CN107759914A - A kind of automobile-used modified ASA material and preparation method thereof - Google Patents

A kind of automobile-used modified ASA material and preparation method thereof Download PDF

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Publication number
CN107759914A
CN107759914A CN201710997237.5A CN201710997237A CN107759914A CN 107759914 A CN107759914 A CN 107759914A CN 201710997237 A CN201710997237 A CN 201710997237A CN 107759914 A CN107759914 A CN 107759914A
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China
Prior art keywords
automobile
used modified
modified asa
asa material
extrudate
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CN201710997237.5A
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Inventor
刘艺
黄志杰
沈岳新
王海华
杨仓先
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Nakahiro Junl (shanghai) New Material Co Ltd
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Nakahiro Junl (shanghai) New Material Co Ltd
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Priority to CN201710997237.5A priority Critical patent/CN107759914A/en
Publication of CN107759914A publication Critical patent/CN107759914A/en
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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

Abstract

The invention discloses a kind of automobile-used modified ASA material, its raw material includes by mass percentage：ASA resin, 30% 50%；Styrene-acrylonitrile, 40% 60%；Makrolon, 8% 18%；Compatilizer, 1% 5%；Weather-proof auxiliary agent, 0.1% 1%；Antioxidant, 0.1% 1%.The invention also discloses a kind of preparation method of automobile-used modified ASA material.The automobile-used modified ASA material of the present invention, toughness reinforcing is carried out using a small amount of siliceous makrolon, can not only effectively improve normal temperature toughness and low-temperature flexibility, and do not influence the weatherability of final products so that final products have high durable, high tenacity；The automobile-used modified ASA material preparation method of the present invention, technical process is simple, cost is low, obtained modified ASA material easy processing, particularly suitable for automotive field.

Description

A kind of automobile-used modified ASA material and preparation method thereof
Technical field
The present invention relates to fields such as chemistry, materials, specially a kind of automobile-used modified ASA material and preparation method thereof.
Background technology
ASA resin has the spies such as excellent weatherability, excellent mechanical strength, excellent heat resistance, high electrical insulating property Property so that the automobile-used exterior trim that it turns into a kind of extensive application exempts from sprayed on material.
Progress lacquer spraying technique flow, which is generally required, using traditional PC/ABS, PC/ASA material can be only achieved automobile to material Apparent various requirement, but lacquer spraying technique not only generates influence to the performance of material, while the cost of product is added, paint Process can also produce certain pollution to environment, run counter to the social theory for nowadays focusing on environmental protection and sustainable development.Vapour Car use exempts to spray ASA, can be without follow-up spraying process, so as to environmental protection and to reduce cost extremely advantageous.
But existing weatherability ASA resin, its tensile strength and impact strength all very it is low (tensile strength 21MPa-35MPa, Impact strength 4KJ/m2-10KJ/m2), the requirement of vehicle material far can not be reached.And only pass through 600KJ/m2Illumination add After fast aging, chromatic aberration Δ E has just exceeded more than 1.5, or even 2.This does not reach the requirement of vehicle material much.
The content of the invention
The purpose of the present invention is：A kind of automobile-used modified ASA material is provided, with excellent weatherability and excellent Toughness.
Realizing the technical scheme of above-mentioned purpose is：A kind of automobile-used modified ASA material, its raw material include by mass percentage： ASA resin, 30%~50%；Styrene-acrylonitrile, 40%~60%；Makrolon, 8%~18%；Compatilizer, 1%~ 5%；Weather-proof auxiliary agent, 0.1%~1%；Antioxidant, 0.1%~1%.
In a preferred embodiment of the invention, the ASA resin is connecing for Acrylate-styrene bipolymer-acrylonitrile composition Graft copolymer, wherein, the quality of the acrylate accounts for the 40%~70% of the graft copolymer.
In a preferred embodiment of the invention, the melt index scope of the styrene-acrylonitrile is 8g/10min- 40g/10min。
In a preferred embodiment of the invention, the makrolon includes siliceous makrolon.
In a preferred embodiment of the invention, the compatilizer includes ABS grafted maleics anhydride copolymer, ASA is grafted At least one of copolymer-maleic anhydride, styrene-grafted copolymer-maleic anhydride.
In a preferred embodiment of the invention, the weather-proof auxiliary agent includes at least one in BTA, phentriazine Kind.
In a preferred embodiment of the invention, described antioxidant is the double β-(the 3- tert-butyl group -4- hydroxyls of triethylene-glycol Base -5- aminomethyl phenyls) propionic ester, four [β-(3,5- di-t-butyl 4- hydroxy phenyls) propionic acid] pentaerythritol esters, three (2,4- bis- uncles Butyl phenyl) phosphite ester, at least one of double stearyl alcohol pentaerythritol diphosphites.
A kind of it is a second object of the invention to provide preparation method of automobile-used modified ASA material
A kind of preparation method of automobile-used modified ASA material, comprises the following steps：Step S1) obtain described raw material；Step S2) blend step S1) in raw material, be thoroughly mixed uniformly, obtain mixture；Step S3) mixture is passed through it is double Screw extruder is extruded, and obtains extrudate；
Step S4) extrudate is cooled down, dried, pelletizing processing, obtain granular modified ASA material.
In a preferred embodiment of the invention, in step S3) in, the screw speed is 150rpm-500rpm, processing Temperature is 200 DEG C -240 DEG C, and the double screw extruder is provided with multiple processing temperature sections along extrusion direction, wherein by feed zone to Processing temperature section at head is respectively：200℃、220℃、230℃、240℃、235℃、235℃、240℃、240℃、235 ℃。
In a preferred embodiment of the invention, the step S4) in, comprise the following steps：Step S41) pass through water cooling Method carries out water cooling to the extrudate；Step S42) extrudate after the water cooling is dried by air dry oven, dry temperature Spend for 90 DEG C -100 DEG C, drying time 3h-5h.
It is an advantage of the invention that：The automobile-used modified ASA material of the present invention, toughness reinforcing is carried out using a small amount of siliceous makrolon, Normal temperature toughness and low-temperature flexibility can be not only effectively improved, and does not influence the weatherability of final products so that final products have High durable, high tenacity；The automobile-used modified ASA material preparation method of the present invention, technical process is simple, cost is low, obtained modification ASA material easy processings, particularly suitable for automotive field.
Embodiment
A kind of automobile-used modified ASA material, its raw material include by mass percentage：ASA resin, 30%~50%；Styrene Acrylonitrile, 40%~60%；Makrolon, 8%~18%；Compatilizer, 1%~5%；Weather-proof auxiliary agent, 0.1%~1%；Antioxygen Agent, 0.1%~1%.The ASA resin is the graft copolymer of Acrylate-styrene bipolymer-acrylonitrile composition, wherein, described third The quality of olefin(e) acid ester accounts for the 40%~70% of the graft copolymer.The melt index scope of the styrene-acrylonitrile is 8g/ 10min-40g/10min。
The makrolon includes siliceous makrolon.The compatilizer includes ABS grafted maleics anhydride copolymer, ASA At least one of grafted maleic anhydride copolymer, styrene-grafted copolymer-maleic anhydride.The weather-proof auxiliary agent includes benzo At least one of triazole, phentriazine.Described antioxidant is the double β-(3- tertiary butyl-4-hydroxy -5- first of triethylene-glycol Base phenyl) propionic ester, four [β-(3,5- di-t-butyl 4- hydroxy phenyls) propionic acid] pentaerythritol esters, three (2,4- di-tert-butyls Base) phosphite ester, at least one of double stearyl alcohol pentaerythritol diphosphites.
The present invention is illustrated below by embodiment.
Embodiment 1
A kind of preparation method of automobile-used modified ASA material, comprises the following steps.
Step S1) obtain raw material.The raw material by mass fraction include 34 parts of ASA resin, 56 parts of styrene-acrylonitrile (AS), Siliceous 8 parts of makrolon, compatilizer are from 3 parts of ABS grafted maleic anhydrides, 0.6 part of weather-proof selection of auxiliary BTA, antioxidant From double β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) 0.4 part of the propionic esters of triethylene-glycol, wherein, every part of quality phase Together, it can be 1g, 10g or 1kg etc..
Step S2) blend step S1) in raw material, be thoroughly mixed uniformly, obtain mixture.
Step S3) mixture is extruded by double screw extruder, obtain extrudate；In step S3) in, the spiral shell Bar rotating speed is 150rpm-500rpm, and processing temperature is 200 DEG C -240 DEG C, and the double screw extruder is provided with more along extrusion direction Individual processing temperature section, wherein being respectively by the processing temperature section of feed zone to head：200℃、220℃、230℃、240℃、 235 DEG C, 235 DEG C, 240 DEG C, 240 DEG C, 235 DEG C (temperature at head).
Step S4) extrudate is cooled down, dried, pelletizing processing, obtain granular modified ASA material.Institute State step S4) in, comprise the following steps：Step S41) by water cooling to the extrudate carry out water cooling；Step S42) pass through Air dry oven is dried to the extrudate after the water cooling, and drying temperature is 90 DEG C -100 DEG C, drying time 3h-5h.
Embodiment 2
A kind of preparation method of automobile-used modified ASA material, comprises the following steps.
Step S1) obtain raw material.The raw material by mass fraction include 32 parts of ASA resin, 53 parts of styrene-acrylonitrile (AS), Siliceous 13 parts of makrolon, compatilizer are from 3 parts of ASA grafted maleic anhydrides, 0.6 part of weather-proof selection of auxiliary BTA, antioxygen Double β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) 0.4 part of the propionic esters of triethylene-glycol are selected in agent, wherein, every part of quality It is identical, can be 1g, 10g or 1kg etc..
Step S2) blend step S1) in raw material, be thoroughly mixed uniformly, obtain mixture.
Step S3) mixture is extruded by double screw extruder, obtain extrudate；In step S3) in, the spiral shell Bar rotating speed is 150rpm-500rpm, and processing temperature is 200 DEG C -240 DEG C, and the double screw extruder is provided with more along extrusion direction Individual processing temperature section, wherein being respectively by the processing temperature section of feed zone to head：200℃、220℃、230℃、240℃、 235 DEG C, 235 DEG C, 240 DEG C, 240 DEG C, 235 DEG C (temperature at head).
Step S4) extrudate is cooled down, dried, pelletizing processing, obtain granular modified ASA material.Institute State step S4) in, comprise the following steps：Step S41) by water cooling to the extrudate carry out water cooling；Step S42) pass through Air dry oven is dried to the extrudate after the water cooling, and drying temperature is 90 DEG C -100 DEG C, drying time 3h-5h.
Embodiment 3
A kind of preparation method of automobile-used modified ASA material, comprises the following steps.
Step S1) obtain raw material.The raw material by mass fraction include 30 parts of ASA resin, 50 parts of styrene-acrylonitrile (AS), Siliceous 18 parts of makrolon, compatilizer are selected from 3 parts of styrene-grafted, 0.6 part of weather-proof selection of auxiliary BTA, antioxidant Double β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) 0.4 part of the propionic esters of triethylene-glycol, wherein, every part identical in quality, Can be 1g, 10g or 1kg etc..
Step S2) blend step S1) in raw material, be thoroughly mixed uniformly, obtain mixture.
Step S3) mixture is extruded by double screw extruder, obtain extrudate；In step S3) in, the spiral shell Bar rotating speed is 150rpm-500rpm, and processing temperature is 200 DEG C -240 DEG C, and the double screw extruder is provided with more along extrusion direction Individual processing temperature section, wherein being respectively by the processing temperature section of feed zone to head：200℃、220℃、230℃、240℃、 235 DEG C, 235 DEG C, 240 DEG C, 240 DEG C, 235 DEG C (temperature at head).
Step S4) extrudate is cooled down, dried, pelletizing processing, obtain granular modified ASA material.Institute State step S4) in, comprise the following steps：Step S41) by water cooling to the extrudate carry out water cooling；Step S42) pass through Air dry oven is dried to the extrudate after the water cooling, and drying temperature is 90 DEG C -100 DEG C, drying time 3h-5h.
Embodiment 4
A kind of preparation method of automobile-used modified ASA material, comprises the following steps.
Step S1) obtain raw material.The raw material by mass fraction include 28 parts of ASA resin, 47 parts of styrene-acrylonitrile (AS), Siliceous 23 parts of makrolon, compatilizer are from 1 part of ABS grafted maleic anhydrides, 1 part of ASA grafted maleic anhydrides, styrene-grafted 1 Part；Weather-proof 0.6 part of selection of auxiliary BTA；Antioxidant selected for four [β-(3,5- di-t-butyl 4- hydroxy phenyls) propionic acid] seasons penta Four 0.4 part of alcohol esters, wherein, every part identical in quality can be 1g, 10g or 1kg etc..
Step S2) blend step S1) in raw material, be thoroughly mixed uniformly, obtain mixture.
Step S3) mixture is extruded by double screw extruder, obtain extrudate；In step S3) in, the spiral shell Bar rotating speed is 150rpm-500rpm, and processing temperature is 200 DEG C -240 DEG C, and the double screw extruder is provided with more along extrusion direction Individual processing temperature section, wherein being respectively by the processing temperature section of feed zone to head：200℃、220℃、230℃、240℃、 235 DEG C, 235 DEG C, 240 DEG C, 240 DEG C, 235 DEG C (temperature at head).
Step S4) extrudate is cooled down, dried, pelletizing processing, obtain granular modified ASA material.Institute State step S4) in, comprise the following steps：Step S41) by water cooling to the extrudate carry out water cooling；Step S42) pass through Air dry oven is dried to the extrudate after the water cooling, and drying temperature is 90 DEG C -100 DEG C, drying time 3h-5h.
Embodiment 5
A kind of preparation method of automobile-used modified ASA material, comprises the following steps.
Step S1) obtain raw material.The raw material by mass fraction include 30 parts of ASA resin, 50 parts of styrene-acrylonitrile (AS), Siliceous 18 parts of makrolon, 0.6 part of weather-proof selection of auxiliary BTA, antioxidant are from double β-(the tertiary fourths of 3- of triethylene-glycol Base -4- hydroxy-5-methyl bases phenyl) 0.4 part of propionic ester, wherein, every part identical in quality can be 1g, 10g or 1kg Etc..
Step S2) blend step S1) in raw material, be thoroughly mixed uniformly, obtain mixture.
Step S3) mixture is extruded by double screw extruder, obtain extrudate；In step S3) in, the spiral shell Bar rotating speed is 150rpm-500rpm, and processing temperature is 200 DEG C -240 DEG C, and the double screw extruder is provided with more along extrusion direction Individual processing temperature section, wherein being respectively by the processing temperature section of feed zone to head：200℃、220℃、230℃、240℃、 235 DEG C, 235 DEG C, 240 DEG C, 240 DEG C, 235 DEG C (temperature at head).
Step S4) extrudate is cooled down, dried, pelletizing processing, obtain granular modified ASA material.Institute State step S4) in, comprise the following steps：Step S41) by water cooling to the extrudate carry out water cooling；Step S42) pass through Air dry oven is dried to the extrudate after the water cooling, and drying temperature is 90 DEG C -100 DEG C, drying time 3h-5h.
Comparative example 1
A kind of preparation method of automobile-used modified ASA material, comprises the following steps.
Step S1) obtain raw material.The raw material by mass fraction include 30 parts of ASA resin, 50 parts of styrene-acrylonitrile (AS), Conventional 18 parts of makrolon, compatilizer are selected from 3 parts of styrene-grafted, 0.6 part of weather-proof selection of auxiliary BTA, antioxidant Double β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) 0.4 part of the propionic esters of triethylene-glycol, wherein, every part identical in quality, Can be 1g, 10g or 1kg etc..
Step S2) blend step S1) in raw material, be thoroughly mixed uniformly, obtain mixture.
Step S3) mixture is extruded by double screw extruder, obtain extrudate；In step S3) in, the spiral shell Bar rotating speed is 150rpm-500rpm, and processing temperature is 200 DEG C -240 DEG C, and the double screw extruder is provided with more along extrusion direction Individual processing temperature section, wherein being respectively by the processing temperature section of feed zone to head：200℃、220℃、230℃、240℃、 235 DEG C, 235 DEG C, 240 DEG C, 240 DEG C, 235 DEG C (temperature at head).
Step S4) extrudate is cooled down, dried, pelletizing processing, obtain granular modified ASA material.Institute State step S4) in, comprise the following steps：Step S41) by water cooling to the extrudate carry out water cooling；Step S42) pass through Air dry oven is dried to the extrudate after the water cooling, and drying temperature is 90 DEG C -100 DEG C, drying time 3h-5h.
Above-described embodiment 1-5 and comparative example 1 properties are tested below, and form table 1.The test of material Method is as follows.
Melt index：Using the standards of ISO 1133,220 DEG C, 10kg load.
Tensile strength：Using the standards of ISO 527, test speed 50mm/min.
Bending strength/bending modulus：Using the standards of ISO 178, test speed 2mm/min.
Notch shock：Using ISO 179-1eA standard simply supported beams, normal temperature condition is 23+/- 2 DEG C, and cryogenic conditions are -30 +/- 2 DEG C, more than 24h is deposited at -30 DEG C, is placed under -30 DEG C of environment and is tested.
Xenon lamp aging test condition：SAE J2527 2500kJ/m2.
Table 1 is the test parameter of the sample of ASA materials made from embodiment 1-5 and comparative example 1.
From above-described embodiment 1-5 and to comparative example 1 as can be seen that siliceous makrolon addition so that modified ASA it is normal Warm toughness and low-temperature flexibility are obtained for raising, but weatherability have dropped；And compatilizer is added without, toughness and weatherability can be caused All decline；If selection common polycarbonate in addition, low-temperature flexibility and weatherability all decline.Therefore, we integrate various property Can, the optimal embodiment 3 of performance balance is obtained, both ensure that the weather resistance of material, also ensure that the normal temperature of material, low temperature are tough Property, reach optimal.Simultaneously because the good fluidity of material, is particularly suitable for being processed as auto parts.
These are only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and All any modification, equivalent and improvement made within principle etc., should be included in the scope of the protection.

Claims (10)

1. a kind of automobile-used modified ASA material, it is characterised in that its raw material includes by mass percentage：
ASA resin, 30% 50%；
Styrene-acrylonitrile, 40% 60%；
Makrolon, 8% 18%；
Compatilizer, 1% 5%；
Weather-proof auxiliary agent, 0.1% 1%；
Antioxidant, 0.1% 1%.
2. automobile-used modified ASA material according to claim 1, it is characterised in that the ASA resin is acrylate-benzene The graft copolymer of ethylene-propylene nitrile composition, wherein, the quality of the acrylate accounts for the 40% of the graft copolymer 70%.
3. automobile-used modified ASA material according to claim 1, it is characterised in that the melting of the styrene-acrylonitrile refers to Number scope is 8g/10min-40g/10min.
4. automobile-used modified ASA material according to claim 1, it is characterised in that the makrolon includes siliceous poly- carbon Acid esters.
5. automobile-used modified ASA material according to claim 1, it is characterised in that the compatilizer includes ABS grafting Malaysia At least one of acid anhydride copolymer, ASA grafted maleics anhydride copolymer, styrene-grafted copolymer-maleic anhydride.
6. automobile-used modified ASA material according to claim 1, it is characterised in that the weather-proof auxiliary agent include BTA, At least one of phentriazine.
7. automobile-used modified ASA material according to claim 1, it is characterised in that described antioxidant is two three second two of contracting Alcohol double β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester, four [β-(3,5- di-t-butyl 4- hydroxy phenyls) propionic acid] seasons In Doutrate, three (2,4- di-tert-butyl-phenyl) phosphite esters, double stearyl alcohol pentaerythritol diphosphites at least It is a kind of.
8. a kind of preparation method of automobile-used modified ASA material, it is characterised in that comprise the following steps：
Step S1）Obtain the raw material any one of claim 1-7；
Step S2）Blend step S1）In raw material, be thoroughly mixed uniformly, obtain mixture；
Step S3）The mixture is extruded by double screw extruder, obtains extrudate；
Step S4）The extrudate is cooled down, dried, pelletizing processing, obtains granular modified ASA material.
9. the preparation method of automobile-used modified ASA material according to claim 8, it is characterised in that in step S3）In, institute It is 150rpm-500rpm to state screw speed, and processing temperature is 200 DEG C -240 DEG C, and the double screw extruder is set along extrusion direction There are multiple processing temperature sections, wherein being respectively by the processing temperature section of feed zone to head：200℃、220℃、230℃、240 ℃、235℃、235℃、240℃、240℃、235℃。
10. the preparation method of automobile-used modified ASA material according to claim 8, it is characterised in that the step S4）In, Comprise the following steps：
Step S41）Water cooling is carried out to the extrudate by water cooling；
Step S42）The extrudate after the water cooling is dried by air dry oven, drying temperature is 90 DEG C -100 DEG C, is dried Time is 3h-5h.
CN201710997237.5A 2017-10-19 2017-10-19 A kind of automobile-used modified ASA material and preparation method thereof Pending CN107759914A (en)

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CN109401102A (en) * 2018-09-25 2019-03-01 上海金山锦湖日丽塑料有限公司 A kind of cold-resistant ASA resin and preparation method thereof
CN109401103A (en) * 2018-09-25 2019-03-01 上海金山锦湖日丽塑料有限公司 A kind of black ASA resin composition of high durable bloom and preparation method thereof
CN110330755A (en) * 2019-04-02 2019-10-15 苏州聚冠复合材料有限公司 A kind of high durable type modified ASA material and preparation process
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