High-gloss black ASA (acrylonitrile-styrene-acrylate) resin as well as preparation method and application thereof

Abstract

The invention provides highlight black ASA (acrylonitrile-styrene-acrylate) resin as well as a preparation method and application thereof. According to the method, the ASA resin is prepared by adopting a polymerization method, and the method comprises the following steps: adding an ASA graft copolymer serving as a rubber phase into a suspension polymerization system which serves as a plastic phase and contains styrene and acrylonitrile in an emulsion state, and adding a phase regulator into the suspension polymerization system to prepare the ASA resin. The ASA resin has the advantages that the ASA graft copolymer is used as a dispersion phase, charge balance on the surfaces of ASA emulsion particles in a suspension polymerization system can be broken, transition from an emulsion state to a suspension state in the suspension polymerization system is realized, and finally polymerization of styrene and acrylonitrile in the suspension state is realized; the ASA resin has the characteristic of an'island 'two-phase structure taking the styrene-acrylonitrile copolymer as a continuous phase, and the micromixing of two phases of rubber and plastic in the ASA resin is more uniform. The ASA resin disclosed by the invention has high gloss and high impact strength, and a high light black effect can be obtained after the ASA resin is dyed by a black dye.

Description

Technical Field

[0001] The present invention relates to the technical field of thermoplastic resins, and particularly relates to a high-gloss black ASA resin, a preparation method thereof, and an application thereof. Background Art

[0002] ASA resin is a weather-resistant resin with high impact strength, copolymerized from acrylonitrile, styrene, and butyl acrylate monomers. As an alternative product to ABS resin, the mainstream industrial preparation process of ASA resin is to melt-blend an ASA graft copolymer with a styrene-acrylonitrile copolymer. Among them, the ASA graft copolymer is prepared by salting-out coagulation of ASA latex. The structure of the ASA graft copolymer is a core-shell type graft copolymer with polybutyl acrylate as the core and a styrene-acrylonitrile copolymer as the shell, and is usually prepared by emulsion polymerization.

[0003] In addition to significant weather resistance, ASA resin also has advantages such as high mechanical strength, good heat resistance, and excellent colorability, and thus has been widely used in many fields such as automobiles, electronic appliances, and construction. Among them, in the automotive field, it is mainly used in components such as automotive exterior rearview mirror housings, radiator grilles, ventilation grilles, tailgate panels, window frames, and lamp housings. Some mid- to high-end brand automobile manufacturers such as BMW and Mercedes-Benz have also started using ASA resin in the automotive interior field. In the field of electronic appliances, it is mainly used in outdoor open-air or humid and corrosive occasions, such as 5G antenna housings, washing machine panels, and refrigerator handles. In the construction field, using an ASA / PVC alloy blend or laminating ASA as a protective layer for PVC can endow the material with excellent weather resistance and colorability, which is a use of ASA resin that has been widely used and rapidly growing in the construction field.

[0004] However, although the ASA resin prepared by the current mainstream process has good color development for most dyes, it still lacks in the color of high-gloss black. The addition of black dyes usually makes the surface of the product foggy and the glossiness decreases. Currently, to solve this problem, the conventional method is to add high-gloss polymethyl methacrylate or introduce methyl methacrylate monomers in the polymerization to improve the surface glossiness of ASA resin. However, this method often reduces the impact strength of ASA resin and has an insignificant improvement in the high-gloss black effect of ASA resin. Summary of the Invention

[0005] In order to improve the deficiencies of the prior art, the present invention provides a high-gloss black ASA resin, its preparation method and applications. The preparation method of the present invention can replace the traditional melt blending method. The method of the present invention realizes the preparation of ASA resin by polymerization. The method is to add the ASA graft copolymer as the rubber phase in the form of an emulsion to the suspension polymerization system containing styrene and acrylonitrile as the plastic phase. By introducing a phase regulator into the suspension polymerization system, the charge balance on the surface of the ASA emulsion particles in the suspension polymerization system can be broken, realizing the transition from the emulsion state to the suspension state in the suspension polymerization system, and finally realizing the polymerization of styrene and acrylonitrile in the suspension state. At the same time, since the ASA graft copolymer is dispersed as the dispersed phase in the droplets of the suspension polymerization system containing styrene and acrylonitrile, and the droplets will polymerize to form a continuous plastic phase during the heating process, finally a "sea-island" two-phase structure formed by more uniformly dispersed rubber and plastic is prepared microscopically. In addition, by introducing a molecular weight regulator into the suspension polymerization system to control the degree of polymerization reaction in the reaction system, the particle size of the butyl acrylate rubber particles in the obtained ASA resin is smaller, making the microscopic mixing of the rubber and plastic phases in the ASA resin more uniform.

[0006] Compared with the traditional ASA resin preparation process, the ASA resin of the present invention has the characteristics of a "sea-island" two-phase structure with the ASA graft copolymer as the dispersed phase and the styrene-acrylonitrile copolymer as the continuous phase, and the microscopic mixing of the rubber and plastic phases in the ASA resin is more uniform. The ASA resin of the present invention has a high gloss and high impact strength, and can obtain a high-gloss black effect after being dyed with a black dye.

[0007] The object of the present invention is achieved by the following technical solutions:

[0008] An ASA resin, wherein the ASA resin comprises an ASA graft copolymer and a styrene-acrylonitrile copolymer, the ASA graft copolymer is the dispersed phase, the styrene-acrylonitrile copolymer is the continuous phase, and the ASA graft copolymer is dispersed in the styrene-acrylonitrile copolymer.

[0009] According to an embodiment of the present invention, the ASA resin has a "sea-island" two-phase structure with the ASA graft copolymer as the dispersed phase and the styrene-acrylonitrile copolymer as the continuous phase.

[0010] According to an embodiment of the present invention, the particle size of the dispersed phase is 50 - 400 nm, preferably 100 - 300 nm, more preferably 150 - 250 nm, such as 60 nm, 80 nm, 100 nm, 120 nm, 150 nm, 160 nm, 180 nm, 200 nm, 220 nm, 240 nm, 250 nm, 260 nm, 280 nm, 300 nm, 320 nm, 350 nm, 360 nm or 400 nm.

[0011] According to an embodiment of the present invention, the mass of the ASA graft copolymer accounts for 20 - 50 wt% of the total mass of the ASA resin, such as 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%.

[0012] According to an embodiment of the present invention, the mass of the styrene - acrylonitrile copolymer accounts for 50 - 80 wt% of the total mass of the ASA resin, such as 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt% or 80 wt%.

[0013] According to an embodiment of the present invention, the styrene - acrylonitrile copolymer is a random copolymer of styrene and acrylonitrile.

[0014] According to an embodiment of the present invention, in the styrene - acrylonitrile copolymer, the mass ratio of styrene to acrylonitrile is 2 - 4:1, such as 2:1, 2.5:1, 3:1, 3.5:1 or 4:1.

[0015] According to an embodiment of the present invention, the polymerization monomers of the ASA graft copolymer include butyl acrylate, styrene and acrylonitrile.

[0016] According to an embodiment of the present invention, the polymerization monomers of the ASA graft copolymer may further include organosiloxane monomers, such as octamethylcyclotetrasiloxane.

[0017] According to an embodiment of the present invention, in the ASA graft copolymer, the mass ratio of styrene to acrylonitrile is 2 - 4:1, such as 2:1, 2.5:1, 3:1, 3.5:1 or 4:1.

[0018] According to an embodiment of the present invention, based on the total weight of the ASA graft copolymer, the mass percentage content of butyl acrylate is 35 - 85 wt%, such as 35 wt%, 36 wt%, 38 wt%, 40 wt%, 42 wt%, 45 wt%, 46 wt%, 48 wt%, 50 wt%, 52 wt% or 55 wt%, 65 wt%, 75 wt%, 80 wt% or 85 wt%; the mass percentage content of the total mass of styrene and acrylonitrile is 15 - 65 wt%, such as 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 48 wt%, 50 wt%, 52 wt%, 55 wt%, 58 wt%, 60 wt%, 62 wt% or 65 wt%; the mass percentage content of the organosiloxane monomer is 0 - 10 wt%, for example, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%.

[0019] According to an embodiment of the present invention, the ASA graft copolymer has a core - shell structure, and the butyl acrylate polymer or the polymer of butyl acrylate and organosiloxane monomer is used as the core, and the copolymer of styrene and acrylonitrile is grafted on the surface of the core to form a shell layer.

[0020] According to an embodiment of the present invention, the ASA graft copolymer is added to the polymerization system in the form of an ASA emulsion, and the particle size of the ASA emulsion is 50 - 400 nm, preferably 100 - 300 nm, more preferably 150 - 250 nm, for example, 60 nm, 80 nm, 100 nm, 120 nm, 150 nm, 160 nm, 180 nm, 200 nm, 220 nm, 240 nm, 250 nm, 260 nm, 280 nm, 300 nm, 320 nm, 350 nm, 360 nm or 400 nm.

[0021] According to an embodiment of the present invention, the solid content of the ASA emulsion is 20 - 40 wt%, for example, 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt%.

[0022] According to an embodiment of the present invention, the ASA emulsion and the ASA graft copolymer are prepared by methods known in the art or obtained through commercial channels.

[0023] The present invention also provides an ASA resin, and the raw materials for preparing the ASA resin include:

[0024] ASA emulsion;

[0025] Phase regulator;

[0026] Styrene and acrylonitrile;

[0027] Crosslinking agent;

[0028] Molecular weight regulator;

[0029] Initiator;

[0030] Dispersant;

[0031] Water.

[0032] According to an embodiment of the present invention, the raw materials for preparing the ASA resin include the following components in parts by weight:

[0033] ASA emulsion (solid content 20 - 40 wt%); 62.5 - 500 parts by weight;

[0034] Phase regulator; 0.01 - 2 parts by weight;

[0035] Styrene and acrylonitrile; 100 parts by weight;

[0036] Crosslinking agent; 0.01 - 2 parts by weight;

[0037] Molecular weight regulator; 0.1 - 1.5 parts by weight;

[0038] Initiator; 0.1 - 2 parts by weight;

[0039] Dispersant; 0.05 - 2 parts by weight;

[0040] Water; 100 - 200 parts by weight.

[0041] According to an embodiment of the present invention, the particle size of the ASA emulsion is 50 - 400 nm, preferably 100 - 300 nm, more preferably 150 - 250 nm. The ASA emulsion and the ASA graft copolymer are prepared by methods known in the art or obtained through commercial channels.

[0042] According to an embodiment of the present invention, relative to 100 parts by weight of styrene and acrylonitrile, the addition amount of the ASA emulsion is 62.5 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, 200 parts by weight, 220 parts by weight, 250 parts by weight, 260 parts by weight, 280 parts by weight, 300 parts by weight, 320 parts by weight, 350 parts by weight, 360 parts by weight, 380 parts by weight, 400 parts by weight, 420 parts by weight, 450 parts by weight, 480 parts by weight or 500 parts by weight.

[0043] According to an embodiment of the present invention, the phase regulator is selected from alkali metal salts, preferably metal sodium salts or metal potassium salts; exemplarily, the phase regulator is selected from one or more of sodium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium chloride, potassium carbonate, potassium bicarbonate, potassium sulfate, potassium phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate.

[0044] According to an embodiment of the present invention, with respect to 100 parts by weight of styrene and acrylonitrile, the addition amount of the phase regulator is 0.01 part by weight, 0.02 part by weight, 0.05 part by weight, 0.1 part by weight, 0.2 part by weight, 0.5 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 part by weight, 1.5 part by weight, 1.6 part by weight, 1.8 part by weight, or 2 parts by weight.

[0045] According to an embodiment of the present invention, the mass ratio of styrene to acrylonitrile is 2 - 4:1, for example, 2:1, 2.5:1, 3:1, 3.5:1, or 4:1.

[0046] According to an embodiment of the present invention, the crosslinking agent is selected from one or more of divinylbenzene, 1,4 - butanediol diacrylate, ethylene glycol dimethacrylate, and trimethylolpropane triacrylate, preferably divinylbenzene.

[0047] According to an embodiment of the present invention, with respect to 100 parts by weight of styrene and acrylonitrile, the addition amount of the crosslinking agent is 0.01 part by weight, 0.05 part by weight, 0.1 part by weight, 0.2 part by weight, 0.5 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 part by weight, 1.5 part by weight, 1.6 part by weight, 1.8 part by weight, or 2 parts by weight.

[0048] According to an embodiment of the present invention, the molecular weight regulator is selected from n - dodecyl mercaptan and / or tert - dodecyl mercaptan.

[0049] According to an embodiment of the present invention, with respect to 100 parts by weight of styrene and acrylonitrile, the addition amount of the molecular weight regulator is 0.1 part by weight, 0.2 part by weight, 0.5 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 part by weight, or 1.5 part by weight.

[0050] According to an embodiment of the present invention, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, cumene hydroperoxide, and tert - butyl hydroperoxide.

[0051] According to an embodiment of the present invention, the addition amount of the initiator is 0.1 part by weight, 0.2 part by weight, 0.5 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 part by weight, 1.5 part by weight, 1.6 part by weight, 1.8 part by weight or 2 parts by weight relative to 100 parts by weight of styrene and acrylonitrile.

[0052] According to an embodiment of the present invention, the dispersant is selected from one or more of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, alkylphenol polyoxyethylene ethers, cellulose, methylcellulose, hydroxypropyl methylcellulose, cellulose ethers, polyvinyl alcohol, polyvinylpyrrolidone and calcium carbonate.

[0053] According to an embodiment of the present invention, the addition amount of the dispersant is 0.05 part by weight, 0.1 part by weight, 0.2 part by weight, 0.5 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 part by weight, 1.5 part by weight, 1.6 part by weight, 1.8 part by weight or 2 parts by weight relative to 100 parts by weight of styrene and acrylonitrile.

[0054] According to an embodiment of the present invention, the addition amount of the water is 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight or 200 parts by weight relative to 100 parts by weight of styrene and acrylonitrile.

[0055] The present invention also provides a method for preparing the above-mentioned ASA resin, and the preparation method includes the following steps:

[0056] Mix styrene, acrylonitrile, crosslinking agent, molecular weight regulator, initiator, water and dispersant; then add ASA emulsion, raise the temperature of the reaction system, and when the temperature of the reaction system reaches 45-60 °C, add a phase regulator, stir for a certain time, then raise the temperature of the reaction system, and when the temperature of the reaction system reaches 70-75 °C, carry out the reaction to prepare the ASA resin.

[0057] According to an embodiment of the present invention, stir for 20-40 minutes after adding the phase regulator.

[0058] According to an embodiment of the present invention, when the temperature of the reaction system reaches 70-75 °C, react for 3-4 hours.

[0059] According to an embodiment of the present invention, preferably, add the phase regulator when the temperature of the reaction system reaches 45-55 °C.

[0060] According to an embodiment of the present invention, the reaction is carried out under an inert atmosphere; exemplarily, the reaction is carried out under a nitrogen atmosphere.

[0061] According to an embodiment of the present invention, after the reaction, it preferably further includes post-treatment steps such as filtration, washing, and drying.

[0062] The present invention provides an ASA resin, which is prepared by the above method.

[0063] The present invention provides an ASA resin composition, which comprises the following components:

[0064] ASA resin;

[0065] Dye;

[0066] Lubricant;

[0067] Antioxidant.

[0068] According to an embodiment of the present invention, the ASA resin composition comprises the following components in parts by weight:

[0069] 100 parts by weight of ASA resin;

[0070] 0.1 - 2 parts by weight of dye;

[0071] 0.1 - 5 parts by weight of lubricant;

[0072] 0.1 - 2 parts by weight of antioxidant.

[0073] According to an embodiment of the present invention, relative to 100 parts by weight of ASA resin, 0.1 part by weight, 0.2 part by weight, 0.5 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight of dye are added.

[0074] According to an embodiment of the present invention, the dye is selected from black toner or black masterbatch.

[0075] According to an embodiment of the present invention, relative to 100 parts by weight of ASA resin, 0.1 part by weight, 0.2 part by weight, 0.5 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight of lubricant are added.

[0076] According to an embodiment of the present invention, the lubricant is selected from one or more of ethylene bisstearamide, zinc stearate, calcium stearate, sodium stearate, fatty amide, etc.

[0077] According to an embodiment of the present invention, 0.1 part by weight, 0.2 part by weight, 0.5 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 part by weight, 1.5 part by weight, 1.6 part by weight, 1.8 part by weight, or 2 parts by weight of an antioxidant is added relative to 100 parts by weight of the ASA resin.

[0078] According to an embodiment of the present invention, the antioxidant is selected from a combination of a hindered phenol antioxidant and a phosphite antioxidant or a combination of an amine antioxidant and a phosphite antioxidant; exemplarily, the antioxidant is selected from antioxidants 1010, 168, 1076, etc.

[0079] The present invention provides a high-gloss black ASA resin, and the raw materials for preparing the high-gloss black ASA resin include the above-mentioned ASA resin composition.

[0080] According to an embodiment of the present invention, the high-gloss black ASA resin is prepared from the above-mentioned ASA resin composition.

[0081] According to an embodiment of the present invention, the high-gloss black ASA resin is prepared from the above-mentioned ASA resin composition by a melt blending method.

[0082] Advantages of the present invention:

[0083] (1) The ASA resin of the present invention is prepared by a polymerization method, and the degree of the polymerization reaction is controlled by a molecular weight regulator, so that the particle size of the butyl acrylate rubber particles in the obtained ASA resin is smaller. At the same time, the emulsion reaction system is improved by adding a phase regulator, making the microscopic mixing of the rubber and plastic phases in the resin more uniform, thereby enabling the obtained ASA resin to have higher gloss and excellent impact resistance; at the same time, a molecular weight regulator is added during the polymerization process, and the molecular weight regulator and the phase regulator are used in combination, which can more excellently control the degree of the polymerization reaction occurring in the reaction system, making the particle size of the rubber particles in the obtained ASA resin smaller and more uniform, and further making the microscopic mixing of the rubber and plastic phases in the ASA resin more uniform, which can obtain a high-gloss black dyed ASA resin with excellent properties.

[0084] (2) The ASA resin of the present invention does not introduce polymethyl methacrylate (PMMA) or other acrylic rubber components, and can significantly improve the gloss of the ASA resin without reducing the impact resistance of the ASA resin, and a high-gloss black effect can be obtained after being dyed with black toner or black masterbatch.

[0085] (3) The preparation process is simple and suitable for large-scale production. Description of the Drawings

[0086] Figure 1SEM image of the ASA resin prepared in Example 1 of the present invention. Detailed implementation manners

[0087] The technical solutions of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are only for illustrative explanation of the present invention and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0088] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; unless otherwise specified, the reagents, materials, etc. used in the following examples can all be obtained from commercial channels.

[0089] Example 1

[0090] Preparation of ASA resin

[0091] A four-necked round-bottom flask equipped with a stirrer, a thermometer, and a condenser was used as the reactor. The reactor was purged with high-purity nitrogen for 30 minutes, and then the system was maintained in a nitrogen atmosphere. A monomer mixture was prepared by mixing 75 parts by weight of styrene, 25 parts by weight of acrylonitrile, 0.5 part by weight of n-dodecyl mercaptan, and 1 part by weight of azobisisobutyronitrile. 126 parts by weight of water, 0.2 part by weight of polyvinyl alcohol, and 100 parts by weight of ASA emulsion (emulsion particle size 180 nm, solid content 35%, the proportion of butyl acrylate in the dry matter is 50 wt%, and the mass ratio of styrene to acrylonitrile is 3:1) were added to the reaction kettle. After stirring evenly, the monomer mixture was added to the kettle at one time. The system was heated up. When the system temperature reached 45 °C, 1.5 parts by weight of sodium bicarbonate was added, and the mixture was stirred at a constant temperature for 20 minutes. Then the system was heated up to 75 °C and reacted for 3 hours. After the reaction was completed, the temperature was lowered, and the product was filtered, washed, and dried to obtain ASA resin.

[0092] Preparation of high-gloss black-dyed ASA resin

[0093] 100 parts by weight of the ASA resin prepared above, 0.8 part by weight of black color powder, 0.5 part by weight of EBS lubricant, 0.2 part by weight of antioxidant 1010, and 0.2 part by weight of antioxidant 168 were mixed evenly in a high-speed mixer and granulated by co-mixing using a twin-screw extruder to obtain high-gloss black-dyed ASA resin.

[0094] Testing of product performance:

[0095] (1) Determination of impact strength: According to the requirements of GB / T 1843-2008, an injection molding machine was used to inject the blended resin into sheets, and the Izod notched impact strength at room temperature was tested.

[0096] (2) Glossiness test: According to the requirements of GB / T 8807-1988, a 3nh glossiness meter was used to measure the glossiness of the spline at a 60° angle.

[0097] (3) Lab value test: An X-rite Ci7800 desktop spectrophotometer was used to characterize the color plates after injection molding.

[0098] Figure 1 This is the scanning electron micrograph of the ASA resin prepared in Example 1 of the present invention; Figure 1 The white area in [Figure] is the dispersed phase formed by the ASA graft copolymer, and the gray area is the continuous phase formed by the styrene-acrylonitrile copolymer.

[0099] Example 2

[0100] Other operations were the same as in Example 1, except that in the preparation of the ASA resin:

[0101] 126 parts by weight of water, 0.2 parts by weight of polyvinyl alcohol, and 100 parts by weight of ASA emulsion (emulsion particle size 180 nm, solid content 35%, the proportion of butyl acrylate in the dry matter is 50 wt%, and the mass ratio of styrene to acrylonitrile is 3:1) were added to the reaction kettle. After stirring evenly, the monomer mixture was added to the kettle at one time. The system was heated up. When the system temperature reached 45 °C, 0.38 parts by weight of sodium bicarbonate and 0.8 parts by weight of sodium carbonate were added. After stirring at a constant temperature for 20 minutes, the system was heated to 75 °C and continued to react for 3 hours. After the reaction, the temperature was lowered, filtered, washed, and dried to obtain the ASA resin.

[0102] Example 3

[0103] Other operations were the same as in Example 1, except that in the preparation of the ASA resin:

[0104] 126 parts by weight of water, 0.2 parts by weight of polyvinyl alcohol, and 100 parts by weight of ASA emulsion (emulsion particle size 180 nm, solid content 35%, the proportion of butyl acrylate in the dry matter is 50 wt%, and the mass ratio of styrene to acrylonitrile is 3:1) were added to the reaction kettle. After stirring evenly, the monomer mixture was added to the kettle at one time. The system was heated up. When the system temperature reached 45 °C, 2.34 parts by weight of disodium hydrogen phosphate was added. After stirring at a constant temperature for 20 minutes, the system was heated to 75 °C and continued to react for 3 hours. After the reaction, the temperature was lowered, filtered, washed, and dried to obtain the ASA resin.

[0105] Example 4

[0106] Other operations were the same as in Example 1, except that in the preparation of the ASA resin:

[0107] Add 126 parts by weight of water, 0.2 parts by weight of polyvinyl alcohol, and 100 parts by weight of ASA emulsion (emulsion particle size 180 nm, solid content 35%, butyl acrylate accounts for 50 wt% in dry matter, and the mass ratio of styrene to acrylonitrile is 3:1) into the reaction kettle. After stirring evenly, add the monomer mixture into the kettle at one time. The system starts to heat up. When the system temperature reaches 55 °C, add 2.34 parts by weight of disodium hydrogen phosphate, stir at a constant temperature for 20 minutes, then raise the temperature of the system to 75 °C and continue to react for 3 hours. After the reaction is completed, cool down, filter, wash, and dry to obtain ASA resin.

[0108] Example 5

[0109] Other operations are the same as in Example 3, except in the preparation of the high-gloss black dyed ASA resin:

[0110] Take 100 parts by weight of the ASA resin prepared above, 1 part by weight of black color powder, 0.5 part by weight of EBS lubricant, 0.2 part by weight of antioxidant 1010, and 0.2 part by weight of antioxidant 168. Mix them evenly in a high-speed mixer, and use a twin-screw extruder for blending and pelletizing to obtain the high-gloss black dyed ASA resin.

[0111] Example 6

[0112] Other operations are the same as in Example 3, except in the preparation of the high-gloss black dyed ASA resin:

[0113] Take 100 parts by weight of the ASA resin prepared above, 2.5 parts by weight of black color masterbatch (where the color powder concentration is 40%), 0.5 part by weight of EBS lubricant, 0.2 part by weight of antioxidant 1010, and 0.2 part by weight of antioxidant 168. Mix them evenly in a high-speed mixer, and use a twin-screw extruder for blending and pelletizing to obtain the high-gloss black dyed ASA resin.

[0114] Example 7

[0115] Other operations are the same as in Example 1, except in the preparation of the ASA resin:

[0116] Add 126 parts by weight of water, 0.2 parts by weight of polyvinyl alcohol, and 100 parts by weight of ASA emulsion (emulsion particle size 120 nm, solid content 35%, butyl acrylate accounts for 50 wt% in dry matter, octamethylcyclotetrasiloxane accounts for 5 wt%, and the mass ratio of styrene to acrylonitrile is 3:1) into the reaction kettle. After stirring evenly, add the monomer mixture into the kettle at one time. The system starts to heat up. When the system temperature reaches 45 °C, add 1.5 parts by weight of sodium bicarbonate, stir at a constant temperature for 20 minutes, then raise the temperature of the system to 75 °C and continue to react for 3 hours. After the reaction is completed, cool down, filter, wash, and dry to obtain ASA resin.

[0117] Comparative Example 1

[0118] Other operations were the same as in Example 1, except that in the preparation of the ASA resin:

[0119] 126 parts by weight of water, 0.2 part by weight of polyvinyl alcohol, and 100 parts by weight of an ASA emulsion (emulsion particle size 180 nm, solid content 35%, butyl acrylate accounted for 50 wt% in the dry matter, and the mass ratio of styrene to acrylonitrile was 3:1) were added to the reaction kettle. After stirring evenly, the monomer mixture was added to the kettle at one time. The system was heated up, and the system was heated to 75 °C for reaction. When the system reacted for about 2 hours, a lot of resin particles appeared in the reaction system. Continuing to stir, the resin particles gradually coalesced and finally agglomerated into a whole spherical shape, and the stirring paddle failed, resulting in the failure of the reaction.

[0120] Comparative Example 2

[0121] Other operations were the same as in Example 1, except that in the preparation of the ASA resin:

[0122] 126 parts by weight of water, 0.2 part by weight of polyvinyl alcohol, and 100 parts by weight of an ASA emulsion (emulsion particle size 180 nm, solid content 35%, butyl acrylate accounted for 50 wt% in the dry matter, and the mass ratio of styrene to acrylonitrile was 3:1) were added to the reaction kettle. After stirring evenly, the monomer mixture was added to the kettle at one time. The system was heated up, and when the system temperature reached 45 °C, 1.5 parts by weight of magnesium sulfate was added, and the mixture was stirred at a constant temperature for 20 minutes. Subsequently, the system was heated to 75 °C and continued to react. When the system reacted for about 1.5 hours, the system viscosity suddenly increased, a lot of resin particles appeared, the solution system presented a paste-like state, and the stirring paddle failed, so the reaction was terminated.

[0123] Comparative Example 3

[0124] Other operations were the same as in Example 1, except that in the preparation of the ASA resin: n-dodecyl mercaptan as a molecular weight regulator was not added.

[0125] Comparative Example 4

[0126] 90 parts by weight of commercially available ASA resin (ASA resin with the brand of LI-912 from LG Chem, South Korea), 10 parts by weight of PMMA resin, 0.8 part by weight of black color powder, 0.5 part by weight of EBS lubricant, 0.2 part by weight of antioxidant 1010, and 0.2 part by weight of antioxidant 168 were mixed evenly in a high-speed mixer and granulated by co-mixing using a twin-screw extruder to obtain a high-gloss black-dyed ASA resin.

[0127] Comparative Example 5

[0128] Take 100 parts by weight of a commercially available ASA resin (ASA resin with the trade name LI-912 from LG Chem, Korea), 0.8 parts by weight of black color powder, 0.5 parts by weight of EBS lubricant, 0.2 parts by weight of antioxidant 1010, 0.2 parts by weight of antioxidant 168. Mix them evenly in a high-speed mixer and perform co-blending and pelletizing using a twin-screw extruder to obtain a high-gloss black-dyed ASA resin.

[0129] Table 1 Composition and performance test results of high-gloss black-dyed ASA resins in examples and comparative examples

[0130]

[0131] It can be seen from the comparison between Comparative Example 4 and Comparative Example 5 in Table 1 that introducing PMMA resin into the ASA resin system will improve the gloss of the ASA resin to a certain extent (from 88 to 95), but will significantly decrease the notched impact strength of the ASA resin. At the same time, it has little effect on the Lab value of the ASA resin. This shows that even if PMMA resin is introduced into the ASA resin system, the high-gloss black-dyed effect cannot be achieved because of the high Lab value and low gloss of the ASA resin.

[0132] It can be seen from the comparison between Examples 1-4 and Comparative Examples 1-2 in Table 1 that the emulsion-suspension polymerization combined process proposed by the present invention can prepare an ASA resin with a high-gloss black-dyed effect; specifically, by adding a specific phase regulator of the present application during the suspension polymerization process, the ASA emulsion can be transformed into an ASA graft copolymer during the polymerization process, and form a rubber-plastic two-phase mixture with a sea-island structure with styrene-acrylonitrile copolymer, thereby preparing an ASA resin with a high-gloss black-dyed effect. Moreover, the prepared ASA resin can maintain a high notched impact strength while having a high gloss and a low Lab value after being dyed with black powder, indicating that the prepared high-gloss black-dyed ASA resin has a high-gloss black color effect.

[0133] It can be seen from the comparison between Examples 3, 5-6 that by adjusting the components and content of the dye in the ASA resin composition, it has little effect on the notched impact resistance and flexural modulus of the high-gloss black-dyed ASA resin, and good high-gloss black performance can be achieved.

[0134] It can be seen from the comparison between Example 1 and Example 7 that by adjusting the particle size of the ASA emulsion, the notched impact strength and gloss of the high-gloss black-dyed ASA resin can be adjusted, and the smaller the particle size of the ASA emulsion, the lower the notched impact strength and the higher the gloss of the high-gloss black-dyed ASA resin.

[0135] It can be seen from the comparison between Example 1 and Comparative Example 3 that not adding a molecular weight regulator during the emulsion-suspension polymerization process will significantly increase the molecular weight of the styrene-acrylonitrile copolymer obtained in the suspension polymerization system, and will also cause the particle size of the butyl acrylate rubber particles in the obtained ASA resin to become larger and uneven, which will lead to poor notched impact strength, slightly poor gloss and increased Lab value of the high-gloss black-dyed ASA resin.

[0136] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An ASA resin, wherein, The ASA resin comprises an ASA graft copolymer and a styrene-acrylonitrile copolymer. The ASA graft copolymer is the dispersed phase, and the styrene-acrylonitrile copolymer is the continuous phase. The ASA graft copolymer is dispersed in the styrene-acrylonitrile copolymer.

2. The ASA resin according to claim 1, wherein, The ASA resin has a "sea-island" two-phase structure with the ASA graft copolymer as the dispersed phase and the styrene-acrylonitrile copolymer as the continuous phase. Preferably, the particle size of the dispersed phase is 50 - 400 nm. Preferably, the mass of the ASA graft copolymer accounts for 20 - 50 wt% of the total mass of the ASA resin; the mass of the styrene-acrylonitrile copolymer accounts for 50 - 80 wt% of the total mass of the ASA resin. Preferably, in the styrene-acrylonitrile copolymer, the mass ratio of styrene to acrylonitrile is 2 - 4:

1.

3. The ASA resin according to claim 1 or 2, wherein The polymerization monomers of the ASA graft copolymer include butyl acrylate, styrene, and acrylonitrile. Preferably, the polymerization monomers of the ASA graft copolymer may further include organosiloxane monomers, such as octamethylcyclotetrasiloxane. Preferably, in the ASA graft copolymer, the mass ratio of styrene to acrylonitrile is 2 - 4:

1. Preferably, based on the total weight of the ASA graft copolymer, the mass percentage content of butyl acrylate is 35 - 85 wt%; the mass percentage content of the total mass of styrene and acrylonitrile is 15 - 65 wt%; the mass percentage content of the organosiloxane monomers is 0 - 10 wt%. Preferably, the ASA graft copolymer has a core-shell structure, with a butyl acrylate polymer or a polymer of butyl acrylate and organosiloxane monomers as the core, and a copolymer of styrene and acrylonitrile grafted on the surface of the core to form a shell layer.

4. An ASA resin, the preparation raw materials of the ASA resin comprising: ASA emulsion; Phase regulator; Styrene and acrylonitrile; Crosslinking agent; Molecular weight regulator; Initiator; Dispersant; Water.

5. The ASA resin according to claim 4, wherein, The preparation raw materials of the ASA resin comprise the following components in parts by weight: ASA emulsion; 62.5 - 500 parts by weight; Phase regulator; 0.01 - 2 parts by weight; Styrene and acrylonitrile; 100 parts by weight; Crosslinking agent; 0.01 - 2 parts by weight; Molecular weight regulator; 0.1 - 1.5 parts by weight; Initiator; 0.1 - 2 parts by weight; Dispersant; 0.05 - 2 parts by weight; Water; 100 - 200 parts by weight.

6. The ASA resin according to claim 4 or 5, wherein The phase regulator is selected from alkali metal salts, preferably metal sodium salts or metal potassium salts; exemplarily, the phase regulator is selected from one or more of sodium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium chloride, potassium carbonate, potassium bicarbonate, potassium sulfate, potassium phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate. Preferably, the mass ratio of styrene to acrylonitrile is 2 - 4:

1. Preferably, the crosslinking agent is selected from one or more of divinylbenzene, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, and trimethylolpropane triacrylate, preferably divinylbenzene. Preferably, the molecular weight regulator is selected from n-dodecyl mercaptan and / or tert-dodecyl mercaptan. Preferably, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide. Preferably, the dispersant is selected from one or more of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, alkylphenol polyoxyethylene ethers, cellulose, methylcellulose, hydroxypropyl methylcellulose, cellulose ether, polyvinyl alcohol, polyvinylpyrrolidone, and calcium carbonate.

7. A method for preparing the ASA resin according to any one of claims 1-6, the preparation method comprising the following steps: Mix styrene, acrylonitrile, crosslinking agent, molecular weight regulator, initiator, water, and dispersant; then add the ASA emulsion, heat up the reaction system, and when the temperature of the reaction system reaches 45-60 °C, add the phase regulator. After stirring for a certain time, heat up the reaction system, and when the temperature of the reaction system reaches 70-75 °C, carry out the reaction to prepare the ASA resin.

8. An ASA resin, which is prepared by the method according to claim 7.

9. An ASA resin composition, the ASA resin composition comprising the following components: The ASA resin according to any one of claims 1-6, 8; Dye; Lubricant; Antioxidant. Preferably, the ASA resin composition comprises the following components in parts by weight: 100 parts by weight of ASA resin; 0.1-2 parts by weight of dye; 0.1-5 parts by weight of lubricant; 0.1-2 parts by weight of antioxidant.

10. A high-gloss black ASA resin, wherein, The raw materials for preparing the high-gloss black ASA resin include the ASA resin composition according to claim 9.

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