CN108250606B - Ultra-low temperature resistant ASA composite material and preparation method thereof - Google Patents
Ultra-low temperature resistant ASA composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultra-low temperature resistant ASA composite material and a preparation method thereof, wherein the raw materials comprise the following components in parts by weight: 30-60 parts of AS resin; 20-50 parts of ASA rubber powder; 5-20 parts of a low-temperature modifier; 5-10 parts of a toughening agent; 0.5-2 parts of weather resistant agent. The low-temperature modifier prepared from AES resin and modified silicone rubber has both mechanical property and low-temperature toughness, and is blended with other related auxiliary agents such AS AS resin, ASA rubber powder, toughening agent and the like. The components can be better dispersed by extruding and granulating through a double-stage extruder, so that the ASA material with high fluidity, high weather resistance and low temperature resistance is obtained. The ASA material prepared by the invention has excellent glossiness and fluidity, and can meet the appearance effect and processing requirements of automobiles and large-scale household electrical appliances; meanwhile, the paint has ultrahigh low-temperature toughness and weather resistance, and can ensure the normal use of the product under low-temperature conditions and outdoor environment.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an ultra-low temperature resistant ASA composite material and a preparation method thereof.
Background
ASA resins, also known as AAS resins, are ternary graft copolymers composed of acrylonitrile (A), styrene (S) and acrylic esters (A). Compared with ABS, the acrylic rubber without double bonds is used to replace butadiene rubber, so the weather resistance is improved substantially and is about 10 times higher than that of ABS. And the impact strength and the elongation rate are hardly reduced and the color is hardly changed when the glass is exposed to sunlight for 9-15 months. The mechanical properties, processability, electrical insulation and chemical resistance of ASA are similar to those of ABS, but the glass transition temperature of acrylate rubber is only-30 ℃ and is far lower than that of butadiene rubber. Therefore, ASA has much poorer low-temperature impact than ABS resin, which severely limits the application range of ASA.
The modification equipment commonly used in the market at present is a double-screw extruder, and for ASA powder with high glue content, the dispersion is difficult, so that the performance fluctuates in a large range.
The patent CN106810809A proposes to prepare an ASA material with ultralow gloss and ultralow temperature resistance, the low-temperature resistance toughness is improved by adding a core-shell structure copolymer, the effect of the low-temperature resistance of core-structure rubber is weakened, the normal-temperature impact and the fluidity of the obtained material are low, and the obtained material has problems in the processing and the use of some large parts.
Patent No. cn201610410631.x proposes a method for improving low-temperature impact toughness of ASA, which uses EMA-GMA, EBA-GMA, EEA-MAH as low-temperature impact toughness improver, and improves low-temperature toughness while the overall fluidity and gloss of the material are greatly reduced, so that the method is not suitable for some appearance parts and large parts.
Therefore, how to develop the ultra-low temperature resistant ASA composite material to improve low temperature impact has important practical significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a super low temperature resistant ASA composite material and a preparation method thereof by adopting a blending modification technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
the ultra-low temperature resistant ASA composite material comprises the following raw materials in parts by weight: 30-60 parts of AS resin; 20-50 parts of ASA rubber powder; 5-20 parts of a low-temperature modifier; 5-10 parts of a toughening agent; 0.5-2 parts of a weather resistant agent;
the toughening agent is ethylene propylene diene monomer grafted maleic anhydride, so that the low-temperature toughness of the ethylene propylene diene monomer is maintained, and the maleic anhydride is grafted, so that the compatibility of the ethylene propylene diene monomer grafted maleic anhydride with other materials is improved, and the ethylene propylene diene monomer grafted maleic anhydride is a bright point.
Further, the AS resin is acrylonitrile-styrene copolymer, the weight average molecular weight is 5-15 ten thousand, the acrylonitrile content is 20-30%, and the melt index under the test condition of 220 ℃/10kg is 20-70g/10 min.
Furthermore, the ASA rubber powder is a terpolymer of styrene-acrylonitrile-acrylate, the content of the acrylate is 40-60%, and the melt index under the test condition of 220 ℃/10kg is 5-25g/10 min.
Further, the weather resisting agent is 2' - (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -ditert-pentylphenyl) benzotriazole, 2- (2' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, bis (2,2,6, 6-tetramethylpiperidyl) sebacate, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] -1, 6-diadipyl [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] ] ].
Further, the low-temperature modifier comprises the following raw materials in parts by weight: 20-70 parts of AES resin, 20-70 parts of silicon rubber, 1-5 parts of DOP plasticizer (dioctyl phthalate), 1-5 parts of compatilizer, 1-5 parts of silane coupling agent, 0.5-2 parts of processing aid and 0.5-2 parts of antioxidant.
Further, the AES resin is a terpolymer of acrylonitrile-styrene-ethylene propylene diene monomer, the content of the ethylene propylene diene monomer is 50-70%, and the melt index under the test condition of 220 ℃/10kg is 5-25g/10 min.
Further, the silicone rubber is one or more of methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber and ethyl silicone rubber.
Furthermore, the compatilizer is one or more of ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer and active silane grafted ethylene-propylene rubber, and the antioxidant is one or more of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tris (2, 4-di-tert-butylphenyl) phosphite or dioctadecyl pentaerythritol diphosphite.
Further, the processing aid is one or more of N, N' -ethylene bis stearamide, oxidized polyethylene wax, pentaerythritol fatty acid ester or carrier-free silicone master batch.
A preparation method of an ultra-low temperature resistant ASA composite material specifically comprises the following steps:
(1) preparing a low-temperature modifier:
a. accurately weighing the silicon rubber and the DOP plasticizer according to the proportion, and performing premixing treatment to obtain modified silicon rubber;
b. accurately weighing the AES resin, the compatilizer, the coupling agent, the processing aid and the antioxidant according to the proportion, simultaneously adding the AES resin, the compatilizer, the coupling agent, the processing aid and the antioxidant and the modified silicone rubber into a high-mixing pot for mixing for 3-5min, and then drawing strips and granulating through a double-screw extruder to prepare the low-temperature modifier;
(2) preparing the ultra-low temperature resistant ASA composite material:
a. accurately weighing ASA rubber powder, a low-temperature modifier, a toughening agent and a weather-resistant agent according to a proportion, adding the ASA rubber powder, the low-temperature modifier, the toughening agent and the weather-resistant agent into a high-speed mixing kettle, mixing for 3-5min, and taking out to serve as a first component;
b. accurately weighing AS resin according to the proportion to be used AS a second component;
c. adding the uniformly mixed first component into a double-screw extruder of a double-stage extruder, wherein the length-diameter ratio of the double-screw extruder is 36, the extrusion temperature is 200-; and continuously adding the second component into a single-screw extruder of a double-stage extruder according to the proportion, wherein the length-diameter ratio of the single-screw extruder is 7, the extrusion temperature is 200-240 ℃, the screw rotation speed is 50-70rpm, and the ultra-low temperature resistant ASA composite material is obtained by single-screw shearing, extrusion, granulation and drying.
The invention has the beneficial effects that:
the invention uses the low-temperature modifier prepared from AES resin and modified silicon rubber, has both mechanical property and low-temperature toughness, and is blended with other related auxiliary agents such AS AS resin, ASA rubber powder, toughening agent and the like. The ASA rubber powder with high rubber content can be better dispersed and granulated by a double-stage extruder to obtain the ultra-low temperature resistant ASA composite material with excellent and stable performance, so that the excellent weather resistance of ASA and the low temperature resistance of silicone rubber are kept, the low temperature toughness and the aging resistance of AES resin are exerted to the greatest extent, and the normal use of the product in outdoor environment and low temperature condition is ensured, thereby prolonging the service life of the product to the greatest extent, being widely applied to materials in low temperature environment and sunlight illumination for a long time, and solving the problems of use and transportation of some household appliances and outdoor products in severe cold outdoor condition.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following embodiments.
A preparation method of an ultra-low temperature resistant ASA composite material specifically comprises the following steps:
(1) preparing a low-temperature modifier:
a. accurately weighing the silicon rubber and the DOP plasticizer according to the proportion, and performing premixing treatment to obtain modified silicon rubber; the crystallization temperature of the silicone rubber is reduced, and the low temperature resistance of the silicone rubber is improved;
b. accurately weighing the AES resin, the compatilizer, the coupling agent, the processing aid and the antioxidant according to the proportion, simultaneously adding the AES resin, the compatilizer, the coupling agent, the processing aid and the antioxidant and the modified silicone rubber into a high-mixing pot for mixing for 3-5min, and then drawing strips and granulating through a double-screw extruder to prepare the low-temperature modifier;
the silicon rubber is the rubber with the best low-temperature resistance, the glass transition temperature reaches-120 ℃, and meanwhile, the silicon rubber has good weather resistance, so that the silicon rubber becomes the best choice for improving the low-temperature toughness without influencing the weather resistance of the ASA material. In order to further expand the low temperature resistance of the silicone rubber, the plasticizer DOP is added to weaken the interaction between silicon rubber molecular chains and increase the molecular chain activity, so that the glass transition temperature is reduced and the low temperature resistance is improved. However, the silicone rubber has excellent cold resistance and poorer physical and mechanical properties, and the AES and the premixed silicone rubber are extruded and granulated firstly, so that the mechanical properties of the silicone rubber are improved by the AES on the basis of ensuring the low-temperature toughness of the silicone rubber.
(2) Preparing the ultra-low temperature resistant ASA composite material:
a. accurately weighing ASA rubber powder, a low-temperature modifier, a toughening agent and a weather-resistant agent according to a proportion, adding the ASA rubber powder, the low-temperature modifier, the toughening agent and the weather-resistant agent into a high-speed mixing kettle, mixing for 3-5min, and taking out to serve as a first component;
b. accurately weighing AS resin according to the proportion to be used AS a second component;
c. adding the uniformly mixed first component into a double-screw extruder of a double-stage extruder, wherein the length-diameter ratio of the double-screw extruder is 36, the extrusion temperature is 200-; and continuously adding the second component into a single-screw extruder of a double-stage extruder according to the proportion, wherein the length-diameter ratio of the single-screw extruder is 7, the extrusion temperature is 200-240 ℃, the screw rotation speed is 50-70rpm, and the ultra-low temperature resistant ASA composite material is obtained by single-screw shearing, extrusion, granulation and drying.
The AES resin is terpolymer polymerized by acrylonitrile, styrene and ethylene propylene diene monomer, and has the same mechanical property and weather resistance as ASA. The difference is that: the glass transition temperature of the ethylene propylene diene monomer is-60 ℃, which is far higher than that of acrylate rubber in ASA, so that the low-temperature toughness of the ASA can be effectively improved; the AS resin is styrene-acrylonitrile polymer, on one hand, because the compatibility of AS/ASA/AES is very good, the advantages of each material can be fully exerted, and the product has excellent processability and appearance hardness. And on the other hand, the cost of the AS is low, and the market competitiveness of the ASA can be greatly improved.
The invention also utilizes a novel processing technology: a double stage extruder. Due to the high glue content and the high addition proportion of the ASA glue powder, the problem of uneven dispersion exists in the processing process, and the instability of material performance is caused. In order to solve the problem, the invention modifies the existing double-stage extruder, and the modified double-stage extruder is divided into two stages: the first step is a high-speed co-rotating parallel double-screw extruder to realize shearing and pre-dispersion of materials; the second stage is a low speed single screw extruder, which plasticizes and mixes the material again. The two are arranged perpendicularly and orthogonally. A charging barrel, a detector and a weightless scale are arranged at the vertical joint of the double-screw extruder and the single-screw extruder, so that when the materials in the double screws reach the joint, the other part of the materials can be accurately discharged according to the proportion. By firstly melting one part and then adding the other part, the method not only ensures complete plasticization, but also can uniformly disperse.
In the specific operation: adding ASA powder and other additives into a double-screw extruder of a double-stage extruder, ensuring that the powder and each additive are completely melted and uniformly mixed, adding AS granules according to a proportion, synchronously feeding the granules into a single-screw extruder of the double-stage extruder, and ensuring that the powder and each additive are completely and uniformly mixed. The whole processing process is as follows compared with a double-screw extruder: by firstly melting one part and then adding the other part, not only is the complete plasticization of the powder ensured, but also the dispersive mixing of all the materials is completed.
Example 1
The ultra-low temperature resistant ASA composite material comprises the following raw materials, by weight, 1 part of DOP plasticizer (dioctyl phthalate), 20 parts of methyl vinyl silicone rubber, 70 parts of AES resin, 4 parts of ethylene-vinyl acetate copolymer, 4 parts of silane coupling agent, 0.5 part of N, N' -ethylene bis stearamide and 0.5 part of tetra [ β - (3, 5 di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and is prepared by mixing and extruding through a double screw.
60 parts of AS resin, 50 parts of ASA rubber powder, 15 parts of low-temperature modifier, 5 parts of ethylene propylene diene monomer grafted maleic anhydride and 0.5 part of 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole. And extruding the mixture by a double-stage extruder, drying the obtained material for 2-4h in a blower drying oven at 90 ℃, and then performing injection molding to prepare a test sample strip.
Example 2
The super low temperature resistant ASA composite material comprises the following raw materials, by weight, 5 parts of DOP plasticizer (dioctyl phthalate), 70 parts of methyl phenyl vinyl silicone rubber, 20 parts of AES resin, 2 parts of ethylene-vinyl acetate copolymer, 2 parts of silane coupling agent, 0.5 part of N, N' -ethylene bis stearamide and 0.5 part of tetra [ β - (3, 5 di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and is prepared by mixing and extruding through double screws.
50 parts of AS resin, 40 parts of ASA rubber powder, 10 parts of low-temperature modifier, 5 parts of ethylene propylene diene monomer grafted maleic anhydride, 0.5 part of 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole and 0.5 part of bis (2,2,6, 6-tetramethyl piperidyl) sebacate. And extruding the mixture by a double-stage extruder, drying the obtained material for 2-4h in a blower drying oven at 90 ℃, and then performing injection molding to prepare a test sample strip.
Example 3
The ultra-low temperature resistant ASA composite material comprises the following raw materials, by weight, 4 parts of DOP plasticizer (dioctyl phthalate), 25 parts of methyl vinyl silicone rubber, 25 parts of methyl phenyl vinyl silicone rubber, 35 parts of AES resin, 4 parts of ethylene-vinyl acetate copolymer, 5 parts of silane coupling agent, 0.5 part of N, N' -ethylene bis stearamide, 0.5 part of carrier-free silicone master batch, 0.5 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.5 part of tris (2, 4-di-tert-butylphenyl) phosphite, and is mixed and extruded by a double screw to prepare the low temperature modifier.
45 parts of AS resin, 25 parts of ASA rubber powder, 10 parts of low-temperature modifier, 10 parts of ethylene propylene diene monomer grafted maleic anhydride, 0.8 part of 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole and 0.5 part of bis (2,2,6, 6-tetramethyl piperidyl) sebacate. And extruding the mixture by a double-stage extruder, drying the obtained material for 2-4h in a blower drying oven at 90 ℃, and then performing injection molding to prepare a test sample strip.
Example 4
The super low temperature resistant ASA composite material comprises the following raw materials, by weight, 2.5 parts of DOP plasticizer (dioctyl phthalate), 40 parts of methyl vinyl silicone rubber, 50 parts of AES resin, 5 parts of ethylene-ethyl acrylate copolymer, 1 part of silane coupling agent, 0.8 part of carrier-free silicone master batch, 0.7 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 0.5 part of tris (2, 4-di-tert-butylphenyl) phosphite.
30 parts of AS resin, 30 parts of ASA rubber powder, 5 parts of low-temperature modifier, 5 parts of ethylene propylene diene monomer grafted maleic anhydride, 1 part of 2- (2' -hydroxy-3 ',5' -ditert-amyl-phenyl) benzotriazole and 0.5 part of 2- (2' -hydroxy-5 ' -tert-octyl phenyl) benzotriazole. And extruding the mixture by a double-stage extruder, drying the obtained material for 2-4h in a blower drying oven at 90 ℃, and then performing injection molding to prepare a test sample strip.
Example 5
The super low temperature resistant ASA composite material comprises the following raw materials, by weight, 1 part of DOP plasticizer (dioctyl phthalate), 25 parts of ethyl silicone rubber, 65 parts of AES resin, 1 part of active silane grafted ethylene propylene rubber, 4 parts of silane coupling agent, 1 part of oxidized polyethylene wax, 1 part of pentaerythritol fatty acid ester, 1 part of tetra [ β - (3, 5 di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1 part of dioctadecyl pentaerythritol diphosphite, and the raw materials are mixed and extruded by a double screw to prepare the low temperature modifier.
60 parts of AS resin, 20 parts of ASA rubber powder, 20 parts of low-temperature modifier, 10 parts of ethylene propylene diene monomer grafted malan anhydride, 1 part of 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, and 1 part of poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] -1, 6-diadipyl [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] ] ]1 part. And extruding the mixture by a double-stage extruder, drying the obtained material for 2-4h in a blower drying oven at 90 ℃, and then performing injection molding to prepare a test sample strip.
The properties of the products of examples 1 to 5 were tested and evaluated by the following methods.
(1) Notched Izod impact strength: testing according to an ASTMD256 standard; the normal temperature impact test condition is 23 +/-2 ℃, the low temperature impact test condition is that the mixture is frozen for 2-4h at the temperature of-23 +/-2 ℃, and the test is completed within 10 s.
(2) Melt flow rate: the test is carried out according to the standard of ASTM D1238, and the test condition is 220 ℃/10 kg.
(3) Tensile strength: the test speed is 50mm/min according to the standard method of ASTM D638.
(4) Bending strength: the test speed is 2mm/min according to the ASTM D790 standard method.
(5) Ultraviolet aging: the test duration was 500h, according to the ASTM G154 standard.
Comparative example 1
The ultra-low temperature resistant ASA composite material comprises the following raw materials in parts by weight:
60 parts of AS resin, 50 parts of ASA rubber powder, 0 part of low-temperature modifier, 0 part of ethylene propylene diene monomer grafted maleic anhydride and 0.5 part of 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole. And extruding the mixture by a double-stage extruder, drying the obtained material for 2-4h in a blower drying oven at 90 ℃, and then performing injection molding to prepare a test sample strip.
Comparative example 2
The ultra-low temperature resistant ASA composite material comprises the following raw materials, by weight, 1 part of DOP plasticizer (dioctyl phthalate), 20 parts of methyl vinyl silicone rubber, 70 parts of AES resin, 4 parts of ethylene-vinyl acetate copolymer, 4 parts of silane coupling agent, 0.5 part of N, N' -ethylene bis stearamide and 0.5 part of tetra [ β - (3, 5 di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and is prepared by mixing and extruding through a double screw.
60 parts of AS resin, 50 parts of ASA rubber powder, 15 parts of low-temperature modifier, 0 part of ethylene propylene diene monomer grafted maleic anhydride and 0.5 part of 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole. And extruding the mixture by a double-stage extruder, drying the obtained material for 2-4h in a blower drying oven at 90 ℃, and then performing injection molding to prepare a test sample strip.
Comparative example 3
The ultra-low temperature resistant ASA composite material comprises the following raw materials in parts by weight:
60 parts of AS resin, 50 parts of ASA rubber powder, 0 part of low-temperature modifier, 5 parts of ethylene propylene diene monomer grafted maleic anhydride and 0.5 part of 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole. And extruding the mixture by a double-stage extruder, drying the obtained material for 2-4h in a blower drying oven at 90 ℃, and then performing injection molding to prepare a test sample strip.
The performance test results of the ASA composite materials prepared in the examples 1-5 are shown in the following table:
performance test results of the ultra-low temperature resistant ASA composite materials obtained in examples 1 to 5
As can be seen from Table 1, the ultra-low temperature resistant ASA composite material has stable performance, maintains the original mechanical properties and weather resistance of the ASA material, and can improve the low temperature resistance toughness of the material. Examples 1-5 show that as the proportion of low temperature modifier is increased, the impact of the material is increased, especially the low temperature impact, the weather resistance and the tensile/flexural strength are relatively stable, the melt index is slightly reduced, and the processing requirements of the material can be completely met. On the basis of example 1, three comparative examples were made. From comparative examples 1 to 3: when the low-temperature modifier and the ethylene propylene diene monomer grafted maleic anhydride are not added, the normal/low-temperature impact of the ASA material is greatly reduced; when only the low-temperature modifier is added, the normal-temperature impact is improved to a certain extent, and the low-temperature impact is improved remarkably; when only the ethylene propylene diene monomer grafted maleic anhydride is added, the improvement of normal temperature impact is particularly obvious, on one hand, the toughening agent endows the material with toughness, and on the other hand, the ethylene propylene diene monomer grafted maleic anhydride has the function of a part of compatilizer, so that the toughening effect of the ethylene propylene diene monomer grafted maleic anhydride is exerted to the utmost extent. Therefore, the low-temperature resistant ASA composite material obtained by the invention can meet the use requirements of the current market in terms of mechanical properties, processing and weather resistance.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (9)
1. The ultra-low temperature resistant ASA composite material is characterized by comprising the following raw materials in parts by weight: 30-60 parts of AS resin; 20-50 parts of ASA rubber powder; 5-20 parts of a low-temperature modifier; 5-10 parts of a toughening agent; 0.5-2 parts of a weather resistant agent;
the toughening agent is ethylene propylene diene monomer grafted maleic anhydride;
the low-temperature modifier comprises the following raw materials in parts by weight: 20-70 parts of AES resin, 20-70 parts of silicon rubber, 1-5 parts of DOP plasticizer, 1-5 parts of compatilizer, 1-5 parts of silane coupling agent, 0.5-2 parts of processing aid and 0.5-2 parts of antioxidant.
2. The ASA composite material AS claimed in claim 1, wherein the AS resin is an acrylonitrile-styrene copolymer with a weight average molecular weight of 5-15 ten thousand, an acrylonitrile content of 20-30%, and a melt index of 20-70g/10min at 220 ℃/10 kg.
3. The ASA composite material as claimed in claim 1, wherein the ASA rubber powder is a styrene-acrylonitrile-acrylate terpolymer, the acrylate content is 40-60%, and the melt index under the test condition of 220 ℃/10kg is 5-25g/10 min.
4. The ASA composite of claim 1, wherein the weathering agent is 2' - (2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -ditert-pentylphenyl) benzotriazole, 2- (2' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, bis (2,2,6, 6-tetramethylpiperidinyl) sebacate, poly [ [6- [ (1,1,3, 3-tetramethylbutyl) amine ] -1,3, 5-triazine-2, 4-diyl ] [ (2,2,6, 6-tetramethyl-4-piperidi ne ] -1, 6-diadipyl [ (2,2,6, 6-tetramethyl-4-piperidine) imine ] ] ] or a plurality of types thereof.
5. The ASA composite material as claimed in claim 1, wherein the AES resin is a terpolymer of acrylonitrile-styrene-ethylene propylene diene monomer, the content of the ethylene propylene diene monomer is 50-70%, and the melt index under the test condition of 220 ℃/10kg is 5-25g/10 min.
6. The ASA composite material as claimed in claim 1, wherein the silicone rubber is one or more of methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber, and ethyl silicone rubber.
7. The ASA composite material as claimed in claim 1, wherein the compatibilizer is one or more selected from ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and active silane grafted ethylene-propylene rubber, and the antioxidant is one or more selected from pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, and dioctadecyl pentaerythritol diphosphite.
8. The ASA composite material as claimed in claim 1, wherein the processing aid is one or more of N, N' -ethylene bis stearamide, oxidized polyethylene wax, pentaerythritol fatty acid ester or carrier-free silicone master batch.
9. The ASA composite material with ultra-low temperature resistance as claimed in claim 1, wherein the preparation method comprises the following steps:
(1) preparing a low-temperature modifier:
a. accurately weighing the silicon rubber and the DOP plasticizer according to the proportion, and performing premixing treatment to obtain modified silicon rubber;
b. accurately weighing the AES resin, the compatilizer, the coupling agent, the processing aid and the antioxidant according to the proportion, simultaneously adding the AES resin, the compatilizer, the coupling agent, the processing aid and the antioxidant and the modified silicone rubber into a high-mixing pot for mixing for 3-5min, and then drawing strips and granulating through a double-screw extruder to prepare the low-temperature modifier;
(2) preparing the ultra-low temperature resistant ASA composite material:
a. accurately weighing ASA rubber powder, a low-temperature modifier, a toughening agent and a weather-resistant agent according to a proportion, adding the ASA rubber powder, the low-temperature modifier, the toughening agent and the weather-resistant agent into a high-speed mixing kettle, mixing for 3-5min, and taking out to serve as a first component;
b. accurately weighing AS resin according to the proportion to be used AS a second component;
c. adding the uniformly mixed first component into a double-screw extruder of a double-stage extruder, and after shearing and melting by a first-stage double screw, feeding the first component into a second-stage single-screw extruder; and continuously adding the second component into a single-screw extruder of a double-stage extruder according to the proportion, and shearing, extruding, granulating and drying the second component by using a single screw to obtain the ultra-low temperature resistant ASA composite material.
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| CN109517373B (en) * | 2018-11-20 | 2020-11-03 | 安徽江淮汽车集团股份有限公司 | PA6/AES composite material and preparation method thereof |
| CN109721927A (en) * | 2018-12-31 | 2019-05-07 | 苏州洛瑞卡新材料科技有限公司 | A kind of preparation method of flexibility high durable ASA material |
| CN112210182B (en) * | 2020-10-26 | 2023-06-16 | 上海金发科技发展有限公司 | ASA composite material for outdoor use and preparation method thereof |
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| JP2000302941A (en) * | 1999-04-21 | 2000-10-31 | Kanegafuchi Chem Ind Co Ltd | Impact-resistant resin composition |
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| EP0037608B1 (en) * | 1980-04-04 | 1985-03-13 | Stamicarbon B.V. | Polymer composition |
| US4550138A (en) * | 1984-04-23 | 1985-10-29 | Uniroyal, Inc. | Polycarbonate compositions with improved low temperature impact strength |
| US4946894A (en) * | 1986-08-15 | 1990-08-07 | The Dow Chemical Company | Blend comprising large proportions of a EPDM graft terpolymer and relatively smaller proportions of an acrylate rubber |
| DE3839584A1 (en) * | 1988-11-24 | 1990-05-31 | Bayer Ag | AGING-RESISTANT POLYMER ALLOYS |
| DE10054274A1 (en) * | 2000-11-02 | 2002-05-08 | Bayer Ag | Thermoplastic blends with improved low-temperature toughness |
| CN105504634A (en) * | 2015-12-30 | 2016-04-20 | 宁波科普特新材料有限公司 | Low temperature resistant and weather-proof ASA (acrylonitrile styrene acrylate copolymer) material and preparation method thereof |
| CN105860316B (en) * | 2016-06-13 | 2019-05-14 | 上海锦湖日丽塑料有限公司 | Improve the ASA resin composition and preparation method thereof of low-temperature impact toughness |
| CN106188927A (en) * | 2016-08-10 | 2016-12-07 | 深圳毅彩鸿翔新材料科技有限公司 | Uvioresistant weatherability ASA resin, coextruded plastic goods, thin film and goods |
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