CN109401165A - The heat-resisting AES resin combination and its preparation that tiger fur line is reduced or eliminated - Google Patents
The heat-resisting AES resin combination and its preparation that tiger fur line is reduced or eliminated Download PDFInfo
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- CN109401165A CN109401165A CN201811116131.0A CN201811116131A CN109401165A CN 109401165 A CN109401165 A CN 109401165A CN 201811116131 A CN201811116131 A CN 201811116131A CN 109401165 A CN109401165 A CN 109401165A
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The heat-resisting AES resin combination being reduced or eliminated the invention discloses a kind of tiger fur line and its preparation；The composition includes following components and parts by weight content: acrylonitrile-ethylene propylene diene rubber -30-50 parts of phenylethene grafted copolymer, and 40-65 parts of acrylonitritrile-styrene resin, 5-20 parts of heat-resistant agent, 0.1-5.0 parts of processing aid；The acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer ethylene propylene diene rubber degree of cross linking is 40-70wt%.Method of the invention is simple and easy, thermoplasticity AES resin combination obtained, can not only avoid the tiger fur line defect on moulding surface completely, while having excellent mechanical performance, larger especially suitable for some sizes, the more complicated automobile exterior trimming parts product of structure；Such as, automobile grills, pillar panel, empennage decorative panel etc..
Description
Technical field
The present invention relates to technical field of polymer materials, specifically, being related to what a kind of tiger fur line was reduced or eliminated
Heat-resisting AES resin combination and preparation method thereof.
Background technique
Acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (AES) is a kind of weatherability engineering plastics, with third
Alkene nitrile-butadiene-styrene graft copolymer (ABS) structure is similar, and remains splendid machine of the ABS as engineering plastics
Tool physical property, also, compared with ASA resin, there is more preferably resistance to low temperature.Majority be applied to have certain weatherability and
The more demanding outdoor occasion of resistance to low temperature, such as automobile exterior trimming parts, co-extrusion section bar, outdoor fence etc..
But when AES resin is in molding massive article, such as when automobile grills, empennage decorative panel, product surface is easy
Existing tiger fur line defect, seriously affects products appearance.Tiger fur line defect is flow instabilities of resin during machine-shaping
Caused by, it is that a kind of surface in product shows alternate speckle shape defect, the decorative pattern of similar tiger, therefore tiger fur line of gaining the name,
Academia is referred to as " Tiger stripe " or " flow mark ".In particular for the Injection moulded part of the long process of thin-walled, such as radiate
Grid, pillar panel and empennage decorative panel etc., this tiger fur line defect can be easier to occur more serious, it is clear that this appearance lacks
The beauty for directly influencing product is fallen into, enables consumer be difficult to receive, this just greatly limits AES resin in automobile exterior field
Using；In addition, automobile exterior trimming parts such as heat dissipation grid etc. also has higher requirement to heat resisting temperature, therefore, invention designs a kind of tiger
The heat-resisting AES resin that dermatoglyph is reduced or eliminated has important scientific meaning and commercial value.
Currently, the effective ways for improving resin tiger fur line mainly use small-molecule substance, which can preferably improve
Tiger fur line defect, but would generally cause resin heat resistance can be with the reduction of mechanical strength；Patent CN102964686B is disclosed
A kind of PP composite material and preparation method thereof for eliminating tiger fur line, be made of the following components: polypropylene 39.2-80% disappears
Tiger fur line auxiliary agent 5-15%, filling mineral 10-40%, antioxidant 0.3-1%, lubricant 0.5-5%, compatilizer 1-10%；It should
Inventing PP composite material obtained has stronger tensile strength, notch strength, but does not provide the change of material thermal resistance
Change；The tiger fur line auxiliary agent that disappears used in the patent is small molecule polypropylene, and in fact, the use of this small-molecule substance would generally
Material thermal resistance can be impacted.Patent CN 105419143A discloses a kind of heat-resisting ASA resin combination for eliminating tiger fur line
Object and preparation method thereof eliminates tiger fur line defect by using the SAN resin of low molecular weight well.
In addition, the effective ways for improving resin tiger fur line also improve the dispersion effect or compatible in resin between each component
Effect；Patent CN101914243 disclose it is a kind of for be molded with good appearance automotive part polypropene composition and its
Preparation method is made of the following components: acrylic resin 50-78%, elastomer 2-20%, Ethylene-Propylene Block Copolymer 2-
10%, surplus is auxiliary agent, improved by addition Ethylene-Propylene Block Copolymer dispersion of the elastomer in polypropylene base and
Elastomer and polypropylene base phase boundary surface intensity, so that overcoming product generates tiger fur line open defect.Chinese patent
CN101885878A discloses a kind of polypropylene resin composite, including polypropylene, filler, toughener, heat stabilizer, lubricant
With appearance modifier, the appearance modifier is the carboxylic olefin-vinyl terpolymer of acrylate-or epoxy group fat
Race's polymer, since the compatibility of the components such as appearance modifier itself and polypropylene, toughener is preferable, and polar group with fill out
The compatibility of the components such as material, lubricant is preferable, so as to avoid the generation of the open defects such as tiger fur line or current mark.
However, being reduced or eliminated AES resin combination and preparation method thereof about a kind of tiger fur line, yet there are no
Report.
Summary of the invention
The purpose of the present invention is to deficiency in the prior art, provide a kind of tiger fur line be reduced or eliminated it is resistance to
Hot AES resin combination and preparation method thereof.
To achieve the above object, the technical solution adopted by the present invention is that:
The present invention relates to a kind of heat-resisting AES resin combinations, and the composition includes each component of following parts by weight:
The acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer ethylene propylene diene rubber degree of cross linking is 40-
70wt%.
Preferably, acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer weight average molecular weight is 50,000-
500,000, ethylene propylene diene rubber weight percent content is 20-80wt%.
Preferably, the weight average molecular weight of the acrylonitritrile-styrene resin is 100,000-500,000, acrylonitrile
Weight percent content is 15-40wt%.
Preferably, the heat-resistant agent is N-phenylmaleimide-styrene-maleic anhydride copolymer.Other are common
Heat-resistant agent has: the copolymer and α-methylstyrene-acrylonitrile copolymer of N-phenylmaleimide；However, N- phenyl Malaysia
Imido copolymer molecule chain rigidity, polarity are big, with acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer and benzene second
Alkene-acrylonitrile copolymer poor compatibility, processing fluidity is poor, is easy to produce flow instabilities, and tiger fur line is obvious；Alpha-Methyl benzene
The high-temperature thermal stability difference and heat-resisting low efficiency of ethylene-propylene lonitrile copolymer, are all unsuitable for eliminating the tiger fur line of heat-resisting AES.
Preferably, the processing aid includes the mixture of one or more of lubricant, antioxidant, release agent.
Preferably, the lubricant be pentaerythritol stearate or ethylene bis stearic acid amide, the antioxidant be by
Phenols or phosphite ester antioxidant are hindered, the release agent is silicone release agent.
The invention further relates to the preparation method for the heat-resisting AES resin combination that the tiger fur line is reduced or eliminated, institutes
Preparation method is stated to include the following steps:
S1, it after weighing raw material according to the ratio, is premixed in super mixer；
S2, by premix obtained in step S1 through metering device be sent into double screw extruder in, screw rod conveying, cut
It cuts and is kneaded down, it is material melting, compound, then through extrusion, tie rod, cooling, pelletizing step, obtain the heat-resisting AES resin combination
Object.
Preferably, the screw slenderness ratio of the double screw extruder be 36-44, extrusion temperature be 180-250 DEG C between,
Screw speed is 200-500 revs/min.
Compared with prior art, the invention has the following beneficial effects:
1, the present composition is copolymerized by using acrylonitrile-ethylene propylene diene rubber-styrene-grafted of the different degrees of cross linking
Object and it is heat-resisting it is high-efficient, processing fluidity is good, with the good heat-resistant agent collective effect of AES resin compatible, tiger is mitigated or eliminated
Dermatoglyph defect；And it is prepared in acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer degree of cross linking in 40-70%
The tiger fur line defect of AES resin combination is available to be mitigated or eliminated well.On the one hand, in system of the invention, ternary
The EP rubbers degree of cross linking is too low, and in injection moulding process, rubber is easy to be deformed AES resin, and this flow instabilities hold very much
Easily lead to the generation of tiger fur line；On the other hand, in system of the invention, the ethylene propylene diene rubber degree of cross linking is excessively high, in AES resin
Ethylene propylene diene rubber is really up to the mark, can cause mechanical degradation, influences the actual use of moulded products.
2, preparation method technical process of the invention is simple, at low cost and preparation process is easily controlled, and will not generate and appoint
What side reaction, is very suitable to industrialized production, the elimination tiger fur line defect that the AES resin combination of preparation can not only be good, simultaneously
It is good with mechanical performance and heat resistance, it is highly suitable to be applied for the fields such as automobile exterior, outdoor products.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after having read the content of the invention recorded, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Raw materials used in embodiment, parameter and the trade mark are as follows:
Acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer weight average molecular weight is 50,000-500,000, ternary
Ethylene-propylene rubber content is 20-80wt%, and the ethylene propylene diene rubber degree of cross linking is 20-90wt%.The weight of acrylonitritrile-styrene resin
Average molecular weight is 100,000-500,000, and the weight percent content of acrylonitrile is 15-40wt%.Heat-resistant agent is N- phenyl horse
Carry out acid imide-styrene-maleic anhydride copolymer.Processing aid includes that (pentaerythritol stearate or ethylene are double hard for lubricant
Resin acid amide), antioxidant (Hinered phenols or phosphite ester antioxidant), one or more of silicone release agent, dosage
It can be the arbitrary value in 0.5-3.0 parts by weight；Compare for convenience, the processing aid in following embodiment and comparative example is lubricant
The IG-1076 (the two mass ratio is 1:1) of EBS and antioxidant Ciba, dosage is 0.6 parts by weight.
Embodiment 1
30 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 40%), propylene
65 parts of nitrile-styrol copolymer, 5 parts of heat-resistant agent (N-phenylmaleimide-styrene-maleic anhydride copolymer), processing help
0.6 part of agent.Weigh raw material according to above-mentioned component part, prepare with the following method the tiger fur line be reduced or eliminated it is heat-resisting
AES resin combination:
(1) raw material prepared is sufficiently mixed 30min in super mixer；
(2) premix for preparing step 1 is sent into double screw extruder through metering device, conveying, shearing in screw rod
It is material melting, compound under mixing, then through extrusion, tie rod, cooling, pelletizing step, obtain what tiger fur line was reduced or eliminated
Heat-resisting AES resin combination.The screw slenderness ratio of the double screw extruder be 36-44, extrusion temperature be 180-250 DEG C it
Between, screw speed is 200-500 revs/min.
Embodiment 2
40 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 50%), propylene
50 parts of nitrile-styrol copolymer, 10 parts of heat-resistant agent (N-phenylmaleimide-styrene-maleic anhydride copolymer), processing help
0.6 part of agent.
Specific preparation method is same as Example 1.
Embodiment 3
50 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 60%), propylene
40 parts of nitrile-styrol copolymer, 10 parts of heat-resistant agent (N-phenylmaleimide-styrene-maleic anhydride copolymer), processing help
0.6 part of agent.
Specific preparation method is same as Example 1.
Embodiment 4
35 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 70%), propylene
45 parts of nitrile-styrol copolymer, 20 parts of heat-resistant agent (N-phenylmaleimide-styrene-maleic anhydride copolymer), processing help
0.6 part of agent.
Specific preparation method is same as Example 1.
Embodiment 5
35 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 50%), propylene
45 parts of nitrile-styrol copolymer, 20 parts of heat-resistant agent (N-phenylmaleimide-styrene-maleic anhydride copolymer), processing help
0.6 part of agent.
Specific preparation method is same as Example 1.
Embodiment 6
30 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 70%), propylene
65 parts of nitrile-styrol copolymer, 5 parts of heat-resistant agent (N-phenylmaleimide-styrene-maleic anhydride copolymer), processing help
0.6 part of agent.
Specific preparation method is same as Example 1.
Comparative example 1
30 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 90%), propylene
65 parts of nitrile-styrol copolymer, 5 parts of heat-resistant agent (N-phenylmaleimide-styrene-maleic anhydride copolymer), processing help
0.6 part of agent.
Specific preparation method is same as Example 1.
Comparative example 2
40 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 80%), propylene
50 parts of nitrile-styrol copolymer, 10 parts of heat-resistant agent (N-phenylmaleimide-styrene-maleic anhydride copolymer), processing help
0.6 part of agent.
Specific preparation method is same as Example 1.
Comparative example 3
50 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 30%), propylene
40 parts of nitrile-styrol copolymer, 10 parts of heat-resistant agent (N-phenylmaleimide-styrene-maleic anhydride copolymer), processing help
0.6 part of agent.
Specific preparation method is same as Example 1.
Comparative example 4
35 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 20%), propylene
45 parts of nitrile-styrol copolymer, 20 parts of heat-resistant agent (N-phenylmaleimide-styrene-maleic anhydride copolymer), processing help
0.6 part of agent.
Specific preparation method is same as Example 1.
Comparative example 5
It is 90 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 50%), heat-resisting
10 parts, 0.6 part of processing aid of agent (N-phenylmaleimide-styrene-maleic anhydride copolymer).
Specific preparation method is same as Example 1.
Comparative example 6
40 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 50%), propylene
50 parts of nitrile-styrol copolymer, 10 parts, 0.6 part of processing aid of heat-resistant agent (copolymer of N-phenylmaleimide).
Specific preparation method is same as Example 1.
Comparative example 7
40 parts of acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer (the ethylene propylene diene rubber degree of cross linking 50%), propylene
50 parts of nitrile-styrol copolymer, 10 parts, 0.6 part of processing aid of heat-resistant agent (α-methylstyrene-acrylonitrile copolymer).
Specific preparation method is same as Example 1.
Performance test
The AES resin combination that above-described embodiment 1-5 and comparative example 1-4 are prepared, according to identical injecting condition
Test bars are prepared, specific physical property, light aging resisting property and Anti-mildew capability detection project are as follows:
Tensile strength: being tested according to ISO527 standard, test speed 50mm/min,
Bending modulus: being tested according to ISO178 standard, test speed 1mm/min；
23 DEG C of Izod notched impact strengths: it is tested according to ISO180 standard, batten is with a thickness of 4mm；
Heat distortion temperature: being tested according to ISO75 standard, test condition 0.45MPa；
Melt flow rate (MFR): being tested according to ISO1183 standard, and test condition is 220 DEG C/10kg
Tiger fur line: it is visually commented in the black foil having a size of 350mm (length) * 100mm (width) * 3.2mm (thickness)
Valence shows that the tendency of tiger fur line, the black foil are extruded compound injection molding by using injector with the injection speed of 30mm/s
To be made.Tiger fur line on black foil surface is measured below the light source of the fluorescent lamp of 40W by naked eyes." elimination " is
Refer on entire sheet surface in this test condition there is no the thin slice of any tiger fur line." obvious " means in this test condition
There is tiger fur line on experiment sheet surface." clearly " mean to test in this test condition on sheet surface and occur very
Apparent tiger fur line." slight ", which means to test in this test condition, there is slight tiger fur line but unknown on sheet surface
It is aobvious.
The performance test of table 1 embodiment and comparative example
AES resin has been mitigated or eliminated in AES resin combination of the invention well it can be seen from the result of table 2
Tiger fur line problem.It can be seen that the ethylene propylene diene rubber degree of cross linking in 40-70% by embodiment 1-5 and comparative example 1-4.AES
The tiger fur line of resin has obtained good mitigation or elimination；By embodiment 2, embodiment 5 with comparative example 4 as can be seen that working as
When the ethylene propylene diene rubber degree of cross linking is 40%, even if heat-resisting agent content is also very light for the tiger fur line defect of 20%, AES resin surface
Micro-, tiger fur line at this moment is main related with the melt index reduction after the heat-resisting agent content increase；And when heat-resisting agent content is
When 20%, compared with the degree of cross linking is 40% AES resin, the tiger fur line for the AES resin that the degree of cross linking is 20% wants serious more, says
The degree of cross linking of bright ethylene propylene diene rubber influences the tiger fur line severity of AES resin very big.By comparing embodiment 2 and comparison
Example 5, it can be seen that be added without acrylonitritrile-styrene resin, melt flow rate (MFR), tensile strength and the bending modulus of resin
All very poor, tiger fur line phenomenon is very serious, that is, inside such resin system, even with the degree of cross linking of the invention limited
It can not play a role.By comparing embodiment 2, comparative example 6-7, it can be seen that the copolymer of N-phenylmaleimide and
α-methylstyrene-acrylonitrile copolymer is as heat-resistant agent, and the tiger fur line of AES resin is all very serious, this is primarily due to: N- phenyl
Copolymer molecule chain rigidity, the polarity of maleimide are big, with acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer and
The poor compatibility of styrene-acrylonitrile copolymer, processing fluidity is poor, is easy to produce flow instabilities, and tiger fur line is obvious；α-first
The high-temperature thermal stability difference and heat-resisting low efficiency of base styrene-acrylonitrile copolymer, are all unsuitable for eliminating the tiger fur line of heat-resisting AES.
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention.More than it should be pointed out that
Embodiment is merely to illustrate the present invention, and the protection scope being not intended to restrict the invention.For the common skill of the art
For art personnel, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as this hair
Bright protection scope.
Claims (8)
1. a kind of heat-resisting AES resin combination, which is characterized in that the composition includes each component of following parts by weight:
The acrylonitrile-ethylene propylene diene rubber-phenylethene grafted copolymer ethylene propylene diene rubber degree of cross linking is 40-70wt%.
2. heat-resisting AES resin combination according to claim 1, which is characterized in that the acrylonitrile-ethylene-propylene-diene monomer
Glue-phenylethene grafted copolymer weight average molecular weight is 50,000-500,000, and ethylene propylene diene rubber weight percent content is
20-80wt%.
3. heat-resisting AES resin combination according to claim 1, which is characterized in that the styrene-acrylonitrile copolymer
Weight average molecular weight be 100,000-500,000, the weight percent content of acrylonitrile is 15-40wt%.
4. heat-resisting AES resin combination according to claim 1, which is characterized in that the heat-resistant agent is N- phenyl Malaysia
Acid imide-styrene-maleic anhydride copolymer.
5. heat-resisting AES resin combination according to claim 1, which is characterized in that the processing aid include lubricant,
The mixture of one or more of antioxidant, release agent.
6. heat-resisting AES resin combination according to claim 5, which is characterized in that the lubricant is that pentaerythrite is hard
Resin acid ester or ethylene bis stearic acid amide；The antioxidant is Hinered phenols or phosphite ester antioxidant；The release agent is
Silicone release agent.
7. a kind of preparation method of heat-resisting AES resin combination according to claim 1, which is characterized in that the preparation
Method includes the following steps:
S1, it after weighing raw material according to the ratio, is premixed in super mixer；
S2, by premix obtained in step S1 through metering device be sent into double screw extruder in, screw rod conveying, shearing and
It is material melting, compound under mixing, then through extrusion, tie rod, cooling, pelletizing step, obtain the heat-resisting AES resin combination.
8. the preparation method of heat-resisting AES resin combination according to claim 7, which is characterized in that the twin-screw
The screw slenderness ratio of extruder is 36-44, and extrusion temperature is between 180-250 DEG C, and screw speed is 200-500 revs/min.
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| CN201811116131.0A CN109401165B (en) | 2018-09-25 | 2018-09-25 | Heat-resistant AES resin composition with tiger skin lines reduced or eliminated and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811116131.0A CN109401165B (en) | 2018-09-25 | 2018-09-25 | Heat-resistant AES resin composition with tiger skin lines reduced or eliminated and preparation thereof |
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| CN109401165B CN109401165B (en) | 2021-05-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759852A (en) * | 2020-12-29 | 2021-05-07 | 金发科技股份有限公司 | Acrylonitrile-styrene copolymer material and preparation method thereof |
| CN113512252A (en) * | 2021-07-06 | 2021-10-19 | 上海金发科技发展有限公司 | Polypropylene composition and preparation method thereof |
| CN116082784A (en) * | 2023-04-10 | 2023-05-09 | 佛山市塑聚新材料科技有限公司 | Flame-retardant composite material and preparation method and application thereof |
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| CN105419143A (en) * | 2015-12-24 | 2016-03-23 | 上海锦湖日丽塑料有限公司 | Heat-resistant ASA resin composition with tiger wrinkle defect eliminated and preparation method thereof |
| CN107245214A (en) * | 2017-06-29 | 2017-10-13 | 上海锦湖日丽塑料有限公司 | Efficient antifungi AES resin combinations and preparation method thereof |
| EP3299415A1 (en) * | 2015-05-19 | 2018-03-28 | Denka Company Limited | Heat-resistant resin composition and method for producing same |
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| CN102391607A (en) * | 2011-08-31 | 2012-03-28 | 上海锦湖日丽塑料有限公司 | Polylactic acid/styrene resin composition and preparation method thereof |
| EP3299415A1 (en) * | 2015-05-19 | 2018-03-28 | Denka Company Limited | Heat-resistant resin composition and method for producing same |
| CN105419143A (en) * | 2015-12-24 | 2016-03-23 | 上海锦湖日丽塑料有限公司 | Heat-resistant ASA resin composition with tiger wrinkle defect eliminated and preparation method thereof |
| CN107245214A (en) * | 2017-06-29 | 2017-10-13 | 上海锦湖日丽塑料有限公司 | Efficient antifungi AES resin combinations and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759852A (en) * | 2020-12-29 | 2021-05-07 | 金发科技股份有限公司 | Acrylonitrile-styrene copolymer material and preparation method thereof |
| CN113512252A (en) * | 2021-07-06 | 2021-10-19 | 上海金发科技发展有限公司 | Polypropylene composition and preparation method thereof |
| CN116082784A (en) * | 2023-04-10 | 2023-05-09 | 佛山市塑聚新材料科技有限公司 | Flame-retardant composite material and preparation method and application thereof |
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| Publication number | Publication date |
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| CN109401165B (en) | 2021-05-04 |
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