CN109651743A - ASA/PMMA resin combination and preparation method thereof - Google Patents
ASA/PMMA resin combination and preparation method thereof Download PDFInfo
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- CN109651743A CN109651743A CN201811540047.1A CN201811540047A CN109651743A CN 109651743 A CN109651743 A CN 109651743A CN 201811540047 A CN201811540047 A CN 201811540047A CN 109651743 A CN109651743 A CN 109651743A
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of ASA/PMMA resin combinations and preparation method thereof.The ASA/PMMA resin combination includes the raw material of following parts by weight: 20-50 parts of ASA resin；20-50 parts of PMMA resin；15-35 parts of organosilicon acrylic ester copolymerization object；0.4-1 parts of auxiliary agent；The organosilicon acrylic ester copolymerization object is core-shell structure, and core is organosilicon/acrylic acid compounded rubber, and shell is acrylonitritrile-styrene resin；The weight ratio that the organosilicon accounts for the organosilicon acrylic ester copolymerization object is 20%-40%.Invention resin composition scratch resistance, chemical resistance are good, glossiness is good, and higher toughness is shown under low-temperature condition.
Description
Technical field
The present invention relates to engineering material fields, more particularly to ASA/PMMA resin combination and preparation method thereof.
Background technique
The ternary graft copolymer that ASA engineering material is made of esters of acrylic acid rubber, acrylonitrile and styrene, this three
Kind substance has reapective features.Compared with ABS material, ASA is free of double bond, thus ASA material has good weatherability, in addition,
There are also good mechanical strengths, good heat resistance by ASA.PMMA material have excellent comprehensive performance, have excellent light transmittance,
Wear-resisting property and good glossiness.Both ASA/PMMA alloy material combination ASA and PMMA feature has good impact
Property, weatherability, dimensional stability, excellent surface gloss the features such as, ASA/PMMA material is widely used outside mechanical, automobile
The fields such as decorations, building decoration.
In recent years, automobile exterior materials demand is increasing, and requirement of the people to material is higher and higher, ASA/PMMA alloy
Automobile exterior, such as automobile grills, rearview mirror, vehicle window panel is widely applied in material.ASA/PMMA material chemicals-resistant is poor, meets
It is easy to crack to chemicals such as gasoline, diesel oil, ethyl acetate.There is general toughness, but automobile exterior under ASA/PMMA material room temperature
Rearview mirror, vehicle window panel use at low temperature, and toughness of material drastically reduces, and influence product service condition.In view of the above-mentioned problems, needing
People are wanted to pay close attention to and solve jointly.
Chinese patent CN 106832723A discloses a kind of high heat resistance high durable ASA/PMMA composite material and its preparation side
Method.The composite material includes following weight percentage components: AAS acrylonitrile acryloid styrene 30-60%, being gathered
Polymethyl methacrylate resin 30-60%, heat-proof modifier 1-10%, compatilizer 1-5%, mineral black 1-3%, light stabilizer
0.1-1.5%, ultraviolet absorbing agent 0.1-1.5%, antioxidant 0.1-1.5%, lubricant 0.1-2%.The ASA/PMMA of invention
Composite material has excellent heat-resisting and weather resistance, and high surface gloss, high comprehensive performance, Vicat softening point is 100
DEG C or more.
Chinese patent CN 108384168A discloses a kind of high-gloss high-impact automobile ASA/PMMA material and its preparation
Method, parts by weight of raw materials: ASA100 parts, PMMA40-60 parts, 2-8 parts of maleic anhydride, 2,4- dichlorobenzoperoxide
3-8 parts, MBS10-20 parts of impact modifying agent, 5-12 parts of cumyl peroxide, 0.5-2 parts of antioxidant and Halogen bloom grease
0.5-3 parts of mineral black；Resulting material has high glaze, high-impact, higher weatherability.
Chinese patent CN 103665814A discloses a kind of PMMA/ASA and meets material and preparation method thereof, by quality hundred
Divide content ingredient: PMMA 49-82%；ASA 10-25%；Toughener 5-20%；Antioxidant 0.2-0.4%；Processing aid 0.5-
1%.The composite material overall performance rigidity-toughness balanced, intensity height, scratch resistance, flexible, appearance are beautiful.
Chinese patent CN 105504569A discloses a kind of high durable, high glaze, wear-resisting ASA/PMMA blend and its system
Preparation Method includes methyl methacrylate 25-60 parts；25-60 parts of styrene-acrylonitrile copolymer；Impact modifier 10-30
Part；0.4-1 parts of antioxidant；0.3-1 parts of light absorber；0.3-1 parts of light stabilizer, resulting blend has excellent weather-proof
Property, high glaze and wear-resisting property.
Chinese patent CN 105419205A disclose a kind of high glaze exempt from spraying PMMA/ASA alloy resin composition and
Preparation method, including 35-60 parts of PMMA resins, 30-60 parts of ASA resins, 5-20 parts of toughener, 1-5 parts of compatilizers, black masterbatch
0.5-2 parts；0.6-1.5 parts of processing aid, obtained composition mechanical performance is excellent, glossiness is good.
But these proprietary materials do not have chemical resistance first, easy to crack when encountering the chemicals such as gasoline；Secondly
Also do not have low-temperature flexibility, toughness drastically reduces at low ambient temperatures, and material application range can be restricted significantly.
Summary of the invention
Based on this, the present invention provides a kind of scratch-resistant, chemicals-resistant, the ASA/PMMA tree that glossiness is good and low-temperature flexibility is high
Oil/fat composition.
The specific technical proposal is:
A kind of ASA/PMMA resin combination, includes the raw material of following parts by weight:
The organosilicon acrylic ester copolymerization object is core-shell structure, and core is organosilicon/acrylic acid compounded rubber, shell third
Alkene nitrile-styrol copolymer；
The weight ratio that the organosilicon accounts for the organosilicon acrylic ester copolymerization object is 20%-40%.
The ASA/PMMA resin combination includes the raw material of following parts by weight in one of the embodiments:
The organosilicon accounts for the weight ratio of the organosilicon acrylic ester copolymerization object and is in one of the embodiments,
20%-30%.
In one of the embodiments, in the ASA resin, the content of acrylonitrile is 25%-35%.
The ASA resin melt flow rate (MFR) is 20-48g/ at 220 DEG C/10kg in one of the embodiments,
10min。
The hardness number of the PMMA is 3H-5H in one of the embodiments,.
The PMMA melt flow rate (MFR) is 40-65g/10min at 220 DEG C/10kg in one of the embodiments,.
The auxiliary agent includes in antioxidant, stabilizer, lubricant, dispersing agent and carbon black in one of the embodiments,
One or more.
The present invention also provides the preparation methods of above-mentioned ASA/PMMA resin combination.
Specific technical solution the following steps are included:
The ASA resin, PMMA resin, organosilicon acrylic ester copolymerization object and auxiliary agent are mixed, extrusion molding,
To obtain the final product.
The revolving speed of the mixing is 250 revs/min -350 revs/min in one of the embodiments, the time 10
- 20 minutes minutes；
The technological parameter of the extrusion molding includes: that the draw ratio of double screw extruder is in one of the embodiments,
30-40:1 is arranged from the first warm area to the operating temperature of the tenth warm area are as follows: 170 DEG C -200 DEG C of an area, two 190 DEG C -210 DEG C of areas,
Three 200 DEG C -230 DEG C of areas, four 210 DEG C -230 DEG C of areas, five 220 DEG C -235 DEG C of areas, six 220 DEG C -235 DEG C of areas, seven 220 DEG C -235 of areas
DEG C, eight 220 DEG C -235 DEG C of areas, nine 210 DEG C -230 DEG C of areas, ten 210 DEG C -230 DEG C of areas, 210 DEG C -220 DEG C of head area；Double spiral shells
Bar extruder revolving speed is 200 revs/min -500 revs/min.
Compared with prior art, the invention has the following advantages:
By organosilicon acrylic ester copolymerization object, (core-shell structure, core are that organosilicon/acrylic acid is compound to above-mentioned resin combination
Rubber, shell are acrylonitritrile-styrene resin) it is added to the resin system of ASA/PMMA, shell provides the compatibility with substrate, core
Toughening effect is provided.Wherein, good as the silicone molecules chain flexibility of core, silicon-oxygen (Si-O) key is than carbon-to-carbon (C-C) key
Bond energy is high, and intermolecular force is weaker than hydrocarbon, enables the low advantage of composition surface tension and surface of preparation, cooperation
The higher PMMA of hardness, improves its scraping and wiping resistance performance to a certain extent.Organosilicon compounded rubber relative to common toughener,
Since main chain is silicon oxygen chain, bond length is long, and bond angle and bond energy are high, and the silicon oxygen chain of composition is very soft, and viscous activation energy is very low, leads
Cause its glass transition temperature low, so strand relaxation will not sharply slow down at low ambient temperatures, hardness, modulus and
Intramolecular friction will not dramatically increase, and still be able to maintain certain toughening effect.The organosilicon of core-shell structure is generally configured with centainly
Geometric shape, when excessively be distributed in material surface, light irradiation when, will form diffusing reflection, will affect material in a certain range
The glossiness of material.Silicon-acrylic acid has excellent chemical resistance simultaneously, can be obviously improved composition chemical resistance；When
When the content of organosilicon is 20%-40% in organosilicon acrylic ester copolymerization object, it can assign material more balanced comprehensive
Energy.Invention resin composition passes through ASA resin, the organosilicon acrylic ester copolymerization of PMMA resin and particular silicone content
Object cooperates, and thermal stability is high, not only can be with high temperature resistant, can also be low temperature resistant, and shows under low-temperature condition higher
Toughness；Wherein, the content of acrylonitrile may be up to 25%-35% in ASA resin, be also beneficial to improve the resistance to molten of the present composition
Agent, chemical-resistant.Meanwhile the present composition has preferable glossiness, is conducive to do the black product of bloom, is suitable for automobile
The components such as casing of rearview mirror, grid, vehicle window panel in exterior trim.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.The present invention can be with many not
With form realize, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes to this
Disclosure of the invention content understanding is more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
Modified epoxy resin curing agent of the invention and preparation method thereof is made below in conjunction with specific embodiment further detailed
Thin explanation.
Raw material in following specific embodiments derives from commercially available.
Wherein, ASA resin is the ASA 350 of odd beauty；PMMA resin is Mitsubishi PMMA IRH70；Organosilicon/propylene
Acid ester copolymer is Mitsubishi SX-006, and the content of organosilicon is about 30%.
Carbon black is U.S.'s Cabot C205；Antioxidant is selected from the mixing of antioxidant 1076 and irgasfos 168；Lubricant is profit
Lubrication prescription EBS；Wherein, antioxidant 1076 selects Jin Haiyabao AT-76；Irgasfos 168 selects Jin Haiyabao D-168；Lubricate EBS
Select Japanese Kao EB-FF.
Embodiment 1
The present embodiment provides a kind of ASA/PMMA resin combination, preparation method is as follows:
Step 1: each raw material is weighed by following parts by weight:
Step 2: above-mentioned raw materials are added in high-speed mixer, are mixed, in the case where revolving speed is 300 revs/min, stirring 12
Minute, be subsequently poured into double screw extruder, after extrusion pelletizing to get.
The draw ratio of above-mentioned double screw extruder is 35:1, and temperature-adjustable has ten warm areas, from the first warm area to the tenth
The operating temperature of warm area is arranged are as follows: 170 DEG C -200 DEG C of an area, two 190 DEG C -210 DEG C of areas, three 200 DEG C -230 DEG C of areas, four areas 210
DEG C -230 DEG C, five 220 DEG C -235 DEG C of areas, six 220 DEG C -235 DEG C of areas, seven 220 DEG C -235 DEG C of areas, eight 220 DEG C -235 DEG C of areas, 9th area
210 DEG C -230 DEG C, ten 210 DEG C -230 DEG C of areas, 210 DEG C -220 DEG C of head area.Double screw extruder revolving speed is set as 200 revs/min
- 500 revs/min of clock.
Embodiment 2-5
It is made embodiment 2-5's using preparation method same as Example 1 according to raw material shown in table 1 and dosage
ASA/PMMA composition, and embodiment 1-5 is tested for the property, the specific method is as follows:
Tensile strength: it is tested according to ISO 527/2 (50mm/min)；
Bending strength and bending modulus: it is tested according to ISO 178 (2mm/min)；
Izod notched impact strength: it is tested according to ISO 180；
Melt flow rate (MFR): it is tested according to ISO 1133 (220 DEG C/10Kg)；
Heat distortion temperature (HDT): it under the conditions of 0.45MPa, is tested according to ISO 75/2；
Scratch resistance: it is tested by GMW 14688 in K31 dermatoglyph face；
Glossiness: pressing ASTM D2457 standard testing, and test angle is 60 °；
Chemical-resistant: shield gasoline and acetic acid are applied on tensile bars surface, after room temperature 48 hours, observes face crack
Situation.
Test result is shown in Table 1.
Table 1
Comparative example 1-6
It is made comparative example 1-6's using preparation method same as Example 1 according to raw material shown in table 2 and dosage
ASA/PMMA composition, and performance test methods identical with embodiment 1-5 are used, the ASA/PMMA of comparative example 1-6 is combined
The correlated performance of object is tested.Test result is as shown in table 2.
Table 2
Wherein, Mitsubishi S-2001 is organosilicon acrylic ester copolymerization object, and center is organosilicon/acrylic acid compounded rubber,
Shell is acrylonitritrile-styrene resin, silicone content < 5%.
Clock deep pool MR-01 is organosilicon acrylic ester copolymerization object, and center is siloxanes/butyl acrylate copolymer, and shell is
Acrylonitritrile-styrene resin, silicone content are > 60%.
As shown in Table 1, with the difference of each raw material dosage, the properties of each embodiment are not quite similar, in embodiment 3,
When the additional amount of SX-006 is 25 parts, 40 parts of PMMA content, 35 parts of ASA content, composition properties are preferable, in embodiment 1,2,
As the additional amount of SX-006 reduces, the additional amount of PMMA increases, the room temperature of composition, low-temperature flexibility decrease, but gloss
Degree and scratch resistance slightly improve.Meanwhile in embodiment 4 and 5, with the increase of SX-006 content, ASA content drop can be made up
The reduction of low bring chemical resistance, while thermodynamic property is also kept, but processing performance (melt flows speed
Rate) slightly reduce.Above embodiments explanation: the dosage of organosilicon acrylic ester copolymerization object, PMMA resin, ASA resin, to group
Room temperature, low-temperature flexibility, scratch resistance and the chemical resistance for closing object have a major impact.
In table 2, comparing embodiment 3, the performance of comparative example 1,2 are it is found that relative to embodiment 3, toughener in comparative example 1
SX-006 additive amount is on the low side, although processing performance, thermal property are kept very well, toughness of material is obviously insufficient, solvent resistant
Performance is also poor；And comparative example 2, compared to embodiment 3, since toughener additive amount is excessive, Material Thermodynamics reduced performance is bright
Aobvious, processing performance is also negatively affected.It is to increase with S-2001 (silicone content < 5%) in comparative example 3 and comparative example 4
Tough dose of replacement SX-006, although room temperature impacts more excellent low-temperature flexibility, decline is obvious, when additive amount is less chemicals also compared with
Difference；And additive amount it is excessive when, thermodynamics, processing performance and glossiness are all substantially reduced.In comparative example 5 and comparative example 6, with
MR-01 (silicone content > 60%) is that toughener replaces SX-006, although low-temperature impact decline is also unobvious, glossiness is bright
It is inadequate, show the glossiness that material can be significantly affected after the core-shell structure organosilicon ratio excess in toughener, this is because
On the surface of the material, diffusing reflection ratio increases, and glossiness can be substantially reduced for excessive organosilicon aggregation.
Table 2 statistics indicate that, in organosilicon acrylic ester copolymerization object the content of organosilicon to the low-temperature flexibility of composition,
Scratch resistance, chemical-resistant have a major impact.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of ASA/PMMA resin combination, which is characterized in that include the raw material of following parts by weight:
The organosilicon acrylic ester copolymerization object is core-shell structure, and core is organosilicon/acrylic acid compounded rubber, and shell is acrylonitrile-
Styrol copolymer；
The weight ratio that the organosilicon accounts for the organosilicon acrylic ester copolymerization object is 20%-40%.
2. ASA/PMMA resin combination according to claim 1, which is characterized in that include the original of following parts by weight
Material:
3. ASA/PMMA resin combination according to claim 1, which is characterized in that the organosilicon accounts for described organic
Silicon/acrylate copolymer weight ratio is 20%-30%.
4. ASA/PMMA resin combination according to claim 1-3, which is characterized in that in the ASA resin,
The content of acrylonitrile is 25%-35%.
5. ASA/PMMA resin combination according to claim 4, which is characterized in that the ASA resin melt flows speed
Rate is 20-48g/10min at 220 DEG C/10kg.
6. ASA/PMMA resin combination according to claim 1-3, which is characterized in that the hardness of the PMMA
Value is 3H-5H.
7. ASA/PMMA resin combination according to claim 6, which is characterized in that the PMMA melt flow rate (MFR) exists
It is 40-65g/10min under 220 DEG C/10kg.
8. ASA/PMMA resin combination according to claim 1-3, which is characterized in that the auxiliary agent includes
One or more of antioxidant, stabilizer, lubricant, dispersing agent and carbon black.
9. a kind of preparation method of the described in any item ASA/PMMA resin combinations of claim 1-8, which is characterized in that including
Following steps:
By the ASA resin, PMMA resin, organosilicon acrylic ester copolymerization object and auxiliary agent be mixed, extrusion molding to get.
10. preparation method according to claim 9, which is characterized in that the revolving speed of the mixing be 250 revs/min-
350 revs/min, the time is -20 minutes 10 minutes；
The technological parameter of the extrusion molding includes: that the draw ratio of double screw extruder is 30-40:1, from the first warm area to the tenth
The operating temperature of warm area is arranged are as follows: 170 DEG C -200 DEG C of an area, two 190 DEG C -210 DEG C of areas, three 200 DEG C -230 DEG C of areas, four areas 210
DEG C -230 DEG C, five 220 DEG C -235 DEG C of areas, six 220 DEG C -235 DEG C of areas, seven 220 DEG C -235 DEG C of areas, eight 220 DEG C -235 DEG C of areas, 9th area
210 DEG C -230 DEG C, ten 210 DEG C -230 DEG C of areas, 210 DEG C -220 DEG C of head area；The double screw extruder revolving speed is 200 revs/min
- 500 revs/min of clock.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256798A (en) * | 2019-07-11 | 2019-09-20 | 常州威材新材料科技有限公司 | A kind of PMMA/ASA alloy material and preparation method thereof |
| CN111690222A (en) * | 2020-07-09 | 2020-09-22 | 东莞市奥能工程塑料有限公司 | PMMA/ASA alloy material with high heat resistance and high blackness and brightness, preparation method and application thereof |
| CN112646361A (en) * | 2020-12-14 | 2021-04-13 | 上海金发科技发展有限公司 | Highlight black spraying-free PA/ASA composition and preparation method thereof |
| CN112745615A (en) * | 2019-10-29 | 2021-05-04 | 合肥杰事杰新材料股份有限公司 | PMMA/ASA material and preparation method thereof |
| CN113150480A (en) * | 2021-02-03 | 2021-07-23 | 山东道恩高分子材料股份有限公司 | High-black high-brightness spraying-free scratch-resistant super-weather-resistant PMMA/ASA alloy material |
-
2018
- 2018-12-17 CN CN201811540047.1A patent/CN109651743A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256798A (en) * | 2019-07-11 | 2019-09-20 | 常州威材新材料科技有限公司 | A kind of PMMA/ASA alloy material and preparation method thereof |
| CN112745615A (en) * | 2019-10-29 | 2021-05-04 | 合肥杰事杰新材料股份有限公司 | PMMA/ASA material and preparation method thereof |
| CN112745615B (en) * | 2019-10-29 | 2023-08-15 | 合肥杰事杰新材料股份有限公司 | PMMA/ASA material and preparation method thereof |
| CN111690222A (en) * | 2020-07-09 | 2020-09-22 | 东莞市奥能工程塑料有限公司 | PMMA/ASA alloy material with high heat resistance and high blackness and brightness, preparation method and application thereof |
| CN112646361A (en) * | 2020-12-14 | 2021-04-13 | 上海金发科技发展有限公司 | Highlight black spraying-free PA/ASA composition and preparation method thereof |
| CN113150480A (en) * | 2021-02-03 | 2021-07-23 | 山东道恩高分子材料股份有限公司 | High-black high-brightness spraying-free scratch-resistant super-weather-resistant PMMA/ASA alloy material |
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Application publication date: 20190419 |
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| WW01 | Invention patent application withdrawn after publication |