CN101985510A - High-weather-resistance acrylate resin composition and preparation method thereof - Google Patents
High-weather-resistance acrylate resin composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-weather-resistance acrylate resin composition and a preparation method thereof. The raw materials of the high-weather-resistance acrylate resin composition comprise the following components in part by weight: 10 to 30 parts of acrylate rubber powder 1, 10 to 30 parts of acrylate rubber powder 2, 30 to 60 parts of SAN resin 1, 5 to 20 parts of heat-resistant modifier, 5 to 15 parts of weather-resistant master batch, 0.3 to 3 parts of lubricant and 0.05 to 0.5 part of antioxidant. The preparation method comprises the following steps of: stirring the raw materials except the weather-resistant master batch to obtain a mixture; adding the mixture from a main feed inlet of a double-screw extruder, and adding the weather-resistant master batch from a side feed inlet; and extruding and pelleting the raw materials by the double-screw extruder to obtain a sample. The high-weather-resistance acrylate resin composition prepared by the method has higher heat resistance, low-temperature impact resistance, weather resistance, excellent size stability and processing property, and is particularly suitable for automobile exterior trim parts, such as radiator grilles, rear-view mirrors, license plates, central pillar plates, outdoor triangular blocks and the like, with high requirements on weather resistance, heat resistance and low-temperature impact resistance.
Description
Technical field
The present invention relates to a kind of resin combination and preparation method thereof, especially relate to a kind of high weatherable acrylate resin composition and method of making the same.
Background technology
The less energy-consumption low emission is the future trend of development of automobile, and according to estimates, in 10 years futures, the weight of automobile also will reduce more than 20%, and plastics are as one of best optional material, and the application on automobile also more and more widely.The application of ABS resin in automotive upholstery is extremely successful, and owing to contain undersaturated carbon-carbon double bond in its used polybutadiene rubber, weather resistance is very poor, can't directly apply in the automobile exterior spare.The ABS product that is used for automobile exterior spare at present all needs to improve its weather resistance through surface-treated methods such as spraying, plating, but further surface treatment procedure is not only wasted time and energy, also can bring the serious environmental pollution problem, deterioration along with global environment, the application of high pollution technologies such as spraying, plating will be restricted, this just need solve the problem of its weather-proof difference from the ABS resin base-material, develop a kind of high weather-proof, high strength, high heat-resisting, high low-temperature impact-resistant, be fit to the resin that automobile exterior spare uses.
ASA resin, AES resin and ACS resin have substituted undersaturated polybutadiene rubber in the ABS resin with saturated acrylic elastomer, terpolymer EP rubber and polyvinyl chloride rubber, weather resistance is greatly increased, but because the second-order transition temperature of these rubber all is higher than polybutadiene rubber, so their resistance to low temperature all is not so good as ABS resin, be easy to generate the problem of cold cracking when in automobile exterior spare, using.In addition, automobile all is placed on outdoor, and noon in summer, surface temperature was spent up to more than 100, also necessary this high temperature of ability of used material, otherwise be easy to generate problems such as buckling deformation, material softening.
The acrylic resin composition that the present invention is directed to the problems referred to above exploitations be on the basis of ASA resin improved its low temperature resistant and resistance to elevated temperatures, and further improved its weather resistance, can satisfy the automobile exterior spare application requiring in severe environment such as outdoor, high temperature, low temperature for a long time fully.
At first, select for use the fluoropolymer of Gao Naihou, polymkeric substance, methyl methacrylate polymer, uv-absorbing agent and the photostabilizer of silicon rubber to make weather-proof master batch, Gao Naihou composition in the weather-proof master batch compiles and is evenly dispersed in the surface of goods easily on the one hand, farthest bring into play its weather resistance, can prevent the problem of the dispersion inequality that light absorber and photostabilizer cause because addition is few on the other hand again.
Secondly, add high rigidity, heat-proof modifier that second-order transition temperature is high and can improve the heat-drawn wire of material, and the fluoropolymer that adds and the polymkeric substance of silicon rubber have very high low-temperature impact-resistant performance, thereby can make product satisfy the application of automobile in high temperature and low temperature environment simultaneously.
In addition, select the composite use of esters of acrylic acid rubber of big particle diameter and small particle size for use, can farthest bring into play on the one hand the toughening effect of rubber, when improving toughness of material and keep sufficiently high rigidity and processing fluidity.
Summary of the invention
Purpose of the present invention is exactly the high weatherable acrylate resin composition and method of making the same that provides a kind of mobile height for the defective that overcomes above-mentioned prior art existence, has very high low-temperature impact-resistant performance, the sufficiently high rigidity of maintenance and processing fluidity.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of high weatherable acrylate resin composition is characterized in that said composition comprises following component and weight part content:
Esters of acrylic acid rubber powder 1 10～30;
Esters of acrylic acid rubber powder 2 10～30;
SAN resin 1 30～60;
Heat-proof modifier 5～20;
Weather-proof master batch 5～15;
Lubricant 0.3～3;
Oxidation inhibitor 0.05～0.5.
Described esters of acrylic acid rubber powder 1 is acrylic elastomer and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, methacrylic ester rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing or ethylene methacrylate rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, weight-average molecular weight is 400000～1000000, average particulate diameter is 500～1200nm, second-order transition temperature is-40～-60 ℃, and relative density is 1.04～1.11g/cm
3, melt temperature is 190～220 ℃.
Described esters of acrylic acid rubber powder 2 is acrylic elastomer and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, methacrylic ester rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing or ethylene methacrylate rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, weight-average molecular weight is 10000～200000, average particulate diameter is 200～600nm, second-order transition temperature is-40～-60 ℃, and relative density is 1.0～1.09g/cm
3, melt temperature is 190～220 ℃.
Described SAN resin 1 is vinyl cyanide and cinnamic multipolymer, and acrylonitrile content is 28～38wt%, and weight-average molecular weight is 100000～250000.
Described heat-proof modifier is one or more in the multiple copolymer of maleic anhydride and methyl methacrylate and cinnamic terpolymer, maleic anhydride and vinyl cyanide and cinnamic terpolymer, N-phenylmaleimide and maleic anhydride and cinnamic terpolymer, alpha-methyl styrene and vinyl cyanide and cinnamic terpolymer or N-phenylmaleimide and maleic anhydride and alpha-methyl styrene and vinyl cyanide, and the second-order transition temperature of heat-proof modifier is 140～250 ℃.
Described weather-proof master batch comprises following component and weight part content:
SAN resin 2 10～30;
Methyl methacrylate polymer 30～70;
Fluoropolymer 5～10;
The polymkeric substance 5～10 of silicon rubber;
Compatilizer 3～8;
Light absorber 3～10;
Photostabilizer 3～10;
Oxidation inhibitor 3～10.
Described SAN resin 2 is superelevation mobile vinyl cyanide and cinnamic multipolymer, and acrylonitrile content is 15～25wt%, and weight-average molecular weight is 30000～80000.
The weight-average molecular weight of described methyl methacrylate polymer is 10000～50000.
Described fluoropolymer is one or more in polyvinylidene difluoride (PVDF), tetrafluoroethylene and ethylene copolymer, vinylidene and TFE copolymer, trifluorochloroethylene and ethylene copolymer or the Meltability polytetrafluorethyletubular.
Silicon rubber content is 60～80wt% in the polymkeric substance of described silicon rubber, and the second-order transition temperature of rubber is lower than subzero 100 ℃.
Described compatilizer is one or more in ethylene-methyl acrylate-maleic anhydride, ethylene-butyl acrylate-maleic anhydride, ethylene-methyl acrylate-glycidyl methacrylate or ethylene-butyl acrylate-glycidyl methacrylate ternary atactic copolymer.
Described light absorber is 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole, 2-(2 ' hydroxyl-6 '-aminomethyl phenyl) benzotriazole, 2,4-dihydroxy benzophenone, 3-[3-(benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl] methyl propionate, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2, one or more in 4-di-t-butyl phenyl ester or 2-(2H-benzotriazole-2-yl) p-cresol.
Described photostabilizer is Succinic Acid and (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcohol) polymkeric substance, poly-[[6-[(1,1,3, the 3-tetramethyl butyl) amine]-1,3,5-triazines-2,4-two bases] [(2,2,6,6-tetramethyl--4-piperidines) imines]-1,6-two dihexyls [(2,2,6,6-tetramethyl--4-piperidines) imines]]], sebacic acid two (2,2,6,6-tetramethyl-piperidyl) ester, sebacic acid (1,2,2,6,6-pentamethyl-piperidines alcohol) ester or two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) one or more in the sebate.
Described oxidation inhibitor is the mixture of single phenol, bis-phenol or polyphenolic substance and bi-ester of phosphite of being obstructed.
Described weather-proof master batch adopts the following steps preparation:
(1) polymkeric substance, 3～8 weight part compatilizers and 3～10 weight part oxidation inhibitor of the silicon rubber of the fluoropolymer of 30～70 weight part methacrylate resins, 10～30 weight part SAN resins, 2,5～10 weight parts, 5～10 weight parts put into homogenizer stir 5～30min after discharging obtain mixture;
(2) the main charging opening of mixture from twin screw extruder added, with 3～10 weight part light absorbers and 3～10 weight part photostabilizers elder generation mixing, from the side loading mouth of twin screw extruder, add again, the barrel zone temperature of control forcing machine is 140～300 ℃, screw speed is 180～600rpm, and extruding pelletization obtains weather-proof master batch.
Described lubricant is that EBS, siloxanes, PE are cured, in Zinic stearas or the Magnesium Stearate one or more.
A kind of high weatherable acrylate resin preparation of compositions method is characterized in that this method may further comprise the steps:
(1) preparation of weather-proof master batch:
Get the raw materials ready according to following component and weight part content:
SAN resin 2 10～30,
Methyl methacrylate polymer 30～70,
Fluoropolymer 5～10,
The polymkeric substance 5～10 of silicon rubber,
Compatilizer 3～8,
Light absorber 3～10,
Photostabilizer 3～10,
Oxidation inhibitor 3～10,
Discharging obtained mixture after polymkeric substance, compatilizer and the oxidation inhibitor of methacrylate resin, SAN resin 2, fluoropolymer, silicon rubber put into homogenizer and stir 5～30min, the main charging opening of mixture from twin screw extruder added, with light absorber and photostabilizer elder generation mixing, from the side loading mouth of twin screw extruder, add again, the barrel zone temperature of control forcing machine is 140～300 ℃, screw speed is 180～600rpm, and extruding pelletization obtains weather-proof master batch;
(2) prepare raw material according to following component and weight part:
Esters of acrylic acid rubber powder 1 10～30,
Esters of acrylic acid rubber powder 2 10～30,
SAN resin 1 30～60,
Heat-proof modifier 5～20,
Weather-proof master batch 5～15,
Lubricant 0.3～3,
Oxidation inhibitor 0.05～0.5;
(3) esters of acrylic acid rubber powder 1, esters of acrylic acid rubber powder 2, SAN resin 1, heat-proof modifier, lubricant and oxidation inhibitor put into homogenizer stir 5～30min after discharging obtain mixture;
(4) the main charging opening of mixture from twin screw extruder added, weather-proof master batch is added from the side loading mouth of twin screw extruder, and the barrel zone temperature of control forcing machine is 180～260 ℃, and screw speed is 180～600rpm, through the twin screw extruder extruding pelletization, obtain sample.
Compared with prior art, the present invention has the following advantages:
(1) adopt the method for weather-proof master batch can solve light absorber on the one hand and photostabilizer disperses uneven problem, adopt fluoropolymer, the polymkeric substance of silicon rubber, the methyl methacrylate polymer of Gao Naihou in the weather-proof on the other hand master batch, mobile high, when injection moulding, can be distributed to the surface of product, thereby effective weather-proof composition is taken and be dispersed in uniformly to the surface of goods, farthest bring into play its weather resistance.
(2) adding in the side direction charging opening of weather resisting agent from twin screw extruder, can be when guaranteeing light absorber and photostabilizer dispersiveness and thermolysis do not take place.
(3) add the heat-drawn wire that high rigidity, heat-proof modifier that second-order transition temperature is high can improve material, and the fluoropolymer that adds and the polymkeric substance of silicon rubber have very high low-temperature impact-resistant performance, thereby can make product satisfy the application of automobile in high temperature and low temperature environment simultaneously.
(4) select the composite use of esters of acrylic acid rubber of big particle diameter and small particle size for use, big particle diameter acrylic elastomer particle can absorb energy, bring out crazing, the small particle size rubber grain then can suppress the crazing development, bring out shear zone, thereby can farthest bring into play the toughening effect of rubber, when improving toughness of material and keep sufficiently high rigidity and processing fluidity.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
Polymkeric substance, 4Kg compatilizer, the 3Kg oxidation inhibitor of 25Kg SAN resin 2,46Kg methyl methacrylate, 7Kg fluoropolymer, 7Kg silicon rubber are joined stirring discharging after 20 minutes in the high-speed mixer, obtain mixture A.
Mixture A is added from the main charging opening of twin screw extruder, with 4Kg light absorber and 4Kg photostabilizer elder generation mixing, from the side loading mouth of twin screw extruder, add again, extruding pelletization obtains weather-proof master batch, the barrel zone temperature of forcing machine is 140 ℃, and screw speed is 180 rev/mins.
With 20KgASA resin 1,15KgASA resin 2,45KgSAN resin 1,10Kg heat-proof modifier, 0.5Kg lubricant, 0.3Kg oxidation inhibitor is put into homogenizer and is stirred that discharging obtains mixture B after 5 minutes.
Mixture B is added from the main charging opening of twin screw extruder, the weather-proof master batch of 10Kg is added from the side loading mouth of twin screw extruder, extruding pelletization obtains the finished product, and the barrel zone temperature of forcing machine is 200 ℃, and screw speed is 180 rev/mins.
Embodiment 2-4
In order to embody the characteristics of the weather-proof acrylic resin composition of above-mentioned height preferably, the present invention has used embodiment 2-4, compared the influence to product performance of different weather-proof master batch consumptions, different heat-proof modifier consumption, concrete material prescription sees table 1 for details, and step is with embodiment 1.
Comparative Examples 1-3
In order to embody the characteristics of the weather-proof acrylic resin composition of above-mentioned height preferably, the present invention has also used and has not added weather-proof master batch, single interpolation ASA resin 1 and ASA resin 2, as a comparative example, and concrete major ingredient prescription sees table 1 for details.
Table 1
For the above high weatherable acrylic resin composition for preparing according to embodiment 1-5 and Comparative Examples 1-3, prepare test bars according to identical injecting condition, concrete physicals test item is as follows:
Tensile strength: measure tensile strength according to ASTM D 178 standards.
Normal temperature notched Izod impact strength: measure the normal temperature notched Izod impact strength according to ASTM D256 standard (1/8 " breach, 23 ℃).
Low temperature notched shock strength: batten is placed in-30 ℃ of cryogenic refrigerators and places 6h, in-30 ℃ of cryostat,s, measure the low temperature notched shock strength then according to ASTM D256 standard (1/8 " breach ,-30 ℃).
Melt flow rate (MFR): (220 ℃ of temperature, load 10Kg) measures melt flow rate (MFR) according to ASTM D 1238 standards.
Heat-drawn wire: the heat-drawn wire of measuring material according to ASTM D 648 standards (batten thickness 6.4mm, loading is 1.82MPa).
Aberration after the photoaging: carry out light aging test, 3000KJ/m according to standard A STM G155-7
2After, measure the aberration of product surface before and after illumination according to standard A STM D2244.
Detected result is as shown in table 2.
Table 2
Performance by table 2 compares, and as can be seen, along with the raising of weather-proof master batch consumption, the weather resistance of material obviously improves, and the flowability of material improves, and the normal temperature shock strength has raising slightly, and low temperature impact strength then significantly improves; Improve the consumption of heat-proof modifier, the heat-drawn wire of material rises, and normal temperature and low temperature impact strength descend, mobile decline; After the composite use of ASA rubber powder of two kinds of different rubber sizes, different molecular weight, different rubber contents, the shock strength of material, flowability and weathering resistance are all good than single ASA rubber powder.Can select ASA rubber powder 1, ASA rubber powder 2, heat-proof modifier, the weather-proof master batch of different amounts according to the performance requriements of client, thereby obtain the material in the ideal goods.
Embodiment 5
A kind of high weatherable acrylate resin preparation of compositions method, this method may further comprise the steps:
(1) preparation of weather-proof master batch:
A, with 10g SAN resin 2, this resin is superelevation mobile vinyl cyanide and cinnamic multipolymer, acrylonitrile content is 15wt%, weight-average molecular weight is 30000, the 30g weight-average molecular weight is 10000 methyl methacrylate polymer, the 5g polyvinylidene difluoride (PVDF), the polymkeric substance of 5g silicon rubber, silicon rubber content is 60wt%, the second-order transition temperature of rubber is lower than subzero 100 ℃, 3g compatilizer ethylene-methyl acrylate-maleic anhydride and 3g oxidation inhibitor, oxidation inhibitor is the mixture of single phenol and bi-ester of phosphite of being obstructed, and discharging obtains mixture after putting into homogenizer and stirring 5min;
B, the main charging opening of mixture from twin screw extruder added, with 3g light absorber 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-and 5-chlorinated benzotriazole and 3g photostabilizer mixing, photostabilizer is Succinic Acid and (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcohol) polymkeric substance adds from the side loading mouth of twin screw extruder again, and the barrel zone temperature of control forcing machine is 140 ℃, screw speed is 600rpm, and extruding pelletization obtains weather-proof master batch;
(2) discharging obtained mixture after 10g put into homogenizer stirring 5min with esters of acrylic acid rubber powder 1,10g esters of acrylic acid rubber powder 2,60g SAN resin 1,20g heat-proof modifier, 0.3g lubricant and 0.05g oxidation inhibitor, wherein esters of acrylic acid rubber powder 1 is acrylic elastomer and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, weight-average molecular weight is 400000, average particulate diameter is 500nm, second-order transition temperature is-40 ℃, and relative density is 1.04g/cm
3, melt temperature is 190 ℃, and esters of acrylic acid rubber powder 2 is acrylic elastomer and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, and weight-average molecular weight is 10000, and average particulate diameter is 200nm, and second-order transition temperature is-40 ℃, and relative density is 1.0g/cm
3Melt temperature is 190 ℃, SAN resin 1 is vinyl cyanide and cinnamic multipolymer, acrylonitrile content is 28wt%, weight-average molecular weight is 100000, and heat-proof modifier is maleic anhydride and methyl methacrylate and cinnamic terpolymer, and second-order transition temperature is 140 ℃, lubricant is EBS, and oxidation inhibitor is the mixture of single phenol and bi-ester of phosphite of being obstructed;
(3) the main charging opening of mixture from twin screw extruder added, the weather-proof master batch that 5g is prepared adds from the side loading mouth of twin screw extruder, the barrel zone temperature of control forcing machine is 180 ℃, and screw speed is 180rpm, obtains sample through the twin screw extruder extruding pelletization.
Embodiment 6
A kind of high weatherable acrylate resin preparation of compositions method, this method may further comprise the steps:
(1) preparation of weather-proof master batch:
A, with 30g SAN resin 2, this resin is superelevation mobile vinyl cyanide and cinnamic multipolymer, acrylonitrile content is 25wt%, weight-average molecular weight is 80000, the 70g weight-average molecular weight is 10000 methyl methacrylate polymer, the mixture of 10g trifluorochloroethylene and ethylene copolymer and Meltability polytetrafluorethyletubular, the polymkeric substance of 10g silicon rubber, silicon rubber content is 80wt%, the second-order transition temperature of rubber is lower than subzero 100 ℃, discharging obtained mixture after 8g compatilizer and 10g oxidation inhibitor were put into homogenizer stirring 30min, wherein compatilizer is the mixture of ethylene-butyl acrylate-maleic anhydride and ethylene-methyl acrylate-glycidyl methacrylate, and oxidation inhibitor is the mixture of hindered bisphenol and bi-ester of phosphite;
B, the main charging opening of mixture from twin screw extruder added, with 10g light absorber and 10g photostabilizer mixing, light absorber is 2,4-dihydroxy benzophenone, 3-[3-(benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl] methyl propionate and 3,5-di-tert-butyl-4-hydroxybenzoic acid-2, the mixture of 4-di-t-butyl phenyl ester, photostabilizer is a sebacic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester and sebacic acid (1,2,2,6,6-pentamethyl-piperidines alcohol) mixture of ester, from the side loading mouth of twin screw extruder, add again, the barrel zone temperature of control forcing machine is 300 ℃, and screw speed is 180rpm, and extruding pelletization obtains weather-proof master batch;
(2) discharging obtained mixture after 30g put into homogenizer stirring 30min with esters of acrylic acid rubber powder 1,30g esters of acrylic acid rubber powder 2,30g SAN resin 1,5g heat-proof modifier, 3g lubricant and 0.5g oxidation inhibitor, wherein esters of acrylic acid rubber powder 1 is methacrylic ester rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, weight-average molecular weight is 1000000, average particulate diameter is 1200nm, second-order transition temperature is-60 ℃, and relative density is 1.11g/cm
3, melt temperature is 220 ℃, esters of acrylic acid rubber powder 2 is methacrylic ester rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, weight-average molecular weight is 200000, average particulate diameter is 600nm, and second-order transition temperature is-60 ℃, and relative density is 1.09g/cm
3Melt temperature is 220 ℃, SAN resin 1 is vinyl cyanide and cinnamic multipolymer, acrylonitrile content is 38wt%, weight-average molecular weight is 250000, and heat-proof modifier is the mixture of N-phenylmaleimide and maleic anhydride and cinnamic terpolymer and alpha-methyl styrene and vinyl cyanide and cinnamic terpolymer, and second-order transition temperature is 250 ℃, lubricant is siloxanes and the cured mixture of PE, and oxidation inhibitor is the mixture of hindered bisphenol and bi-ester of phosphite;
(3) the main charging opening of mixture from twin screw extruder added, the weather-proof master batch that 5g is prepared adds from the side loading mouth of twin screw extruder, the barrel zone temperature of control forcing machine is 260 ℃, and screw speed is 600rpm, obtains sample through the twin screw extruder extruding pelletization.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (17)
1. one kind high weatherable acrylate resin composition is characterized in that, said composition comprises following component and weight part content:
Esters of acrylic acid rubber powder 1 10～30;
Esters of acrylic acid rubber powder 2 10～30;
SAN resin 1 30～60;
Heat-proof modifier 5～20;
Weather-proof master batch 5～15;
Lubricant 0.3～3;
Oxidation inhibitor 0.05～0.5.
2. a kind of high weatherable acrylate resin composition according to claim 1, it is characterized in that, described esters of acrylic acid rubber powder 1 is acrylic elastomer and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, methacrylic ester rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing or ethylene methacrylate rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, weight-average molecular weight is 400000～1000000, average particulate diameter is 500～1200nm, second-order transition temperature is-40～-60 ℃, and relative density is 1.04～1.11g/cm
3, melt temperature is 190～220 ℃.
3. a kind of high weatherable acrylate resin composition according to claim 1, it is characterized in that, described esters of acrylic acid rubber powder 2 is acrylic elastomer and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, methacrylic ester rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing or ethylene methacrylate rubber and vinylbenzene and GRAFT COPOLYMERIZATION OF ACRYLONITRILE thing, weight-average molecular weight is 10000～200000, average particulate diameter is 200～600nm, second-order transition temperature is-40～-60 ℃, and relative density is 1.0～1.09g/cm
3, melt temperature is 190～220 ℃.
4. a kind of high weatherable acrylate resin composition according to claim 1 is characterized in that described SAN resin 1 is vinyl cyanide and cinnamic multipolymer, and acrylonitrile content is 28～38wt%, and weight-average molecular weight is 100000～250000.
5. a kind of high weatherable acrylate resin composition according to claim 1, it is characterized in that, described heat-proof modifier is maleic anhydride and methyl methacrylate and cinnamic terpolymer, maleic anhydride and vinyl cyanide and cinnamic terpolymer, N-phenylmaleimide and maleic anhydride and cinnamic terpolymer, in the multiple copolymer of alpha-methyl styrene and vinyl cyanide and cinnamic terpolymer or N-phenylmaleimide and maleic anhydride and alpha-methyl styrene and vinyl cyanide one or more, the second-order transition temperature of heat-proof modifier are 140～250 ℃.
6. a kind of high weatherable acrylate resin composition according to claim 1 is characterized in that described weather-proof master batch comprises following component and weight part content:
SAN resin 2 10～30;
Methyl methacrylate polymer 30～70;
Fluoropolymer 5～10;
The polymkeric substance 5～10 of silicon rubber;
Compatilizer 3～8;
Light absorber 3～10;
Photostabilizer 3～10;
Oxidation inhibitor 3～10.
7. a kind of high weatherable acrylate resin composition according to claim 6, it is characterized in that, described SAN resin 2 is superelevation mobile vinyl cyanide and cinnamic multipolymer, and acrylonitrile content is 15～25wt%, and weight-average molecular weight is 30000～80000.
8. a kind of high weatherable acrylate resin composition according to claim 6 is characterized in that the weight-average molecular weight of described methyl methacrylate polymer is 10000～50000.
9. a kind of high weatherable acrylate resin composition according to claim 6, it is characterized in that described fluoropolymer is one or more in polyvinylidene difluoride (PVDF), tetrafluoroethylene and ethylene copolymer, vinylidene and TFE copolymer, trifluorochloroethylene and ethylene copolymer or the Meltability polytetrafluorethyletubular.
10. a kind of high weatherable acrylate resin composition according to claim 6 is characterized in that silicon rubber content is 60～80wt% in the polymkeric substance of described silicon rubber, and the second-order transition temperature of rubber is lower than subzero 100 ℃.
11. a kind of high weatherable acrylate resin composition according to claim 6, it is characterized in that described compatilizer is one or more in ethylene-methyl acrylate-maleic anhydride, ethylene-butyl acrylate-maleic anhydride, ethylene-methyl acrylate-glycidyl methacrylate or ethylene-butyl acrylate-glycidyl methacrylate ternary atactic copolymer.
12. a kind of high weatherable acrylate resin composition according to claim 6, it is characterized in that, described light absorber is 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole, 2-(2 ' hydroxyl-6 '-aminomethyl phenyl) benzotriazole, 2,4-dihydroxy benzophenone, 3-[3-(benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl] methyl propionate, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2, one or more in 4-di-t-butyl phenyl ester or 2-(2H-benzotriazole-2-yl) p-cresol.
13. a kind of high weatherable acrylate resin composition according to claim 6 is characterized in that, described photostabilizer is Succinic Acid and (4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcohol) polymkeric substance, poly-[[6-[(1,1,3, the 3-tetramethyl butyl) amine]-1,3,5-triazine-2,4-two bases] [(2,2,6,6-tetramethyl--4-piperidines) imines]-1,6-two dihexyls [(2,2,6,6-tetramethyl--4-piperidines) imines]]], sebacic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester, sebacic acid (1,2,2,6,6-pentamethyl-piperidines alcohol) ester or two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) one or more in the sebate.
14., it is characterized in that described oxidation inhibitor is the mixture of single phenol, bis-phenol or polyphenolic substance and bi-ester of phosphite of being obstructed according to claim 1 or 6 described a kind of high weatherable acrylate resin compositions.
15. a kind of high weatherable acrylate resin composition according to claim 6 is characterized in that, described weather-proof master batch adopts the following steps preparation:
(1) polymkeric substance, 3～8 weight part compatilizers and 3～10 weight part oxidation inhibitor of the silicon rubber of the fluoropolymer of 30～70 weight part methacrylate resins, 10～30 weight part SAN resins, 2,5～10 weight parts, 5～10 weight parts put into homogenizer stir 5～30min after discharging obtain mixture;
(2) the main charging opening of mixture from twin screw extruder added, with 3～10 weight part light absorbers and 3～10 weight part photostabilizers elder generation mixing, from the side loading mouth of twin screw extruder, add again, the barrel zone temperature of control forcing machine is 140～300 ℃, screw speed is 180～600rpm, and extruding pelletization obtains weather-proof master batch.
16. a kind of high weatherable acrylate resin composition according to claim 1 is characterized in that, described lubricant is that EBS, siloxanes, PE are cured, in Zinic stearas or the Magnesium Stearate one or more.
17. one kind high weatherable acrylate resin preparation of compositions method is characterized in that this method may further comprise the steps:
(1) preparation of weather-proof master batch:
Get the raw materials ready according to following component and weight part content:
SAN resin 2 10～30,
Methyl methacrylate polymer 30～70,
Fluoropolymer 5～10,
The polymkeric substance 5～10 of silicon rubber,
Compatilizer 3～8,
Light absorber 3～10,
Photostabilizer 3～10,
Oxidation inhibitor 3～10,
Discharging obtained mixture after polymkeric substance, compatilizer and the oxidation inhibitor of methacrylate resin, SAN resin 2, fluoropolymer, silicon rubber put into homogenizer and stir 5～30min, the main charging opening of mixture from twin screw extruder added, with light absorber and photostabilizer elder generation mixing, from the side loading mouth of twin screw extruder, add again, the barrel zone temperature of control forcing machine is 140～300 ℃, screw speed is 180～600rpm, and extruding pelletization obtains weather-proof master batch;
(2) prepare raw material according to following component and weight part:
Esters of acrylic acid rubber powder 1 10～30,
Esters of acrylic acid rubber powder 2 10～30,
SAN resin 1 30～60,
Heat-proof modifier 5～20,
Weather-proof master batch 5～15,
Lubricant 0.3～3,
Oxidation inhibitor 0.05～0.5;
(3) esters of acrylic acid rubber powder 1, esters of acrylic acid rubber powder 2, SAN resin 1, heat-proof modifier, lubricant and oxidation inhibitor put into homogenizer stir 5～30min after discharging obtain mixture;
(4) the main charging opening of mixture from twin screw extruder added, weather-proof master batch is added from the side loading mouth of twin screw extruder, and the barrel zone temperature of control forcing machine is 180～260 ℃, and screw speed is 180～600rpm, through the twin screw extruder extruding pelletization, obtain sample.
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