic anhydride copolymer SMA-218HF of the Nanjing Yin Xin Chemical Co., Ltd. sold.Hollow glass micropearl is that 3M is commercially available
Hollow glass micropearl, the trade name trade mark be S60, D50 partial size be 30 microns.Silane coupling agent is that the sincere chemical industry of commercially available Nanjing Olympic has
The amino silicane coupling agent KH792 of limit company, chemical name are N-2- aminoethyl -3- aminopropyl trimethoxysilane, are a kind of
Bifunctional silane,.Antioxidant is the 1010 of CIBA company production, chemical name are as follows: four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester.Light stabilizer is the UV-770 of CIBA company production, and chemical name is bis- (2,2,6,6- tetramethyls
Base -4- piperidyl) sebacate is a kind of hindered amine light stabilizer.
By acrylonitritrile-styrene resin, acrylicstyrene-acrylate graft copolymers and polyamide at 100 DEG C
8 hours dry or more at~120 DEG C, compatilizer is 2~4 hours dry at 70 DEG C -100 DEG C；By the acrylonitrile-after drying process
Styrol copolymer, acrylicstyrene-acrylate graft copolymers, polyamide, compatilizer, 1/3 part of hollow glass are micro-
Pearl, coupling agent, antioxidant, light stabilizer are put into high-speed mixer after weighing in proportion, are stirred 5~10 minutes under room temperature；It will
Each component is put into after mixing well in the main spout of double screw extruder；Again by other 2/3 part of hollow glass micropearl point
It for two equal parts, is added in main barrel from two side spouts respectively, screw diameter 35mm, draw ratio L/D=36, machine barrel segmentation
Control temperature, 190~220 DEG C of an area, two 220~240 DEG C of areas, three 230~245 DEG C of areas, four 220~240 DEG C of areas.Engine speed
Be 350 revs/min, obtained after the processes such as melting extrusion, sink cooling, drying process, pelletizing a kind of lightweight of the invention,
Wear-resisting, automobile low noise ASA composite material
Performance evaluation and implementation standard:
The plastic pellet material manufactured according to the above method is placed in drying 4~6 hours in 100 DEG C of air dry oven, so
Dried pellet is subjected to injection moulding sample preparation on injection (mo(u)lding) machine again afterwards.Density is carried out according to ISO1183, specimen size
For 10 × 10 × 4mm, tensile property is carried out according to ISO 527, and specimen size is 170 × 10 × 4mm dumbbell shape batten, stretches speed
Degree is 50mm/min；Bending property test is carried out according to ISO178, and specimen size is 80 × 10 × 4mm, rate of bending 2mm/
Min, span 64mm；Simply supported beam notch impact strength is carried out by ISO 179, and specimen size is 80 × 10 × 4mm, notch depth
It is the 1/3 of specimen width.
Noise dangerous values RPN evaluation, is tested according to German automobiles Industry Association standard, raw using Ziegler
The SSP-02 stick slip vibration code test machine of production, load 10N, speed 10mm/s, this method are that two components of simulation can
The risk of noise can be generated, RPN value is smaller, and the risk for generating noise is smaller, is divided into 10 grades, 0~3 grade of expression noise probability of happening
Low, 4-5 grades of expression noise occurrence risks are medium, and it is high to be greater than 6 grades of expression noise occurrence risks.
The comprehensive performance of material is by testing resulting density, notch impact strength, tensile strength, bending modulus, RPN
Value.Example formulations, comparative formulation and properties test result see below Lie Gebiao:
1 Examples 1 to 5 of table and comparative example 1,2 are formulated (wt%).
2 Examples 1 to 5 of table and comparative example 1,2 test results
From the comparison of Examples 1 to 5 and comparative example 1,2 as can be seen that ASA composite material prepared by the present invention have compared with
Low density and preferable mechanical performance is this light under polyamide and the hollow glass micropearl synergistic effect of self-lubricating function
Matter ASA composite material also has effect wear-resisting and the functionality of noise reduction, the increase of polyamide and hollow glass micropearl content
Facilitate the noise reduction effect of material.It has very big utility value in terms of automobile interior exterior adorns lightweight and noise reduction, this kind of light
Matter, wear-resisting low noise ASA composite material can be used for automobile stand column, grid, panel, and anti-scraping article etc. automobile interior exterior adorns plastics
Part.
The scope of the present invention is not limited by the specific embodiments described, and the embodiment is only intended to as illustrating the present invention
The single example of various aspects further includes function equivalent method and component in the scope of the invention.In fact, in addition to described herein
Content outside, those skilled in the art can easily grasp referring to description above to a variety of improvement of the invention.It is described to change
Into also falling within the scope of the appended claims.
Claims (11)
1. a kind of lightweight, wear-resisting, automobile low noise ASA composite material, it is characterised in that: the original based on following weight percent
Material is formulated:
2. a kind of lightweight, wear-resisting, automobile low noise ASA composite material according to claim 1, it is characterised in that: described
Acrylonitritrile-styrene resin melt flow rate (MFR) in 10~60g/10min, test condition are as follows: 220 DEG C × 10kg.
3. a kind of lightweight, wear-resisting, automobile low noise ASA composite material according to claim 1, it is characterised in that: described
Acrylicstyrene-acrylate graft copolymers by weight percentage acrylic rubber content 40%~80%.
4. a kind of lightweight, wear-resisting, automobile low noise ASA composite material according to claim 1, it is characterised in that: described
Polyamide be PA6, relative viscosity index is 2.0~4.0.
5. a kind of lightweight, wear-resisting, automobile low noise ASA composite material according to claim 1, it is characterised in that: described
Compatilizer be styrene-maleic anhydride copolymer (SMA).
6. a kind of lightweight, wear-resisting, automobile low noise ASA composite material according to claim 1, it is characterised in that: described
Hollow glass micropearl partial size be 5~40 microns.
7. a kind of lightweight, wear-resisting, automobile low noise ASA composite material according to claim 1, it is characterised in that: described
Coupling agent be amino silicane coupling agent.
8. a kind of lightweight, wear-resisting, automobile low noise ASA composite material according to claim 1, it is characterised in that: described
Antioxidant be antioxidant 1010, antioxidant 1076, antioxidant 1010 and antioxidant 619F compound, antioxidant 1076 and antioxygen
One of agent 619F compound.
9. a kind of lightweight, wear-resisting, automobile low noise ASA composite material according to claim 1, it is characterised in that: described
Light stabilizer be one or more of hindered amine light stabilizer.
10. a kind of any lightweight, wear-resisting, automobile low noise ASA composite material preparation method according to claim 1~9,
It is characterized by: the steps include:
(1) by acrylonitritrile-styrene resin, acrylicstyrene-acrylate graft copolymers and polyamide at 100 DEG C
8 hours dry or more at~120 DEG C, compatilizer is 2~4 hours dry at 70 DEG C -100 DEG C；
(2) by the acrylonitritrile-styrene resin, acrylicstyrene-acrylate graft copolymers, poly- after drying process
Amide, compatilizer, 1/3 part of hollow glass micropearl, coupling agent, antioxidant, light stabilizer are put into mixed at high speed after weighing in proportion
In machine, stirred 5~10 minutes under room temperature；
(3) it is put into after mixing well each component in the main spout of double screw extruder；Again by other 2/3 part of hollow glass
Glass microballon is divided into two equal parts, is added in main barrel from two side spouts respectively, screw diameter 35mm, draw ratio L/D=36,
Machine barrel Discrete control temperature, 190~220 DEG C of an area, two 220~240 DEG C of areas, three 230~245 DEG C of areas, four 220~240 DEG C of areas.
Engine speed is 350 revs/min, is obtained after the processes such as melting extrusion, sink cooling, drying process, pelletizing of the invention
A kind of lightweight, wear-resisting, automobile low noise ASA composite material.
11. lightweight, wear-resisting, automobile low noise ASA composite material preparation method, feature exist according to claim 10
In: in step (2), the double screw extruder is bilateral feed screw extruder, and one of side spout is located at distance
At 1/5~3/5 position of discharge port, another side spout is located at the position apart from discharge port 3/5~4/5.
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Cited By (5)
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| CN111073154A (en) * | 2019-12-13 | 2020-04-28 | 青岛海尔新材料研发有限公司 | Resin composite material with abnormal sound prevention function and preparation method thereof |
| CN111234375A (en) * | 2020-01-13 | 2020-06-05 | 南方科技大学 | Sound absorption and noise reduction material, preparation method and application thereof |
| CN112175384A (en) * | 2020-09-30 | 2021-01-05 | 重庆长安汽车股份有限公司 | Matte low-density spray-free material for automotive interior and preparation method thereof |
| CN112480585A (en) * | 2020-12-09 | 2021-03-12 | 浙江普利特新材料有限公司 | Lightweight wear-resistant spraying-free noise-reducing ASA composite material for automobile and preparation method thereof |
| CN112812485A (en) * | 2020-12-28 | 2021-05-18 | 金发科技股份有限公司 | SMA composite material and preparation method and application thereof |
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Application publication date: 20190514 |