CN107523002A - A kind of special high oil resistant high-performance ABS alloy material of battery cell case - Google Patents
A kind of special high oil resistant high-performance ABS alloy material of battery cell case Download PDFInfo
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- CN107523002A CN107523002A CN201710657392.2A CN201710657392A CN107523002A CN 107523002 A CN107523002 A CN 107523002A CN 201710657392 A CN201710657392 A CN 201710657392A CN 107523002 A CN107523002 A CN 107523002A
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- butadiene
- battery cell
- alloy material
- cell case
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of special high oil resistant high-performance ABS alloy material of battery cell case, in percentage by weight, its raw material includes：Styrene butadiene acrylonitle copolymer 10 50%, PBT 10 50%, butadiene type graft rubber 3 20%, compatilizer 1 10%, low temperature resistant modifying agent 1 10%, processing aid 0.5 5%.The special high oil resistant high-performance ABS alloy material of battery cell case prepared by the present invention has excellent mechanical performance, good oil resistance, excellent low temperature falling sphere performance, good processability, the performance requirement of new-energy electric vehicle pond shell is disclosure satisfy that, there are wide market prospects.
Description
Technical field
The present invention relates to technical field of plastic, the special high oil resistant high-performance ABS of specifically a kind of battery cell case
Alloy material.
Background technology
ABS plastic is one of five big synthesis synthetic resin, its impact resistance, heat resistance, lower temperature resistance, chemical proofing
And excellent electrical properties, also have the characteristics that easy processing, product size are stable, lustrous surface is good, easy application, coloring, also
The secondary operation such as surface metallization, plating, welding, hot pressing and bonding can be carried out, are widely used in machinery, automobile, electronics
The industrial circles such as electrical equipment, instrument and meter, weaving and building, it is a kind of extremely wide thermoplastic engineering plastic of purposes.
ABS plastic is the terpolymer of acrylonitrile, butadiene and styrene, and A represents acrylonitrile, and B represents butadiene, S
Represent styrene.Due to being formed with three kinds, and impart its good performance；Acrylonitrile assigns the chemically stable of ABS resin
Property, oil resistivity, certain rigidity and hardness；Butadiene makes its toughness, impact and cold resistance increase；Styrene makes its tool
There are good dielectric properties, and good processability is presented.ABS plastic organically unifies PB, PAN, PS various performances
Come, have the balanced excellent mechanical property of tough, hard, firm phase concurrently.Most of ABS be it is nontoxic, it is waterproof, but slightly moisture vapor permeable, inhale
Water rate is low, and 1 year water absorption rate of room temperature immersion is no more than 1% and physical property does not change.ABS has excellent comprehensive physical and machine
Tool performance, fabulous low-temperature impact resistance, dimensional stability, electrical property, wearability, chemical proof, dyeability, finished product
Processing and machining are preferable.ABS plastic is water-fast, inorganic salts, alkali and acids, insoluble in most of alcohols and varsol, and
It is readily soluble in aldehyde, ketone, ester and some chlorohydrocarbons.ABS plastic heat distortion temperature is low, flammable, and weatherability is poor.Melting temperature exists
217-237 DEG C, heat decomposition temperature is more than 250 DEG C.In the market modified ABS material of today, be all much be doped with regrinding-material,
Reworked material, it is not very stable to cause client's shaped article performance.
For battery case industry, most commonly used is exactly ABS and PP materials, and wherein ABS material is with its excellent mechanical property
Can, good dimensional stability turns into first choice.Conventional storage battery Vehicular battery shell, materials'use are poor, it is desirable to and it is very low, only need
Want material that there is certain impact intensity and low temperature impact strength can to reach the requirement used；And in terms of new-energy automobile,
Due to battery case and engine peripheral contact, this requires material to have higher heatproof, preferable resistance to machine oil（Brake fluid）, it is excellent
Different low temperature falling sphere performance.Because new-energy electric vehicle pond shell needs to meet 90 DEG C of high-temperature oil resistance tests, -40 DEG C of low temperature
The harsh requirements such as falling sphere test, and traditional ABS material heat distortion temperature itself only has 85 DEG C or so, resistance to brake fluid performance
Typically, the low-temperature impact at -40 DEG C is even more relatively low, it is therefore desirable to ABS is modified to realize.
The content of the invention
It is an object of the invention to provide a kind of special high oil resistant high-performance ABS alloy material of battery cell case, with solution
The problem of being proposed in certainly above-mentioned background technology.
To achieve the above object, the present invention provides following technical scheme：
A kind of special high oil resistant high-performance ABS alloy material of battery cell case, in percentage by weight, its raw material includes：
Acrylnitrile-Butadiene-Styrene 10-50%, PBT 10-50%, butadiene type graft rubber 3-20%, compatilizer 1-
10%th, low temperature resistant modifying agent 1-10%, processing aid 0.5-5%.
As the further scheme of the present invention：Butadiene mole contains in the Acrylnitrile-Butadiene-Styrene
Measure as 15-25%.
As further scheme of the invention：The viscosity of the PBT is 0.8-1.2.
As further scheme of the invention：The butadiene type graft rubber is metacrylate-butadiene-benzene
One or both of the ABS high glue powders of ethylene copolymer, butadiene content more than 60% combine.
As further scheme of the invention：The compatilizer is ABS grafts, α-methylstyrene grafting Malaysia acyl
One or more combinations in imines, ethylene methyl methacrylate copolymer.
As further scheme of the invention：The low temperature resistant modifying agent be styrene butadiene thermoplasticelastomer,
Methyl methacrylate-butadiene-styrene copolymer, polyester elastomer, polyolefin elastomer, ethylene-acrylic acid
One or more combinations in butyl ester-glycidyl methacrylate copolymer.
As further scheme of the invention：The processing aid includes primary antioxidant, auxiliary antioxidant, lubricant；
The primary antioxidant be β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester of propionic acid, four [β-(3,5- di-t-butyls-
4- hydroxy phenyls) propionic acid] it is pentaerythritol ester, double（2,4- di-tert-butyl-phenyls）Pentaerythrite, 2,6- di-t-butyl -4-4 cresols
In one or more combinations；The auxiliary antioxidant is three (2,4- di-tert-butyl-phenyls) phosphite esters, thio-2 acid two
One or more combinations in the double stearic alcohol esters of lauryl, thio-2 acid；The lubricant be E waxes, calcium stearate, PE waxes,
One or more combinations in silicone master batch, PETS.
As further scheme of the invention：In percentage by weight, its raw material includes：Styrene-butadiene-the third
Alkene lonitrile copolymer 30%, PBT 40%, butadiene type graft rubber 20%, compatilizer 4.5%, low temperature resistant modifying agent 5%, processing aid
0.5%。
The preparation method of the special high oil resistant high-performance ABS alloy material of the battery cell case, step are as follows：Weigh each
Raw material is added to high mixer high speed and stirred 5 minutes, is sent in the main feeder of extruder, is then added to twin-screw extrusion
Extruding pelletization is carried out in machine, the Temperature Distribution of double screw extruder is as follows：It is respectively to head by feed zone：220℃、245℃、
245 DEG C, 245 DEG C, 240 DEG C, 240 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, die head：240℃；The pellet of extrusion passes through water cooling, pelletizing,
Then pack.
Compared with prior art, the beneficial effects of the invention are as follows：
The special high oil resistant high-performance ABS alloy material of battery cell case prepared by the present invention has excellent mechanical performance, good
Oil resistance well, excellent low temperature falling sphere performance, good processability, disclosure satisfy that new-energy electric vehicle pond shell
Performance requirement, there are wide market prospects.
Embodiment
Technical scheme is described in more detail with reference to embodiment.
A kind of special high oil resistant high-performance ABS alloy material of battery cell case, in percentage by weight, its raw material bag
Include：Acrylnitrile-Butadiene-Styrene 10-50%, PBT 10-50%, butadiene type graft rubber 3-20%, compatilizer 1-
10%th, low temperature resistant modifying agent 1-10%, processing aid 0.5-5%.
The molar content of butadiene is 15-25% in the Acrylnitrile-Butadiene-Styrene.
The viscosity of the PBT is 0.8-1.2.
The butadiene type graft rubber is methacrylate butadi ene styrene copolymer, butadiene content exists
One or both of more than 60% ABS high glue powders combine.
The compatilizer is ABS grafts, α-methylstyrene grafting maleimide, ethylene methyl methacrylate
One or more combinations in copolymer.
The low temperature resistant modifying agent be styrene butadiene thermoplasticelastomer, methyl methacrylate-butadiene-
Styrene copolymer, polyester elastomer, polyolefin elastomer, Ethylene-butyl acrylate-GMA
One or more combinations in copolymer.
The processing aid includes primary antioxidant, auxiliary antioxidant, lubricant.
The primary antioxidant be β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester of propionic acid, four [β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid] it is pentaerythritol ester, double（2,4- di-tert-butyl-phenyls）Pentaerythrite, bis- tertiary fourths of 2,6-
One or more combinations in base -4-4 cresols.
The auxiliary antioxidant is three (2,4- di-tert-butyl-phenyls) phosphite esters, dilauryl thiodipropionate, thio
One or more combinations in the double stearic alcohol esters of dipropionic acid.
The lubricant is one or more combinations in E waxes, calcium stearate, PE waxes, silicone master batch, PETS.
The preparation method of the special high oil resistant high-performance ABS alloy material of the battery cell case is as follows：By styrene-fourth
Butadiene-acrylonitrile copolymer, PBT, butadiene type graft rubber, compatilizer, low temperature resistant modifying agent and processing aid add paramount
Mixed machine high speed stirs 5 minutes, is sent in the main feeder of extruder, then adds and extruded into double screw extruder
It is granulated.The Temperature Distribution of double screw extruder is as follows：It is respectively to head by feed zone：220℃、245℃、245℃、245℃、
240 DEG C, 240 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, die head：240℃.Then the pellet of extrusion is packed by water cooling, pelletizing.Grain
Material is dried 4 hours in air dry oven at 100 DEG C, then prepares test bars by injection machine.
Below in conjunction with two embodiments and three comparative examples, test bars are prepared according to above-mentioned preparation technology..Two realities
The concrete component proportioning for applying example and three comparative examples is as shown in table 1.Prepared test bars are carried out with performance test, test knot
Fruit is as shown in table 2.
The raw material proportioning table of table 1
| Component | Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Comparative example 3 |
| ABS 757K | 85% | 73% | 45% | 30% | 0% |
| PBT 1.0 is viscous | 0% | 12% | 30% | 40% | 85% |
| HR-181 | 10% | 10% | 15% | 20% | 0% |
| Low temperature resistant modifying agent | 4.5% | 0% | 5% | 5% | 10% |
| Compatilizer | 0% | 4.5% | 4.5% | 4.5% | 4.5% |
| Primary antioxidant 1010 | 0.1% | 0.1% | 0.1% | 0.1% | 0.1% |
| Auxiliary antioxidant 168 | 0.1% | 0.1% | 0.1% | 0.1% | 0.1% |
| Lubricant PETS | 0.3% | 0.3% | 0.3% | 0.3% | 0.3% |
Note：Acrylnitrile-Butadiene-Styrene selects ABS 757K, and selected PBT viscosity is 1.0, and butadiene type connects
Branch rubber selects HR-181, and low temperature resistant modifying agent selects styrene butadiene thermoplasticelastomer, and compatilizer selects ethene-first
Base methyl acrylate copolymer, primary antioxidant select four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters
（That is antioxidant 1010）, auxiliary antioxidant selects three (2,4- di-tert-butyl-phenyl) phosphite esters（That is irgasfos 168）, lubrication
PETS is selected in agent.
The performance test results table of table 2
| Performance indications | Testing standard | Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Comparative example 3 |
| Notch impact strength | ISO179-1 | 35 | 25 | 30 | 35 | 25 |
| - 30 DEG C of low temperature notched impact strengths | ISO179-1 | 20 | 15 | 18 | 15 | 12 |
| Normal temperature oil resistant is tested | Enterprise's mark | Difference | It is qualified | It is qualified | It is excellent | It is excellent |
| 80 DEG C of high-temperature oil resistance tests | Enterprise's mark | It is excessively poor | It is unqualified | It is qualified | It is excellent | It is excellent |
| Low temperature falling sphere is tested | Enterprise's mark | It is qualified | It is qualified | Preferably | It is excellent | It is qualified |
| Glue bonding is tested | Enterprise's mark | It is qualified | It is qualified | It is excellent | Preferably | It is unqualified |
As can be seen from the above table, as the increase of PET additions, the impact strength of material are decreased obviously, but PBT addition,
Under the oil resistance of material has one obviously to be lifted, but corresponding material glue adhesive property but has significantly
Drop.Therefore, controlling PBT content turns into key.Material prepared by embodiment 1-2 disclosure satisfy that New-energy electric vehicle is used
The performance requirement of battery case.Wherein, the material property prepared by embodiment 2 is preferable, as preferred embodiment.
Embodiment 3
A kind of special high oil resistant high-performance ABS alloy material of battery cell case, in percentage by weight, its raw material includes：
Acrylnitrile-Butadiene-Styrene 15%, PBT 45%, butadiene type graft rubber 20%, compatilizer 10%, low temperature resistant change
Property agent 5.5%, processing aid 4.5%.
The molar content of butadiene is 25% in the Acrylnitrile-Butadiene-Styrene.
The viscosity of the PBT is 0.8.
The butadiene type graft rubber is methacrylate butadi ene styrene copolymer.
The compatilizer is that α-methylstyrene is grafted maleimide.
The low temperature resistant modifying agent is methyl methacrylate-butadiene-styrene copolymer.
The processing aid includes primary antioxidant, auxiliary antioxidant, lubricant, primary antioxidant, auxiliary antioxidant and lubrication
The weight ratio of agent is 1:1:3.
The primary antioxidant be β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester of propionic acid.
The auxiliary antioxidant is dilauryl thiodipropionate.
The lubricant is calcium stearate.
Embodiment 4
A kind of special high oil resistant high-performance ABS alloy material of battery cell case, in percentage by weight, its raw material includes：
Acrylnitrile-Butadiene-Styrene 50%, PBT 35%, butadiene type graft rubber 5%, compatilizer 5%, low temperature resistant modification
Agent 2.5%, processing aid 2.5%.
The molar content of butadiene is 18% in the Acrylnitrile-Butadiene-Styrene.
The viscosity of the PBT is 1.1.
The butadiene type graft rubber is methacrylate butadi ene styrene copolymer.
The compatilizer is ethylene methyl methacrylate copolymer.
The low temperature resistant modifying agent is Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer.
The processing aid includes primary antioxidant, auxiliary antioxidant, lubricant, primary antioxidant, auxiliary antioxidant and lubrication
The weight ratio of agent is 1:1:3.
The primary antioxidant is double（2,4- di-tert-butyl-phenyls）Pentaerythrite and 2,6- di-t-butyl -4-4 cresols according to
Weight is than 1:1 composition.
The auxiliary antioxidant is the double stearic alcohol esters of thio-2 acid.
The lubricant is E waxes and PETS according to weight ratio 1:2 compositions.
Embodiment 5
A kind of special high oil resistant high-performance ABS alloy material of battery cell case, in percentage by weight, its raw material includes：
Acrylnitrile-Butadiene-Styrene 30%, PBT 35%, butadiene type graft rubber 15%, compatilizer 8%, low temperature resistant modification
Agent 8%, processing aid 4%.
The molar content of butadiene is 25% in the Acrylnitrile-Butadiene-Styrene.
The viscosity of the PBT is 1.2.
The butadiene type graft rubber is methacrylate butadi ene styrene copolymer.
The compatilizer be α-methylstyrene be grafted maleimide, ethylene methyl methacrylate copolymer according to
Weight is than 3:2 compositions.
The low temperature resistant modifying agent is styrene butadiene thermoplasticelastomer and Ethylene-butyl acrylate-metering system
Acid glycidyl ester copolymer is according to weight than 3:5 compositions.
The processing aid includes primary antioxidant, auxiliary antioxidant, lubricant, primary antioxidant, auxiliary antioxidant and lubrication
The weight ratio of agent is 1:1:3.
The primary antioxidant is 2,6- di-t-butyl -4-4 cresols.
The auxiliary antioxidant be dilauryl thiodipropionate, the double stearic alcohol esters of thio-2 acid according to weight than 3:1
Composition.
The lubricant is PE waxes.
Material prepared by embodiment 3-5 equally disclosure satisfy that the performance requirement of new-energy electric vehicle pond shell.
The special high oil resistant high-performance ABS alloy material of battery cell case prepared by the present invention has excellent mechanicalness
Energy, good oil resistance, excellent low temperature falling sphere performance, good processability, it disclosure satisfy that New-energy electric vehicle is used
The performance requirement of battery case, there are wide market prospects.
The better embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party
Formula, can also be on the premise of present inventive concept not be departed from one skilled in the relevant art's possessed knowledge
Various changes can be made.
Claims (9)
1. the special high oil resistant high-performance ABS alloy material of a kind of battery cell case, it is characterised in that according to percentage by weight
Meter, its raw material include：Acrylnitrile-Butadiene-Styrene 10-50%, PBT 10-50%, butadiene type graft rubber 3-
20%th, compatilizer 1-10%, low temperature resistant modifying agent 1-10%, processing aid 0.5-5%.
2. the special high oil resistant high-performance ABS alloy material of battery cell case according to claim 1, it is characterised in that
The molar content of butadiene is 15-25% in the Acrylnitrile-Butadiene-Styrene.
3. the special high oil resistant high-performance ABS alloy material of battery cell case according to claim 1, it is characterised in that
The viscosity of the PBT is 0.8-1.2.
4. the special high oil resistant high-performance ABS alloy material of battery cell case according to claim 1, it is characterised in that
The butadiene type graft rubber is methacrylate butadi ene styrene copolymer, butadiene content more than 60%
One or both of ABS high glue powders combine.
5. the special high oil resistant high-performance ABS alloy material of battery cell case according to claim 1, it is characterised in that
The compatilizer is in ABS grafts, α-methylstyrene grafting maleimide, ethylene methyl methacrylate copolymer
One or more combinations.
6. the special high oil resistant high-performance ABS alloy material of battery cell case according to claim 1, it is characterised in that
The low temperature resistant modifying agent is styrene butadiene thermoplasticelastomer, methyl methacrylate-butadiene-styrene three
In membered copolymer, polyester elastomer, polyolefin elastomer, Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer
One or more combinations.
7. the special high oil resistant high-performance ABS alloy material of battery cell case according to claim 1, it is characterised in that
The processing aid includes primary antioxidant, auxiliary antioxidant, lubricant；The primary antioxidant be β-（3,5- di-t-butyl -4- hydroxyls
Base phenyl）It is the positive octadecanol ester of propionic acid, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, double（2,4-
Di-tert-butyl-phenyl）One or more combinations in pentaerythrite, 2,6- di-t-butyl -4-4 cresols；The auxiliary antioxidant is
One kind in the double stearic alcohol esters of three (2,4- di-tert-butyl-phenyls) phosphite esters, dilauryl thiodipropionate, thio-2 acid
Or multiple combinations；The lubricant is one or more combinations in E waxes, calcium stearate, PE waxes, silicone master batch, PETS.
8. the special high oil resistant high-performance ABS alloy material of battery cell case according to claim 1, it is characterised in that
In percentage by weight, its raw material includes：Acrylnitrile-Butadiene-Styrene 30%, PBT 40%, butadiene type connect
Branch rubber 20%, compatilizer 4.5%, low temperature resistant modifying agent 5%, processing aid 0.5%.
A kind of 9. system of the special high oil resistant high-performance ABS alloy material of battery cell case as described in claim 1-8 is any
Preparation Method, it is characterised in that step is as follows：Weigh each raw material to add to high mixer high speed stirring 5 minutes, be sent to extruder
Main feeder in, then add and extruding pelletization carried out into double screw extruder, the Temperature Distribution of double screw extruder is as follows：
It is respectively to head by feed zone：220 DEG C, 245 DEG C, 245 DEG C, 245 DEG C, 240 DEG C, 240 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, mould
Head：240℃；Then the pellet of extrusion is packed by water cooling, pelletizing.
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| WO2020173490A1 (en) * | 2019-02-28 | 2020-09-03 | 金发科技股份有限公司 | High-polarity flame-retardant styrene composition, preparation method for same, and applications thereof |
| FR3130285A1 (en) * | 2021-12-09 | 2023-06-16 | Sk Geo Centric Co., Ltd. | LOW FLUIDITY POLYMER COMPOSITION CONTAINING ABS COPOLYMER AND TERPOLYMER AND METHOD FOR REDUCING FLUIDITY OF ABS COPOLYMER |
| FR3140885A1 (en) * | 2022-10-18 | 2024-04-19 | Skytech | Extrusion grade styrenic polymer compositions |
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| FR3130285A1 (en) * | 2021-12-09 | 2023-06-16 | Sk Geo Centric Co., Ltd. | LOW FLUIDITY POLYMER COMPOSITION CONTAINING ABS COPOLYMER AND TERPOLYMER AND METHOD FOR REDUCING FLUIDITY OF ABS COPOLYMER |
| FR3140885A1 (en) * | 2022-10-18 | 2024-04-19 | Skytech | Extrusion grade styrenic polymer compositions |
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Application publication date: 20171229 |