A high weather-resistant and high heat-resistant ASA high-rubber powder impact modifier and its preparation method

Abstract

The application discloses a high-weather-resistance and high-heat-resistance ASA high-rubber-powder impact modifier and a preparation method thereof, and belongs to the technical field of high polymer materials.The preparation method of the high-weather-resistance and high-heat-resistance ASA high-rubber-powder impact modifier comprises the following five steps: preparing a seed emulsion, preparing a core layer emulsion, shell layer graft copolymerization, preparing ASA powder and hot blending.The impact strength of the high-weather-resistance and high-heat-resistance ASA high-rubber-powder impact modifier is 25.8-27.8 kJ / m 2 , the Vicat softening temperature is 109.5-114.8 DEG C, the impact strength after weather resistance test is 24.4-26.9 kJ / m 2 , and the amplitude of the decrease of the impact strength before and after the weather resistance test is 1.92-8.55%.

Description

Technical Field

[0001] This invention relates to a high weather-resistant and high heat-resistant ASA high-colloidal powder impact modifier and its preparation method, belonging to the field of polymer materials technology. Background Technology

[0002] ASA high-resin powder is a terpolymer graft copolymer composed of acrylonitrile (A), styrene (S), and acrylate (A), also known as ASA resin, AAS resin, or AAS engineering plastic or ASA engineering plastic. ASA high-resin powder has similar mechanical properties to ABS resin (acrylonitrile-styrene-butadiene copolymer), but because it does not contain double bonds, it has significantly better weather resistance than ABS resin, approximately 10 times higher. ASA high-resin powder can be used alone as an engineering plastic, replacing some ABS, PC, and PVC materials, and is widely used in household appliances, electronics, machinery, transportation, and building materials. However, compared to general-purpose plastics, ASA high-resin powder is relatively expensive and is rarely used alone. In most cases, it is used as an impact modifier to toughen other plastic varieties. In recent years, the application prospects of ASA high-resin powder in the fields of communication equipment and automotive industry have attracted considerable attention. For example, ASA high-resin powder shows promise in meeting the high-performance requirements of 5G communication for high-speed, high-frequency, lossless, and high-capacity information transmission antenna radome products. Furthermore, ASA high-resin powder combines good rigidity and toughness, high gloss, and a less plastic feel than PP, making it very suitable for reinforcing and toughening PP for use as a high-performance automotive grille material. Currently, the use of ASA high-resin powder as an impact modifier in communication equipment and automotive industries still suffers from insufficient weather resistance and heat resistance. Therefore, improving the weather resistance and heat resistance of ASA high-resin powder is of great practical significance.

[0003] The preparation methods for ASA high-rubber powder can be divided into two types: blending and direct synthesis. Direct synthesis involves pre-setting the core-shell ratio of polybutyl acrylate (PBA) and styrene-acrylonitrile (SAN) and then using different polymerization methods (emulsion polymerization, suspension polymerization, or bulk polymerization). Direct synthesis is suitable for the production of specialty materials but has high technical requirements and is rarely used in industrial production. Blending involves mixing two or more different resins to modify the properties of the resin material. For the preparation of ASA high-rubber powder, blending can be further divided into resin blending and emulsion grafting. Resin blending is a purely physical blending method that involves high-temperature blending of polybutyl acrylate rubber (PBA) and styrene-acrylonitrile (SAN) resin. This method produces products with relatively poor performance and is generally not used in industrial production. The process for preparing high-rubber ASA powder via emulsion grafting is very similar to that of ABS resin preparation. The general process includes steps such as synthesizing PBA latex, emulsion graft copolymerization, coagulation, filtration, washing, drying, thermal blending with SAN, and granulation. The emulsion grafting method is simple, the reaction is easy to control, and process parameters such as grafting rate, rubber phase particle size and distribution are easily adjusted. Different grades and properties of high-rubber ASA powder can be produced by adjusting the blending ratio of the core-shell graft copolymer to SAN resin. Due to these advantages, the emulsion grafting method is currently the main method used in industrial production. However, this method also has prominent problems such as poor heat resistance of the core-shell graft copolymer and unsatisfactory heat resistance and weather resistance due to emulsifier residue. Therefore, there is an urgent need to improve the emulsion grafting method to prepare high-rubber ASA powder with excellent weather resistance and heat resistance.

[0004] Chinese patent CN111138610A discloses a high-impact, high-heat-resistant ASA resin, its preparation method, and its applications. The high-impact, high-heat-resistant ASA resin is prepared by mixing a high-impact ASA emulsion with a high-heat-resistant AMS emulsion, co-coagulating under the action of an electrolyte, and then adding polymeric monomers for suspension coating. The high-impact ASA emulsion has a dry basis weight of 50-100% for the gum content. The high-impact, high-heat-resistant ASA resin provided by this invention possesses both good impact resistance and good heat resistance, with a Vicat softening temperature of 100-110℃. The ASA resin prepared by this patent has a high Vicat softening temperature and relatively good heat resistance, but its impact strength fluctuates widely, ranging from 10 to 21 kJ / m. 2 It is not suitable as an impact modifier.

[0005] Chinese patent CN118909199A discloses a grafted latex for high-impact, high-weather-resistant ASA resin, its preparation method, and its application. The preparation method of the grafted latex includes: 1) adding polybutyl acrylate latex, and optionally emulsifiers, chain transfer agents, complexing agents, reducing agents, co-reducing agents, and water to a reactor and stirring until homogeneous, then heating to the polymerization reaction temperature; 2) adding comonomers, initiators, and crosslinking agents dropwise to the reactor for polymerization, wherein the crosslinking agent is added during the first 1 / 3 of the polymerization reaction time. After the reaction is complete, the grafted latex for ASA resin is obtained. This invention improves the integrity of the core-shell structure of the grafted latex during the initial grafting of the polybutyl acrylate latex, thus maintaining the regularity of the dispersed rubber particles. This patent only appropriately improves the weather resistance of ASA resin, but does not improve its heat resistance.

[0006] As can be seen above, the current ASA high-rubber powder impact modifier still has prominent problems such as poor heat resistance, weather resistance, and poor impact strength. Therefore, it is an urgent technical issue with practical application value to prepare a high-weather-resistant and high-heat-resistant ASA high-rubber powder impact modifier. Summary of the Invention

[0007] To address the shortcomings of the existing technology, this invention provides a high-weather-resistant and high-heat-resistant ASA high-rubber powder impact modifier and its preparation method, achieving the following objective: to prepare an ASA high-rubber powder impact modifier with high heat resistance, high weather resistance, and excellent impact strength.

[0008] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0009] A high weather-resistant and high heat-resistant ASA high-rubber powder impact modifier and its preparation method are disclosed. The preparation method of the high weather-resistant and high heat-resistant ASA high-rubber powder impact modifier includes five steps: preparing seed emulsion, preparing core layer emulsion, shell layer graft copolymerization, preparing ASA powder, and hot blending.

[0010] The aforementioned high-weather-resistant and high-heat-resistant ASA high-polymer powder impact modifier has an impact strength of 25.8~27.8 kJ / m. 2 The Vicat softening temperature is 109.5~114.8℃, and the impact strength after weathering resistance testing is 24.4~26.9 kJ / m. 2 The impact strength decreased by 1.92% to 8.55% before and after the weathering test.

[0011] The following are further improvements to the above technical solution:

[0012] Step 1: Prepare seed emulsion

[0013] Under nitrogen protection, deionized water, butyl acrylate, high heat-resistant monomer, high heat-resistant reactive composite emulsifier, and high heat-resistant crosslinking agent are added to the reaction vessel. After high-speed stirring and emulsification into a homogeneous and stable emulsion, the temperature is raised to the reaction temperature, potassium persulfate is added, and the reaction is carried out at a constant temperature and stirred until complete to obtain the seed emulsion.

[0014] The high heat-resistant monomer is one or a mixture of two or more of 2-allylphenylallyl ether, N-vinyloxazolidinone, 3,5-dimethyl-4-vinylisoxazole, 3-acryloyl-2-oxazolidinone, and 2-isopropenyl-2-oxazoline in any mass ratio.

[0015] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0016] The high heat-resistant crosslinking agent is a mixture of one or more of the following in any mass ratio: 1,3,5-benzenetricarboxylic acid triallyl ester, 1,4-diamino-2,5-divinylbenzene, 2,2'-diallyl bisphenol A, bisphenol A dielyl ether, bisphenol A dimethacrylate, 3,3'-diallyl bisphenol A diacetate, 1,2-diphenyl phthalate di-2-propylene ester, 1,3,5-tricyanate triallyl ester, 3-(triallylsilyl)acrylate, and diallyltetramethyldisiloxane.

[0017] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 11~60:23.

[0018] The mass ratio of deionized water, butyl acrylate, high heat-resistant monomer, high heat-resistant reactive composite emulsifier, high heat-resistant crosslinking agent, and potassium persulfate is 120~220:20~60:1~4:1~2.5:0.5~3:0.05~0.3.

[0019] The high-speed stirring emulsification process involves a stirring rate of 2200~4000 rpm.

[0020] The reaction temperature is 60~90℃;

[0021] The constant temperature stirring reaction is complete, the reaction time is 1~3h, and the stirring rate is 600~1000 rpm.

[0022] Step 2: Preparation of core emulsion

[0023] The core layer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water were added to an emulsification kettle. Under nitrogen protection, the mixture was stirred and emulsified into a homogeneous and stable emulsion to obtain the core layer monomer emulsion. Then, the core layer monomer emulsion was added to the seed emulsion, and the temperature was raised and kept constant to the reaction temperature. After the reaction was completed by stirring at constant temperature, the core layer emulsion was obtained.

[0024] The core layer monomer mixture is composed of butyl acrylate and a high heat-resistant monomer.

[0025] The high heat-resistant monomer is one or a mixture of two or more of 2-allylphenylallyl ether, N-vinyloxazolidinone, 3,5-dimethyl-4-vinylisoxazole, 3-acryloyl-2-oxazolidinone, and 2-isopropenyl-2-oxazoline in any mass ratio.

[0026] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0027] The high heat-resistant crosslinking agent is a mixture of one or more of the following in any mass ratio: 1,3,5-benzenetricarboxylic acid triallyl ester, 1,4-diamino-2,5-divinylbenzene, 2,2'-diallyl bisphenol A, bisphenol A dielyl ether, bisphenol A dimethacrylate, 3,3'-diallyl bisphenol A diacetate, 1,2-diphenyl phthalate di-2-propylene ester, 1,3,5-tricyanate triallyl ester, 3-(triallylsilyl)acrylate, and diallyltetramethyldisiloxane.

[0028] The mass ratio of butyl acrylate to high heat-resistant monomer is 100~240:5~30;

[0029] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 11~60:23.

[0030] The mass ratio of the core layer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water is 120~330:8~25:3~9:1~2.5:260~450.

[0031] The mass ratio of the core layer monomer emulsion to the seed emulsion is 100~280:20~60;

[0032] The reaction temperature is 60~90℃;

[0033] The isothermal stirring reaction is completed in 5-8 hours, with a stirring rate of 600-1300 rpm.

[0034] Step 3: Shell graft copolymerization

[0035] The grafted copolymer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water were added to an emulsification kettle. Under nitrogen protection, the mixture was stirred and emulsified into a homogeneous and stable emulsion to obtain a grafted copolymer monomer emulsion. Then, the grafted copolymer monomer emulsion was added to the core layer emulsion, and the temperature was raised and kept constant to the reaction temperature. After the reaction was completed by stirring at constant temperature, the shell layer grafted copolymer emulsion was obtained.

[0036] The grafted copolymer monomer mixture is composed of styrene, acrylonitrile, fluorinated monomers, and high heat-resistant monomers.

[0037] The fluorinated monomer is one or a mixture of two of hexafluorobutyl acrylate and vinyl fluorosilicone oil in any mass ratio;

[0038] The vinyl fluorosilicone oil has a vinyl content of 1.2-2% by mass and a viscosity of 300-1000 mPa·s at 25°C.

[0039] The high heat-resistant monomer is one or a mixture of two or more of 2-allylphenylallyl ether, N-vinyloxazolidinone, 3,5-dimethyl-4-vinylisoxazole, 3-acryloyl-2-oxazolidinone, and 2-isopropenyl-2-oxazoline in any mass ratio.

[0040] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0041] The high heat-resistant crosslinking agent is a mixture of one or more of the following in any mass ratio: 1,3,5-benzenetricarboxylic acid triallyl ester, 1,4-diamino-2,5-divinylbenzene, 2,2'-diallyl bisphenol A, bisphenol A dielyl ether, bisphenol A dimethacrylate, 3,3'-diallyl bisphenol A diacetate, 1,2-diphenyl phthalate di-2-propylene ester, 1,3,5-tricyanate triallyl ester, 3-(triallylsilyl)acrylate, and diallyltetramethyldisiloxane.

[0042] The mass ratio of styrene, acrylonitrile, fluorinated monomer, and high heat-resistant monomer is 40~90:30~110:4~10:2~7;

[0043] The mass ratio of the grafted copolymer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water is 100~220:6~13:2~5:0.3~1:200~390;

[0044] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 11~60:23.

[0045] The mass ratio of the grafted copolymer emulsion to the core layer emulsion is 100~300:90~150;

[0046] The reaction temperature is 65~90℃;

[0047] The isothermal stirring reaction is completed in 5-10 hours, with a stirring rate of 800-1900 rpm.

[0048] Step 4: Prepare ASA powder

[0049] The shell graft copolymer emulsion was kept at a constant temperature of 90-96°C, and then magnesium sulfate aqueous solution was added. The mixture was stirred at a constant temperature for 1-2.5 hours to demulsify. After demulsification, the mixture was cooled to room temperature and filtered. The filtered solid was washed with deionized water and dried thoroughly to obtain ASA powder.

[0050] The magnesium sulfate aqueous solution has a mass concentration of 10-20 wt%.

[0051] The mass ratio of the shell graft copolymer emulsion to the magnesium sulfate aqueous solution is 100~200:30~80;

[0052] The washing with deionized water is performed 3 to 5 times, and the amount of deionized water used each time is equal to the wet mass of the solid being washed.

[0053] The drying process involves a drying temperature of 50-65℃ and a drying time of 15-22 hours.

[0054] Step 5: Hot blending

[0055] ASA powder, SAN resin, and reactive interface compatibilizer are added to a twin-screw extruder and melt-extruded at 220~245℃. After cooling and granulation, ASA high-rubber powder impact modifier is obtained.

[0056] The reactive interface compatibilizer is one or more of the following in any mass ratio: triethoxysilylpropylmaleic acid, 11-maleamidoundecanoic acid, and N-(n-hexadecyl)-maleimide.

[0057] The mass ratio of ASA powder, SAN resin, and reactive interface compatibilizer is 25~50:60~140:1~5.

[0058] Compared with the prior art, the present invention achieves the following beneficial effects:

[0059] 1. This invention improves the Vicat softening temperature of ASA high-rubber powder impact modifier by adding monomers with high-temperature resistance, namely unsaturated compounds containing aromatic rings or heterocycles. The heat-resistant chemical structures of these unsaturated compounds containing aromatic rings or heterocycles mainly include phenyl aromatic rings, oxazole rings, and azoline heterocycles. Through the free radical reaction of unsaturated double bonds, these heat-resistant chemical structures are introduced into the seed kernel, core layer, and shell layer of the ASA high-rubber powder impact modifier. The overall heat resistance of the ASA high-rubber powder impact modifier is greatly improved. Therefore, the ASA high-rubber powder impact modifier obtained by this invention has a very high Vicat softening temperature.

[0060] 2. In order to simultaneously improve the heat resistance and impact strength of ASA high-rubber powder impact modifier, this invention introduces high-heat-resistant crosslinking agents into the seed kernel, core layer, and shell layer of the ASA high-rubber powder impact modifier. The chemical structure of these high-heat-resistant crosslinking agents contains high-heat-resistant aromatic rings or organosilicon groups, and also contains two double bonds. These two double bonds introduce the high-heat-resistant aromatic rings or organosilicon groups into the polymer chain segments of the ASA high-rubber powder impact modifier through free radical reaction, forming a three-dimensional crosslinking network, thereby significantly improving the heat resistance and impact strength of the ASA high-rubber powder impact modifier. In addition, the crosslinking network formed by the aromatic rings or organosilicon groups as bridging segments has a relatively high density, which also plays a certain role in improving the weather resistance of the ASA high-rubber powder impact modifier.

[0061] 3. To systematically and comprehensively improve the heat resistance and impact strength of ASA high-impact powder impact modifier, this invention has also made innovative explorations in the selection of emulsifiers. Conventional nonionic surfactants, such as fatty alcohol polyoxyethylene ethers, do not contain unsaturated carbon-carbon double bonds and are not reactive with the various unsaturated monomers used in the synthesis of ASA high-impact powder impact modifiers. Therefore, they exist in a free monomolecular state within the ASA high-impact powder impact modifier. These monomolecular fatty alcohol polyoxyethylene ethers have a certain plasticizing effect, and their migration during long-term use... It can also affect the weather resistance of impact modifiers, and seriously affect the heat resistance and weather resistance of ASA high-rubber powder impact modifiers. This invention designs a high-heat-resistant reactive composite emulsifier composed of tristyrylphenol polyoxyethylene ether and allyloxy isotridecyl alcohol polyoxyethylene ether. Both of these nonionic surfactants contain unsaturated carbon-carbon double bonds, and can ultimately react into the polymer chain of ASA high-rubber powder impact modifiers in a chemical bonding manner, avoiding the plasticizing effect of conventional surfactants, and thus improving heat resistance, impact strength and weather resistance.

[0062] 4. In order to further improve the weather resistance of ASA high-rubber powder impact modifier, the present invention adds fluorinated monomers during the shell graft copolymerization process. These fluorinated monomers in the shell polymerize into the polymer chain segments of the shell, which can cover and protect the core of the rubber phase. Therefore, it can slow down the aging rate of the core rubber phase and greatly enhance the weather resistance of ASA high-rubber powder impact modifier.

[0063] 5. In the process of shell graft copolymerization, the fluorinated monomer added in this invention will significantly reduce the polarity of the shell, thus causing certain obstacles to the compatibility between the shell and SAN resin. If the compatibility is impaired, it will affect the graft copolymerization reaction between the shell and SAN resin during the hot blending process, resulting in microscopic phase separation. As a result, it will lead to a comprehensive decline in the various properties of the ASA high-impact powder impact modifier. Therefore, this invention adds a reactive interface compatibilizer during the hot blending process. It utilizes the non-polar organosilicon groups or long-chain alkane groups contained in the three substances triethoxysilylpropylmaleic acid, 11-maleamidoundecanoic acid, and N-(n-hexadecyl)-maleimide, as well as the polar structures of maleic acid, maleamide, or maleimide contained in these three substances with strong polarity and unsaturated reactive functional groups, to improve the compatibility between the shell and SAN resin, thereby avoiding microscopic phase separation, and finally obtaining an ASA high-impact powder impact modifier with excellent comprehensive performance.

[0064] 6. The high weather resistance and high heat resistance ASA high-rubber powder impact modifier prepared by this invention has an impact strength of 25.8~27.8 kJ / m. 2 The Vicat softening temperature is 109.5~114.8℃, and the impact strength after weathering resistance testing is 24.4~26.9 kJ / m. 2 The impact strength decreased by 1.92% to 8.55% before and after the weather resistance test. Detailed Implementation

[0065] The preferred embodiments of the present invention are described below. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0066] Example 1: A method for preparing a high weather-resistant and high heat-resistant ASA high-rubber powder impact modifier.

[0067] Step 1: Prepare seed emulsion

[0068] Under nitrogen protection, deionized water, butyl acrylate, high heat-resistant monomer, high heat-resistant reactive composite emulsifier, and high heat-resistant crosslinking agent are added to the reaction vessel. After high-speed stirring and emulsification into a homogeneous and stable emulsion, the temperature is raised to the reaction temperature, potassium persulfate is added, and the reaction is carried out at a constant temperature and stirred until complete to obtain the seed emulsion.

[0069] The high heat-resistant monomer is 2-allylphenylallyl ether;

[0070] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0071] The high heat-resistant crosslinking agent is 1,3,5-benzenetricarboxylic acid triallyl ester;

[0072] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 40:23.

[0073] The mass ratio of deionized water, butyl acrylate, high heat-resistant monomer, high heat-resistant reactive composite emulsifier, high heat-resistant crosslinking agent, and potassium persulfate is 150:50:3:2:1:0.1.

[0074] The high-speed stirring emulsification process involves a stirring rate of 3000 rpm.

[0075] The reaction temperature is 80°C;

[0076] The constant temperature stirring reaction was completed in 2 hours, with a stirring rate of 900 rpm.

[0077] Step 2: Preparation of core emulsion

[0078] The core layer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water were added to an emulsification kettle. Under nitrogen protection, the mixture was stirred and emulsified into a homogeneous and stable emulsion to obtain the core layer monomer emulsion. Then, the core layer monomer emulsion was added to the seed emulsion, and the temperature was raised and kept constant to the reaction temperature. After the reaction was completed by stirring at constant temperature, the core layer emulsion was obtained.

[0079] The core layer monomer mixture is composed of butyl acrylate and a high heat-resistant monomer.

[0080] The high heat-resistant monomer is 2-allylphenylallyl ether;

[0081] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0082] The high heat-resistant crosslinking agent is 1,3,5-benzenetricarboxylic acid triallyl ester;

[0083] The mass ratio of butyl acrylate to the high heat-resistant monomer is 180:15.

[0084] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 40:23.

[0085] The mass ratio of the core layer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water is 180:15:6:2:360.

[0086] The mass ratio of the core layer monomer emulsion to the seed emulsion is 180:50;

[0087] The reaction temperature is 80°C;

[0088] The isothermal stirring reaction was completed in 7 hours at a stirring rate of 900 rpm.

[0089] Step 3: Shell graft copolymerization

[0090] The grafted copolymer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water were added to an emulsification kettle. Under nitrogen protection, the mixture was stirred and emulsified into a homogeneous and stable emulsion to obtain a grafted copolymer monomer emulsion. Then, the grafted copolymer monomer emulsion was added to the core layer emulsion, and the temperature was raised and kept constant to the reaction temperature. After the reaction was completed by stirring at constant temperature, the shell layer grafted copolymer emulsion was obtained.

[0091] The grafted copolymer monomer mixture is composed of styrene, acrylonitrile, fluorinated monomers, and high heat-resistant monomers.

[0092] The fluorinated monomer is hexafluorobutyl acrylate.

[0093] The high heat-resistant monomer is 2-allylphenylallyl ether;

[0094] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0095] The high heat-resistant crosslinking agent is 1,3,5-benzenetricarboxylic acid triallyl ester;

[0096] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 30:23.

[0097] The mass ratio of styrene, acrylonitrile, fluorinated monomer, and high heat-resistant monomer is 70:80:9:5.

[0098] The mass ratio of the grafted copolymer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water is 150:8:4:0.6:290.

[0099] The mass ratio of the grafted copolymer emulsion to the core layer emulsion is 200:120.

[0100] The reaction temperature is 80°C;

[0101] The constant-temperature stirring reaction was completed in 8 hours at a stirring rate of 1100 rpm.

[0102] Step 4: Prepare ASA powder

[0103] The shell graft copolymer emulsion was kept at a constant temperature of 94°C, and then magnesium sulfate aqueous solution was added. The mixture was stirred at a constant temperature for 2 hours to break the emulsion. After the emulsion was broken, the mixture was cooled to room temperature and filtered. The filtered solid was washed with deionized water and dried thoroughly to obtain ASA powder.

[0104] The magnesium sulfate aqueous solution has a mass concentration of 14 wt%.

[0105] The mass ratio of the shell graft copolymer emulsion to the magnesium sulfate aqueous solution is 160:50.

[0106] The deionized water washing is performed 4 times, and the amount of deionized water used each time is equal to the wet mass of the solid being washed.

[0107] The process involves thorough drying at a temperature of 60°C for 20 hours.

[0108] Step 5: Hot blending

[0109] ASA powder, SAN resin, and reactive interface compatibilizer are added to a twin-screw extruder and melt-extruded at 235°C. After cooling and granulation, ASA high-rubber powder impact modifier is obtained.

[0110] The reactive interface compatibilizer is triethoxysilylpropylmaleic acid;

[0111] The mass ratio of ASA powder, SAN resin, and reactive interface compatibilizer is 40:90:4.

[0112] Example 2: A method for preparing a high weather-resistant and high heat-resistant ASA high-polymer powder impact modifier

[0113] Step 1: Prepare seed emulsion

[0114] Under nitrogen protection, deionized water, butyl acrylate, high heat-resistant monomer, high heat-resistant reactive composite emulsifier, and high heat-resistant crosslinking agent are added to the reaction vessel. After high-speed stirring and emulsification into a homogeneous and stable emulsion, the temperature is raised to the reaction temperature, potassium persulfate is added, and the reaction is carried out at a constant temperature and stirred until complete to obtain the seed emulsion.

[0115] The highly heat-resistant monomer is N-vinyloxazolidinone;

[0116] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0117] The high heat-resistant crosslinking agent is 1,4-diamino-2,5-divinylbenzene;

[0118] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 11:23.

[0119] The mass ratio of deionized water, butyl acrylate, high heat-resistant monomer, high heat-resistant reactive composite emulsifier, high heat-resistant crosslinking agent, and potassium persulfate is 120:20:1:1:0.5:0.05.

[0120] The high-speed stirring emulsification process involves a stirring rate of 2200 rpm.

[0121] The reaction temperature is 60°C;

[0122] The constant temperature stirring reaction was completed in 1 hour, and the stirring rate was 600 rpm.

[0123] Step 2: Preparation of core emulsion

[0124] The core layer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water were added to an emulsification kettle. Under nitrogen protection, the mixture was stirred and emulsified into a homogeneous and stable emulsion to obtain the core layer monomer emulsion. Then, the core layer monomer emulsion was added to the seed emulsion, and the temperature was raised and kept constant to the reaction temperature. After the reaction was completed by stirring at constant temperature, the core layer emulsion was obtained.

[0125] The core layer monomer mixture is composed of butyl acrylate and a high heat-resistant monomer.

[0126] The highly heat-resistant monomer is N-vinyloxazolidinone;

[0127] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0128] The high heat-resistant crosslinking agent is 1,4-diamino-2,5-divinylbenzene;

[0129] The mass ratio of butyl acrylate to the high heat-resistant monomer is 100:5;

[0130] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 11:23.

[0131] The mass ratio of the core layer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water is 120:8:3:1:260.

[0132] The mass ratio of the core layer monomer emulsion to the seed emulsion is 100:20;

[0133] The reaction temperature is 60°C;

[0134] The isothermal stirring reaction was completed in 5 hours at a stirring rate of 600 rpm.

[0135] Step 3: Shell graft copolymerization

[0136] The grafted copolymer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water were added to an emulsification kettle. Under nitrogen protection, the mixture was stirred and emulsified into a homogeneous and stable emulsion to obtain a grafted copolymer monomer emulsion. Then, the grafted copolymer monomer emulsion was added to the core layer emulsion, and the temperature was raised and kept constant to the reaction temperature. After the reaction was completed by stirring at constant temperature, the shell layer grafted copolymer emulsion was obtained.

[0137] The grafted copolymer monomer mixture is composed of styrene, acrylonitrile, fluorinated monomers, and high heat-resistant monomers.

[0138] The fluorinated monomer is vinyl fluorosilicone acrylate;

[0139] The vinyl fluorosilicone oil has a vinyl content of 1.5% by mass and a viscosity of 800 mPa·s at 25°C.

[0140] The highly heat-resistant monomer is N-vinyloxazolidinone;

[0141] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0142] The high heat-resistant crosslinking agent is 1,4-diamino-2,5-divinylbenzene;

[0143] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 11:23.

[0144] The mass ratio of styrene, acrylonitrile, fluorinated monomer, and high heat-resistant monomer is 40:30:4:2.

[0145] The mass ratio of the grafted copolymer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water is 100:6:2:0.3:200.

[0146] The mass ratio of the grafted copolymer emulsion to the core layer emulsion is 100:90;

[0147] The reaction temperature is 65°C;

[0148] The constant-temperature stirring reaction was completed in 5 hours at a stirring rate of 800 rpm.

[0149] Step 4: Prepare ASA powder

[0150] The shell graft copolymer emulsion was kept at a constant temperature of 90°C, and then magnesium sulfate aqueous solution was added. The mixture was stirred at a constant temperature for 1 hour to break the emulsion. After the emulsion was broken, the mixture was cooled to room temperature and filtered. The filtered solid was washed with deionized water and dried thoroughly to obtain ASA powder.

[0151] The magnesium sulfate aqueous solution has a mass concentration of 10 wt%.

[0152] The mass ratio of the shell graft copolymer emulsion to the magnesium sulfate aqueous solution is 100:30;

[0153] The deionized water washing is performed three times, with the amount of deionized water used each time being equal to the wet mass of the solid being washed.

[0154] The drying process involves thorough drying at a temperature of 50°C for 15 hours.

[0155] Step 5: Hot blending

[0156] ASA powder, SAN resin, and reactive interface compatibilizer are added to a twin-screw extruder and melt-extruded at 220°C. After cooling and granulation, ASA high-rubber powder impact modifier is obtained.

[0157] The reactive interface compatibilizer is 11-maleamidoundecanoic acid;

[0158] The mass ratio of ASA powder, SAN resin, and reactive interface compatibilizer is 25:60:1.

[0159] Example 3: A method for preparing a high weather-resistant and high heat-resistant ASA high-polymer powder impact modifier

[0160] Step 1: Prepare seed emulsion

[0161] Under nitrogen protection, deionized water, butyl acrylate, high heat-resistant monomer, high heat-resistant reactive composite emulsifier, and high heat-resistant crosslinking agent are added to the reaction vessel. After high-speed stirring and emulsification into a homogeneous and stable emulsion, the temperature is raised to the reaction temperature, potassium persulfate is added, and the reaction is carried out at a constant temperature and stirred until complete to obtain the seed emulsion.

[0162] The highly heat-resistant monomer is 3,5-dimethyl-4-vinylisoxazole;

[0163] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0164] The high heat-resistant crosslinking agent is 2,2'-diallylbisphenol A;

[0165] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 60:23.

[0166] The mass ratio of deionized water, butyl acrylate, high heat-resistant monomer, high heat-resistant reactive composite emulsifier, high heat-resistant crosslinking agent, and potassium persulfate is 220:60:4:2.5:3:0.3.

[0167] The high-speed stirring emulsification process involves a stirring rate of 4000 rpm.

[0168] The reaction temperature is 90°C;

[0169] The constant temperature stirring reaction was completed in 3 hours, with a stirring rate of 1000 rpm.

[0170] Step 2: Preparation of core emulsion

[0171] The core layer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water were added to an emulsification kettle. Under nitrogen protection, the mixture was stirred and emulsified into a homogeneous and stable emulsion to obtain the core layer monomer emulsion. Then, the core layer monomer emulsion was added to the seed emulsion, and the temperature was raised and kept constant to the reaction temperature. After the reaction was completed by stirring at constant temperature, the core layer emulsion was obtained.

[0172] The core layer monomer mixture is composed of butyl acrylate and a high heat-resistant monomer.

[0173] The highly heat-resistant monomer is 3,5-dimethyl-4-vinylisoxazole;

[0174] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0175] The high heat-resistant crosslinking agent is 2,2'-diallylbisphenol A;

[0176] The mass ratio of butyl acrylate to the high heat-resistant monomer is 240:30.

[0177] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 60:23.

[0178] The mass ratio of the core layer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water is 330:25:9:2.5:450.

[0179] The mass ratio of the core layer monomer emulsion to the seed emulsion is 280:60;

[0180] The reaction temperature is 90°C;

[0181] The isothermal stirring reaction was completed in 8 hours at a stirring rate of 1300 rpm.

[0182] Step 3: Shell graft copolymerization

[0183] The grafted copolymer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water were added to an emulsification kettle. Under nitrogen protection, the mixture was stirred and emulsified into a homogeneous and stable emulsion to obtain a grafted copolymer monomer emulsion. Then, the grafted copolymer monomer emulsion was added to the core layer emulsion, and the temperature was raised and kept constant to the reaction temperature. After the reaction was completed by stirring at constant temperature, the shell layer grafted copolymer emulsion was obtained.

[0184] The grafted copolymer monomer mixture is composed of styrene, acrylonitrile, fluorinated monomers, and high heat-resistant monomers.

[0185] The fluorinated monomer is vinyl fluorosilicone acrylate;

[0186] The vinyl fluorosilicone oil has a vinyl content of 1.2% by mass and a viscosity of 300 mPa·s at 25°C.

[0187] The highly heat-resistant monomer is 3,5-dimethyl-4-vinylisoxazole;

[0188] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0189] The high heat-resistant crosslinking agent is 2,2'-diallylbisphenol A;

[0190] The mass ratio of the tristyrene-phenylphenol polyoxyethylene ether to allyloxyisotridecyl alcohol polyoxyethylene ether is 60:23.

[0191] The mass ratio of styrene, acrylonitrile, fluorinated monomer, and high heat-resistant monomer is 90:110:10:7.

[0192] The mass ratio of the grafted copolymer monomer mixture, high heat-resistant crosslinking agent, high heat-resistant reactive composite emulsifier, potassium persulfate, and deionized water is 220:13:5:1:390.

[0193] The mass ratio of the grafted copolymer emulsion to the core layer emulsion is 300:150.

[0194] The reaction temperature is 90°C;

[0195] The isothermal stirring reaction was completed in 10 hours at a stirring rate of 1900 rpm.

[0196] Step 4: Prepare ASA powder

[0197] The shell-grafted copolymer emulsion was kept at a constant temperature of 96°C, and then magnesium sulfate aqueous solution was added. The mixture was stirred at a constant temperature for 2.5 hours to demulsify. After demulsification, the mixture was cooled to room temperature and filtered. The filtered solid was washed with deionized water and dried thoroughly to obtain ASA powder.

[0198] The magnesium sulfate aqueous solution has a mass concentration of 20 wt%.

[0199] The mass ratio of the shell graft copolymer emulsion to the magnesium sulfate aqueous solution is 200:80;

[0200] The deionized water washing is performed 5 times, and the amount of deionized water used each time is equal to the wet mass of the solid being washed.

[0201] The process involves thorough drying at a temperature of 65°C for 22 hours.

[0202] Step 5: Hot blending

[0203] ASA powder, SAN resin, and reactive interface compatibilizer are added to a twin-screw extruder and melt-extruded at 245°C. After cooling and granulation, ASA high-rubber powder impact modifier is obtained.

[0204] The reactive interfacial compatibilizer is N-(n-hexadecyl)-maleimide;

[0205] The mass ratio of ASA powder, SAN resin, and reactive interface compatibilizer is 50:140:5.

[0206] Example 4: A method for preparing a high weather-resistant and high heat-resistant ASA high-polymer powder impact modifier

[0207] The high heat-resistant monomer is 3-acryloyl-2-azolidinone;

[0208] The high heat-resistant crosslinking agent is bisphenol A dielyl ether;

[0209] Other operations are the same as in Example 1.

[0210] Step 2: Preparation of core emulsion

[0211] The high heat-resistant monomer is 3-acryloyl-2-azolidinone;

[0212] The high heat-resistant crosslinking agent is bisphenol A dielyl ether;

[0213] Other operations are the same as in Example 1.

[0214] Step 3: Shell graft copolymerization

[0215] The fluorinated monomer is vinyl fluorosilicone oil;

[0216] The vinyl fluorosilicone oil has a vinyl content of 2% by mass and a viscosity of 1000 mPa·s at 25°C.

[0217] The high heat-resistant monomer is 3-acryloyl-2-azolidinone;

[0218] The high heat-resistant reactive composite emulsifier is a mixture of tristyrene-phenylphenol polyoxyethylene ether and allyloxyisotridecyl alcohol polyoxyethylene ether;

[0219] The high heat-resistant crosslinking agent is bisphenol A dielyl ether;

[0220] Other operations are the same as in Example 1.

[0221] Steps 4 and 5 are the same as in Example 1.

[0222] Example 5: A method for preparing a high weather-resistant and high heat-resistant ASA high-polymer powder impact modifier

[0223] Step 1: Prepare seed emulsion

[0224] The highly heat-resistant monomer is 2-isopropenyl-2-oxazoline;

[0225] The high heat-resistant crosslinking agent is bisphenol A dimethacrylate;

[0226] Other operations are the same as in Example 1.

[0227] Step 2: Preparation of core emulsion

[0228] The highly heat-resistant monomer is 2-isopropenyl-2-oxazoline;

[0229] The high heat-resistant crosslinking agent is bisphenol A dimethacrylate;

[0230] Other operations are the same as in Example 1.

[0231] Step 3: Shell graft copolymerization

[0232] The highly heat-resistant monomer is 2-isopropenyl-2-oxazoline;

[0233] The high heat-resistant crosslinking agent is bisphenol A dimethacrylate;

[0234] Other operations are the same as in Example 1.

[0235] Steps 4 and 5 are the same as in Example 1.

[0236] Example 6: A method for preparing a high weather-resistant and high heat-resistant ASA high-polymer powder impact modifier

[0237] Step 1: Prepare seed emulsion

[0238] The high heat-resistant crosslinking agent is 3,3'-diallyl bisphenol A diacetate, and other operations are the same as in Example 1.

[0239] Step 2: Preparation of core emulsion

[0240] The high heat-resistant crosslinking agent is 3,3'-diallyl bisphenol A diacetate, and other operations are the same as in Example 1.

[0241] Step 3: Shell graft copolymerization

[0242] The high heat-resistant crosslinking agent is 3,3'-diallyl bisphenol A diacetate, and other operations are the same as in Example 1.

[0243] Steps 4 and 5 are the same as in Example 1.

[0244] Example 7: A method for preparing a high weather-resistant and high heat-resistant ASA high-polymer powder impact modifier

[0245] Step 1: Prepare seed emulsion

[0246] The high heat-resistant crosslinking agent is di-2-propenyl 1,2-phthalic acid, and other operations are the same as in Example 1.

[0247] Step 2: Preparation of core emulsion

[0248] The high heat-resistant crosslinking agent is di-2-propenyl 1,2-phthalic acid, and other operations are the same as in Example 1.

[0249] Step 3: Shell graft copolymerization

[0250] The high heat-resistant crosslinking agent is di-2-propenyl 1,2-phthalic acid, and other operations are the same as in Example 1.

[0251] Steps 4 and 5 are the same as in Example 1.

[0252] Example 8: A method for preparing a high weather-resistant and high heat-resistant ASA high-polymer powder impact modifier

[0253] Step 1: Prepare seed emulsion

[0254] The high heat-resistant crosslinking agent is 1,3,5-triallyl cyanurate, and other operations are the same as in Example 1.

[0255] Step 2: Preparation of core emulsion

[0256] The high heat-resistant crosslinking agent is 1,3,5-triallyl cyanurate, and other operations are the same as in Example 1.

[0257] Step 3: Shell graft copolymerization

[0258] The high heat-resistant crosslinking agent is 1,3,5-triallyl cyanurate, and other operations are the same as in Example 1.

[0259] Steps 4 and 5 are the same as in Example 1.

[0260] Example 9: A method for preparing a high weather-resistant and high heat-resistant ASA high-polymer powder impact modifier

[0261] Step 1: Prepare seed emulsion

[0262] The high heat-resistant crosslinking agent is propyl 3-(triallylsilyl)acrylate, and other operations are the same as in Example 1.

[0263] Step 2: Preparation of core emulsion

[0264] The high heat-resistant crosslinking agent is propyl 3-(triallylsilyl)acrylate, and other operations are the same as in Example 1.

[0265] Step 3: Shell graft copolymerization

[0266] The high heat-resistant crosslinking agent is propyl 3-(triallylsilyl)acrylate, and other operations are the same as in Example 1.

[0267] Steps 4 and 5 are the same as in Example 1.

[0268] Example 10: A method for preparing a high weather-resistant and high heat-resistant ASA high-polymer powder impact modifier

[0269] Step 1: Prepare seed emulsion

[0270] The high heat-resistant crosslinking agent is diallyltetramethyldisiloxane, and other operations are the same as in Example 1.

[0271] Step 2: Preparation of core emulsion

[0272] The high heat-resistant crosslinking agent is diallyltetramethyldisiloxane, and other operations are the same as in Example 1.

[0273] Step 3: Shell graft copolymerization

[0274] The high heat-resistant crosslinking agent is diallyltetramethyldisiloxane, and other operations are the same as in Example 1.

[0275] Steps 4 and 5 are the same as in Example 1.

[0276] Comparative Example 1: Based on Example 1, in steps 1 (preparation of seed emulsion), 2 (preparation of core emulsion), and 3 (shell graft copolymerization), no high heat-resistant monomer was added. In steps 1, 2, and 3 involving the addition of high heat-resistant monomers, all were replaced in equal amounts with the corresponding conventional monomers used in those steps. The specific operations are as follows:

[0277] Step 1: Prepare seed emulsion

[0278] Replace 3 parts of high heat-resistant monomer with 3 parts of butyl acrylate in equal amounts, and perform the other operations as in Example 1;

[0279] Step 2: Preparation of core emulsion

[0280] Replace 15 parts of high heat-resistant monomer with 15 parts of butyl acrylate, and perform the other operations as in Example 1;

[0281] Step 3: Shell graft copolymerization

[0282] Replace 5 parts of high heat-resistant monomer with 5 parts of styrene in equal amounts, and perform the other operations as in Example 1;

[0283] Steps 4 and 5 are the same as in Example 1.

[0284] Comparative Example 2: Based on Example 1, in steps 1 (preparation of seed emulsion), 2 (preparation of core emulsion), and 3 (shell graft copolymerization), no high heat-resistant reactive composite emulsifier was added. In steps 1, 2, and 3, the addition of the high heat-resistant reactive composite emulsifier was replaced in equal amounts with fatty alcohol polyoxyethylene ether, specifically brand AEO-9. The specific operation is as follows:

[0285] Step 1: Prepare seed emulsion

[0286] Replace 2 parts of high heat-resistant reactive composite emulsifier with 2 parts of fatty alcohol polyoxyethylene ether AEO-9 in equal amounts, and perform the other operations as in Example 1;

[0287] Step 2: Preparation of core emulsion

[0288] Replace 6 parts of high heat-resistant reactive composite emulsifier with 6 parts of fatty alcohol polyoxyethylene ether AEO-9 in equal amounts, and perform the other operations as in Example 1;

[0289] Step 3: Shell graft copolymerization

[0290] Replace 4 parts of high heat-resistant reactive composite emulsifier with 4 parts of fatty alcohol polyoxyethylene ether AEO-9 in equal amounts, and perform the other operations as in Example 1.

[0291] Steps 4 and 5 are the same as in Example 1.

[0292] Comparative Example 3: Based on Example 1, no high heat-resistant crosslinking agent was added in steps 1 (preparation of seed emulsion), 2 (preparation of core emulsion), and 3 (shell graft copolymerization). In steps 1, 2, and 3, the addition of high heat-resistant crosslinking agents was replaced in equal amounts with the corresponding conventional monomers used in those steps. The specific operations are as follows:

[0293] Step 1: Prepare seed emulsion

[0294] Replace 1 part of high heat-resistant crosslinking agent with 1 part of butyl acrylate, and perform the other operations as in Example 1;

[0295] Step 2: Preparation of core emulsion

[0296] Replace 15 parts of high heat-resistant crosslinking agent with 15 parts of core layer monomer mixture, and perform the same operation as in Example 1.

[0297] Step 3: Shell graft copolymerization

[0298] Replace 8 parts of high heat-resistant crosslinking agent with 8 parts of grafted copolymer monomer mixture, and perform the other operations as in Example 1;

[0299] Steps 4 and 5 are the same as in Example 1.

[0300] Comparative Example 4: Based on Example 1, in step 3, shell graft copolymerization, the fluorinated monomer hexafluorobutyl acrylate was not added, and 9 parts of hexafluorobutyl acrylate were replaced with 9 parts of styrene in equal amounts. The specific operation is as follows:

[0301] Steps 1 and 2 are the same as in Example 1;

[0302] Step 3: Shell graft copolymerization

[0303] Replace all 9 parts of hexafluorobutyl acrylate with 9 parts of styrene in equal amounts, and perform the other operations as in Example 1;

[0304] Steps 4 and 5 are the same as in Example 1.

[0305] Comparative Example 5: Based on Example 2, in step 3, shell graft copolymerization, the fluorinated monomer vinyl fluorosilicone oil was not added, and 4 parts of vinyl fluorosilicone oil were replaced with 4 parts of styrene in equal amounts. The specific operation is as follows:

[0306] Steps 1 and 2 are the same as in Example 1;

[0307] Step 3: Shell graft copolymerization

[0308] Replace all 4 parts of vinyl fluorosilicone oil with 4 parts of styrene in equal amounts, and perform the other operations as in Example 1;

[0309] Steps 4 and 5 are the same as in Example 1.

[0310] Comparative Example 6: Based on Example 1, in step 5, hot blending, no reactive interface compatibilizer was added. Instead, 4 parts of reactive interface compatibilizer were replaced with 4 parts of SAN resin in equal amounts. The specific operation is as follows:

[0311] Steps 1, 2, 3, and 4 are the same as in Example 1;

[0312] Step 5: Hot blending

[0313] Replace all 4 parts of reactive interface compatibilizer with 4 parts of SAN resin in equal amounts, and perform the other operations as in Example 1.

[0314] Performance testing:

[0315] The following indicators were tested on the high weather resistance and high heat resistance ASA high-polymer powder impact modifiers prepared in Examples 1-10 and Comparative Examples 1-6:

[0316] 1. Impact strength: Tested according to GB / T1843-2008 Determination of impact strength of plastic cantilever beams;

[0317] 2. Vicat softening temperature: The Vicat softening temperature (VST) of thermoplastic plastics was tested according to GB / T1633-2000 to evaluate the heat resistance of ASA high-impact powder impact modifier.

[0318] 3. Weather resistance: According to GB / T3681-2011 Natural sunlight weathering of plastics, sunlight weathering after glass filtration and accelerated sunlight weathering by Fresnel lens, the weather resistance test was carried out using the natural sunlight weathering method. The change in impact strength before and after the weather resistance test was used to evaluate the weather resistance of ASA high-resin powder impact modifier.

[0319] The results are shown in Table 1:

[0320] Table 1

[0321]

[0322] As can be seen from the data in Table 1, the impact strength of Examples 1-10 is all 25.8 kJ / m. 2The Vicat softening temperature is above 109.5℃. Furthermore, the impact strength after weathering tests in Examples 1-10 showed only a small decrease compared to before the tests. This indicates that the ASA high-rubber powder impact modifier obtained in this invention possesses excellent properties of high weather resistance and high heat resistance. In Comparative Example 1, no high-heat-resistant monomers were added to any of the seed kernel, core layer, or shell layer of the ASA high-rubber powder impact modifier. The Vicat softening temperature of Comparative Example 1 decreased to 91.2℃, and the impact strength also decreased significantly. Simultaneously, the decrease in impact strength after weathering tests reached 14.51%. This demonstrates the main function of the high-heat-resistant monomers. The high-heat-resistant monomers significantly improve the Vicat softening temperature of the ASA high-impact modifier, thus enhancing its heat resistance. Furthermore, the high-heat-resistant monomers also significantly improve impact strength and weather resistance. In Comparative Example 2, no high-heat-resistant reactive composite emulsifier was added during the synthesis of the seed kernel, core layer, and shell layer of the ASA high-impact modifier. Consequently, the impact strength and Vicat softening temperature of Comparative Example 2 decreased significantly. The decrease in impact strength before and after the weather resistance test was substantial. This indicates that the high-heat-resistant reactive composite emulsifier can improve impact strength and heat resistance, while also improving weather resistance to some extent. Effects: In Comparative Example 3, no high-heat-resistant crosslinking agent was added during the synthesis of the seed kernel, core layer, and shell layer of the ASA high-rubber powder impact modifier. Comparative Example 3 showed a significant decrease in both impact strength and Vicat softening temperature, especially the Vicat softening temperature, which dropped to 93.8℃. The impact strength decreased by 18.06% before and after the weathering test. This indicates that the high-heat-resistant crosslinking agent plays a crucial role in improving the heat resistance and impact strength of the ASA high-rubber powder impact modifier, while also significantly improving weather resistance. In Comparative Examples 4 and 5, during shell graft copolymerization... Neither of the two comparative examples contained fluorinated monomers. The impact strength and Vicat softening temperature of both examples decreased only slightly, but the impact strength decreased significantly before and after the weathering test. This indicates that the fluorinated monomers added during the shell graft copolymerization play a crucial role in improving the weather resistance of the ASA high-resin powder impact modifier. Comparative example 6, without the addition of a reactive interfacial compatibilizer during hot blending, showed a significant decrease in impact strength and Vicat softening temperature. The decrease in impact strength before and after the weathering test was also very significant. This demonstrates that the reactive interfacial compatibilizer plays a critical role in promoting the compatibility of ASA powder and SAN resin.

[0323] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a high-weather-resistance and high-heat-resistance ASA high-rubber-powder impact modifier, characterized in that: the method comprises five steps of preparing a seed emulsion, preparing a core layer emulsion, shell layer graft copolymerization, preparing an ASA powder, and thermal compounding. The seed emulsion is prepared by adding deionized water, butyl acrylate, high-heat-resistance monomers, high-heat-resistance reactive complex emulsifiers, and high-heat-resistance crosslinking agents into a reaction kettle under nitrogen protection, stirring and emulsifying into an emulsion, then raising the temperature to the reaction temperature, adding potassium persulfate, and stirring and reacting at constant temperature until completion to obtain the seed emulsion. The core layer emulsion is prepared by adding a core layer monomer mixture, high-heat-resistance crosslinking agents, high-heat-resistance reactive complex emulsifiers, potassium persulfate, and deionized water into an emulsifying kettle, stirring and emulsifying into a uniform and stable emulsion under nitrogen protection, obtaining a core layer monomer emulsion, then adding the core layer monomer emulsion into the seed emulsion, raising and maintaining the temperature to the reaction temperature, stirring and reacting at constant temperature until completion to obtain the core layer emulsion. The core layer monomer mixture is prepared by mixing butyl acrylate and high-heat-resistance monomers. The graft copolymerization is prepared by adding a graft copolymerization monomer mixture, high-heat-resistance crosslinking agents, high-heat-resistance reactive complex emulsifiers, potassium persulfate, and deionized water into an emulsifying kettle under nitrogen protection, stirring and emulsifying into a uniform and stable emulsion, obtaining a graft copolymerization monomer emulsion, then adding the graft copolymerization monomer emulsion into the core layer emulsion, raising and maintaining the temperature to the reaction temperature, stirring and reacting at constant temperature until completion to obtain the graft copolymerization emulsion. The graft copolymerization monomer mixture is prepared by mixing styrene, acrylonitrile, and high-heat-resistance monomers. The high-heat-resistance monomers are a mixture of 2-allylphenyl allyl ether, N-vinyl oxazolidinone, 3,5-dimethyl-4-vinyl isoxazole, 3-acryloyl-2-oxazolidinone, and 2-isopropenyl-2-oxazoline. The high-heat-resistance reactive complex emulsifier is a mixture of triphenylstyryl phenol polyoxyethylene ether and allyloxy isomeric tridecanol polyoxyethylene ether. The ASA high-rubber-powder impact modifier is prepared by adding the graft copolymerization emulsion into a double-screw extruder, melting and extruding at 220-245°C, then cooling and granulating to obtain the ASA high-rubber-powder impact modifier. The reactive interfacial compatibilizer is a mixture of triethoxysilylpropyl maleic acid, 11-maleamidoundecanoic acid, and N-(n-hexadecyl)-maleimide. The high-heat-resistance monomers are a mixture of 2-allylphenyl allyl ether, N-vinyl oxazolidinone, 3,5-dimethyl-4-vinyl isoxazole, 3-acryloyl-2-oxazolidinone, and 2-isopropenyl-2-oxazoline. The high-heat-resistance reactive complex emulsifier is a mixture of triphenylstyryl phenol polyoxyethylene ether and allyloxy isomeric tridecanol polyoxyethylene ether. ​ The high heat-resistant crosslinking agent is one or two or more of 1,3,5-triallyl benzene-1,3,5-tricarboxylate, 1,4-diamino-2,5-divinyl benzene, 2,2'-diallyl bisphenol A, bisphenol A diallyl ether, bisphenol A dimethacrylate, 3,3'-diallyl bisphenol A diacetate, 1,2-benzene dicarboxylic acid di-2-propenyl ester, 1,3,5-triallyl cyanuric acid, 3-(triallylsilyl) propyl acrylate, and diallyl tetramethyl disiloxane, in a mixture with an arbitrary mass ratio.

2. The method for preparing the high-weather-resistance and high-heat-resistance ASA high-rubber-powder impact modifier according to claim 1, characterized in that: The mass ratio of the triphenylstyryl phenol polyoxyethylene ether and the allyloxy isomeric tridecanol polyoxyethylene ether is 11-60:

23.

3. The method for preparing the high-weather-resistance and high-heat-resistance ASA high-rubber-powder impact modifier according to claim 1, characterized in that: The mass concentration of the magnesium sulfate aqueous solution is 10-20 wt%; The mass ratio of the shell layer graft copolymer emulsion and the magnesium sulfate aqueous solution is 100-200:30-80.

4. The method for preparing the high-weather-resistance and high-heat-resistance ASA high-rubber-powder impact modifier according to claim 1, characterized in that: The mass ratio of the ASA powder, the SAN resin, and the reactive interfacial compatibilizer is 25-50:60-140:1-5.

5. The method for preparing the high-weather-resistance and high-heat-resistance ASA high-rubber-powder impact modifier according to claim 1, characterized in that: The vinyl fluorosilicone oil has a mass content of 1.2-2% of vinyl groups and a viscosity of 300-1000 mPa·s at 25℃.

6. The high-weather-resistance and high-heat-resistance ASA high-rubber-powder impact modifier prepared by the method according to any one of claims 1-5, characterized in that: The high-weather-resistance high-heat-resistance ASA high-gel powder impact modifier has an impact strength of 25.8-27.8 kJ / m 2 , a Vicat softening temperature of 109.5-114.8℃, and an impact strength of 24.4-26.9 kJ / m 2 after weather resistance test, and the impact strength decreases by 1.92-8.55% before and after the weather resistance test.

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