Long-acting and high-color-saturation ASA-based composite material and preparation method and application thereof

Abstract

The invention provides a long-acting, lasting and high-color-saturation ASA-based composite material as well as a preparation method and application thereof. The invention also provides a long-acting, long-lasting and high-color-saturation ASA preform as well as a preparation method and application thereof. The preparation raw materials of the ASA preform comprise the following components: a photosensitive dynamic covalent bond donor; wherein the photosensitive dynamic covalent bond donor is a compound containing a disulfide bond. According to the ASA preform and the ASA-based composite material, the compatibility of ASA resin and toner can be effectively improved, the color saturation of the ASA resin is improved, black is blacker, white is whiter, and meanwhile, the purity of a colored product can be better shown. Meanwhile, the color fastness of the ASA resin color can be improved, and compared with the prior art, the color retention time is longer, so that the application range of an ASA prefabricated object and an ASA resin product is greatly expanded.

Description

A long-lasting, durable, and highly color-saturated ASA-based composite material, its preparation method, and its applications. Technical Field

[0001] This invention belongs to the field of ASA-based composite material technology, specifically relating to a long-lasting, durable, and highly color-saturated ASA-based composite material, its preparation method, and its applications. Background Technology

[0002] ASA resin is a terpolymer composed of acrylonitrile (A), styrene (S) and acrylate (A). Due to the introduction of acrylate rubber without double bonds to replace butadiene rubber, the weather resistance of ASA resin is fundamentally improved, about 10 times higher than that of ABS resin. Other properties such as mechanical properties, processing properties, electrical insulation and chemical resistance are similar to those of ABS resin.

[0003] While ASA resin possesses excellent weather resistance, good processability, chemical resistance, and balanced mechanical properties, it also suffers from drawbacks such as low heat resistance, poor abrasion resistance, poor cold resistance, and poor flame retardancy, limiting its application in certain fields. Taking PC / ASA alloy materials as an example, existing technologies improve the mechanical and heat resistance of ASA resin by alloying it with PC. The resulting PC / ASA alloy materials also exhibit good mechanical properties and weather resistance; the higher the ASA resin content, the better the weather resistance. However, research has found that the weather resistance of PC / ASA alloy materials is affected by color. Generally, black PC / ASA alloy materials have better weather resistance, while light-colored products (such as white and light gray) are more susceptible to the effects of light and heat, resulting in decreased weather resistance. Therefore, due to the specific requirements of ASA resin for colorants, it can only meet the demand for a single color, black, which prevents it from addressing other color needs. Furthermore, PC / ASA alloy materials cannot solve the problem of color saturation in plastic products, failing to meet the market's demand for richer appearances.

[0004] Plastic products are prone to aging after prolonged use, resulting in fading and discoloration, which can easily cause user dissatisfaction. Furthermore, the low color saturation of plastic products makes their color expression less refined, giving them a cheap and low-quality feel, thus limiting their application, especially in high-end fields. Besides the poor weather resistance of the plastic itself leading to yellowing and chalking, the low color saturation and fading over time are caused by two main factors: firstly, poor compatibility between the pigment and the matrix, resulting in increased ineffective addition and an inability to fully express the desired color saturation; secondly, during long-term use, the pigment may separate from the matrix, reducing color fastness, causing pigment precipitation or discoloration, leading to fading and discoloration. Therefore, to achieve long-term use and maintain high color saturation, it is necessary to increase the polarity of the ASA resin to improve its compatibility with the pigment. Summary of the Invention

[0005] To address the shortcomings of existing ASA-based composite materials (including ASA alloys and modified ASA materials) such as low color saturation and fading over long-term use, this invention provides a long-lasting, high-color-saturation ASA preform, its preparation method, and its applications. This invention also provides a long-lasting, high-color-saturation ASA-based composite material, its preparation method, and its applications. Both the ASA preform and the ASA-based composite material exhibit high color saturation and maintain low fading and low discoloration even after long-term use. This invention addresses the polarity issue of ASA resin by introducing photosensitive dynamic covalent bonds into the molecular chain of the ASA resin, improving its compatibility with colorants, thereby enhancing color saturation and color fastness, resulting in low fading and low discoloration even after long-term use.

[0006] The objective of this invention is achieved through the following technical solution: an ASA preform, wherein the raw materials for preparing the ASA preform include the following components: ASA resin; a photosensitive dynamic covalent bond donor; wherein the photosensitive dynamic covalent bond donor is a compound containing disulfide bonds.

[0007] According to an embodiment of the present invention, the raw materials for preparing the ASA preform include the following components in parts by weight: ASA resin; 100 parts by weight; photosensitive dynamic covalent bond donor; 0.5-15 parts by weight.

[0008] According to an embodiment of the present invention, the raw materials for preparing the ASA preform further include at least one selected from an initiator, an antioxidant, a lubricant, and a UV stabilizer. Preferably, the raw materials for preparing the ASA preform further include at least two selected from an initiator, an antioxidant, a lubricant, and a UV stabilizer. More preferably, the raw materials for preparing the ASA preform further include at least three selected from an initiator, an antioxidant, a lubricant, and a UV stabilizer. Even more preferably, the raw materials for preparing the ASA preform further include four selected from an initiator, an antioxidant, a lubricant, and a UV stabilizer.

[0009] According to an embodiment of the present invention, the raw materials for preparing the ASA preform include 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, or 15 parts by weight of a photosensitive dynamic covalent bond donor relative to 100 parts by weight of ASA resin.

[0010] According to an embodiment of the present invention, the raw materials for preparing the ASA preform include 0.1-5 parts by weight of initiator relative to 100 parts by weight of ASA resin; preferably, the raw materials for preparing the ASA preform include 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts 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, or 5 parts by weight of initiator relative to 100 parts by weight of ASA resin.

[0011] According to an embodiment of the present invention, the raw materials for preparing the ASA preform include 0.2-2 parts by weight of antioxidant relative to 100 parts by weight of ASA resin; preferably, the raw materials for preparing the ASA preform include 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts 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, or 2 parts by weight of antioxidant relative to 100 parts by weight of ASA resin.

[0012] According to an embodiment of the present invention, the raw materials for preparing the ASA preform include 0.2-2 parts by weight of lubricant relative to 100 parts by weight of ASA resin; preferably, the raw materials for preparing the ASA preform include 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts 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, or 2 parts by weight of lubricant relative to 100 parts by weight of ASA resin.

[0013] According to an embodiment of the present invention, the raw materials for preparing the ASA preform include 0.2-2 parts by weight of a UV stabilizer relative to 100 parts by weight of ASA resin; preferably, the raw materials for preparing the ASA preform include 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts 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, or 2 parts by weight of a UV stabilizer relative to 100 parts by weight of ASA resin.

[0014] According to an embodiment of the present invention, the raw materials for preparing the ASA preform also include color powder.

[0015] According to an embodiment of the present invention, the raw materials for preparing the ASA preform include 0-30 parts by weight of color powder relative to 100 parts by weight of ASA resin; preferably, the raw materials for preparing the ASA preform include 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts 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, and 2 parts by weight relative to 100 parts by weight of ASA resin. Color powder in parts of 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 parts by weight.

[0016] According to an embodiment of the present invention, the selection of the ASA resin is not particularly defined, and it can be any ASA resin known in the art; for example, the molecular weight of the ASA resin is 100,000-200,000, preferably 150,000-200,000; the particle size of the ASA resin is 50-150 nm, preferably 60-120 nm.

[0017] According to an embodiment of the present invention, the ASA resin can be prepared using methods known in the art, or it can be obtained through commercial purchase.

[0018] According to an embodiment of the present invention, the photosensitive dynamic covalent bond donor is selected from at least one of ethylene glycol dithiodiacrylate, dithiodiallylamine, dithiodiethanol, dithiobis(2-hydroxyethyl) ether, dithiobis(3-mercaptopropionic acid), 3,3'-dithiodipropionic anhydride, and cyclic dithio compounds; preferably ethylene glycol dithiodiacrylate.

[0019] According to an embodiment of the present invention, the initiator is selected from at least one of benzoyl peroxide and dicumyl peroxide.

[0020] According to embodiments of the present invention, the selection of the antioxidant is not particularly limited, and any antioxidant known in the art that can be used in resins may be used. Exemplarily, the antioxidant is any one or a mixture of any two or more of hindered phenols, hindered amines, phosphate esters and heterocyclic antioxidants in any proportion. Also exemplaryly, the antioxidant is selected from at least one of antioxidant B215, antioxidant 168, antioxidant 1010 and antioxidant 1076.

[0021] According to embodiments of the present invention, the selection of the lubricant is not particularly limited, and any lubricant known in the art that can be used in resins may be used; exemplaryly, the lubricant is any one or any mixture of two or more of the following: fluorinated lubricant, silicone lubricant, small molecule polyolefin wax, stearic acid and amide; and also exemplaryly, the lubricant is selected from at least one of lubricant EBS, lubricant PETS and stearate.

[0022] According to embodiments of the present invention, the selection of the UV stabilizer is not particularly limited, and any lubricant known in the art that can be used in resins is acceptable; exemplaryly, the UV stabilizer is any one or a mixture of any two or more of the following: hydroxybenzophenone light stabilizers, hydroxybenzotriazole light stabilizers, or hindered amine light stabilizers in any proportion; also exemplaryly, the UV stabilizer is selected from at least one of Tinuvin 326 (benzotriazole), UV-531 (benzophenone), UV-1051, UV1180, etc.

[0023] According to an embodiment of the present invention, the colorant is selected from inorganic colorants and / or organic colorants; specifically, there is no particular limitation on the inorganic colorant and / or organic colorant, and any ASA resin known in the art and applicable to this application may be used.

[0024] According to an embodiment of the present invention, the ASA preform is a long-lasting, durable ASA preform with high color saturation.

[0025] The present invention also provides a method for preparing the above-mentioned ASA preform, the method comprising the following steps: (1) mixing ASA resin, photosensitive dynamic covalent bond donor, optional initiator, optional antioxidant, optional lubricant, optional UV stabilizer; (2) feeding the mixture obtained in step (1) into a reactive twin-screw extruder for extrusion granulation, and then cooling, pelletizing and drying; (3) pre-polarizing the material obtained in step (2) under ultraviolet irradiation with a wavelength of 365 nm to prepare the ASA preform.

[0026] According to an embodiment of the present invention, in step (1), the mixing time is 1-10 min, for example, 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min or 10 min; the mixing is carried out under stirring conditions, and the stirring speed is 100-500 rpm, for example, 100 rpm, 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm or 500 rpm.

[0027] According to an embodiment of the present invention, in step (2), the extrusion granulation temperature is 200-250°C, for example, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C or 250°C; the screw speed of the reactive twin-screw extruder is 300-600 rpm, for example, 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm or 600 rpm.

[0028] According to an embodiment of the present invention, in step (3), the pre-polarization time is 2-30 min, preferably 5-10 min.

[0029] The present invention also provides an ASA preform, which is prepared by the above method.

[0030] The present invention also provides the application of the above-mentioned ASA prefabricated materials in household appliances, automotive parts and building materials.

[0031] The present invention also provides the application of the above-mentioned ASA preform in the preparation of ASA-based composite materials.

[0032] The present invention also provides an ASA-based composite material, wherein the raw materials for preparing the ASA-based composite material include the above-mentioned ASA preform.

[0033] According to an embodiment of the present invention, the raw materials for preparing the ASA-based composite material further include at least one of a matrix resin, an antioxidant, a lubricant, a UV stabilizer, a flame retardant, and fillers; preferably, the raw materials for preparing the ASA-based composite material further include at least two of a matrix resin, an antioxidant, a lubricant, a UV stabilizer, a flame retardant, and fillers; even more preferably, the raw materials for preparing the ASA-based composite material further include at least three of a matrix resin, an antioxidant, a lubricant, a UV stabilizer, a flame retardant, and fillers.

[0034] According to an embodiment of the present invention, the raw materials for preparing the ASA-based composite material include 4-100 parts by weight of ASA preforms relative to 100 parts by weight of the ASA-based composite material; preferably, the raw materials for preparing the ASA-based composite material include 14 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, or 100 parts by weight of ASA preforms relative to 100 parts by weight of the ASA-based composite material.

[0035] According to an embodiment of the present invention, the raw materials for preparing the ASA-based composite material, relative to 100 parts by weight, include 0-96 parts by weight of a matrix resin; preferably, relative to 100 parts by weight of the ASA-based composite material, the raw materials for preparing the ASA-based composite material include 1 part by weight, 3 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, or 95 parts by weight of a matrix resin.

[0036] According to an embodiment of the present invention, the raw materials for preparing the ASA-based composite material include 0-0.5 parts by weight of antioxidant relative to 100 parts by weight of the ASA-based composite material; preferably, the raw materials for preparing the ASA-based composite material include 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, and 0.5 parts by weight of antioxidant relative to 100 parts by weight of the ASA-based composite material.

[0037] According to an embodiment of the present invention, the raw materials for preparing the ASA-based composite material include 0-0.5 parts by weight of lubricant relative to 100 parts by weight of the ASA-based composite material; preferably, the raw materials for preparing the ASA-based composite material include 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, and 0.5 parts by weight of lubricant relative to 100 parts by weight of the ASA-based composite material.

[0038] According to an embodiment of the present invention, the raw materials for preparing the ASA-based composite material include 0-1 parts by weight of a UV stabilizer relative to 100 parts by weight of the ASA-based composite material; preferably, the raw materials for preparing the ASA-based composite material include 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, and 1 part by weight of a UV stabilizer relative to 100 parts by weight of the ASA-based composite material.

[0039] According to an embodiment of the present invention, relative to 100 parts by weight of the ASA-based composite material, the raw materials for preparing the ASA-based composite material include 0-20 parts by weight of a flame retardant; relative to 100 parts by weight of the ASA-based composite material, the raw materials for preparing the ASA-based composite material include 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, and 1 part by weight. Flame retardant in parts of 1.2, 1.5, 1.6, 1.8, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 parts by weight.

[0040] According to an embodiment of the present invention, relative to 100 parts by weight of the ASA-based composite material, the raw materials for preparing the ASA-based composite material include 0-15 parts by weight of filler additives; relative to 100 parts by weight of the ASA-based composite material, the raw materials for preparing the ASA-based composite material include 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts 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, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, and 15 parts by weight of filler additives.

[0041] According to an embodiment of the present invention, the matrix resin is selected from one or more of ASA resin, PC resin, ABS resin, AS resin, PMMA resin and PET resin.

[0042] According to an embodiment of the present invention, the antioxidant is defined as described above.

[0043] According to an embodiment of the present invention, the lubricant is defined as described above.

[0044] According to an embodiment of the present invention, the UV-resistant agent is defined as described above.

[0045] According to an embodiment of the present invention, the flame retardant is selected from halogenated flame retardants such as bromotriazine and decabromodiphenyl ethane; or from phosphorus-nitrogen flame retardants such as TDP and BDP; or from one or more other types of commercially available flame retardants.

[0046] According to an embodiment of the present invention, the filler is selected from one or more of other common fillers known in the art, such as talc, calcium powder, and compatibilizer.

[0047] According to an embodiment of the present invention, the ASA-based composite material is a long-lasting, durable ASA-based composite material with high color saturation.

[0048] According to an embodiment of the present invention, by introducing "photosensitive dynamic covalent bonds" (such as disulfide bonds) into the molecular chain of ASA resin, these photosensitive dynamic covalent bonds can undergo a "break-recombination" reaction under ultraviolet irradiation, achieving both polarization of the ASA resin and giving it self-healing capabilities. Increasing the polarization of the ASA resin improves its compatibility with pigments, thereby enhancing its color saturation and achieving effects such as ultimate black, ultimate white, and other ultimate colors. Improving the self-healing capability of the ASA resin ensures its long-lasting colorfastness. Specifically, the "break-recombination" reaction involves first introducing disulfide bonds (-SS-) into the molecular chain of the ASA resin through a chemical grafting reaction. These disulfide bonds can break into thiol groups (-SH) under ultraviolet irradiation at a wavelength of 254 nm or after heating. The thiol groups (-SH) can then recombine into disulfide bonds (-SS-) without ultraviolet irradiation. Based on the aforementioned "fracture-recombination" reaction principle, the ASA resin grafted with photosensitive dynamic covalent bonds is blended with pigments under heating conditions (such as extrusion granulation). During heating, some photosensitive dynamic covalent bonds break into thiol groups. Subsequently, under 365nm ultraviolet irradiation, "pre-polarization" occurs. During pre-polarization, the thiol groups form hydrogen bonds with the amino groups (-NH2) on the pigment surface, effectively preventing pigment shedding. If, during long-term use, ultraviolet irradiation causes some hydrogen bonds to break (at which point the pigment in the ASA-based composite material is at risk of shedding), high-intensity ultraviolet light (such as 254nm ultraviolet light during outdoor exposure) can be used for irradiation. This triggers more disulfide bonds to break into thiol groups. The newly generated thiol groups can re-form hydrogen bonds with the amino groups on the pigment surface, achieving self-healing polarization of the ASA-based composite material. Simultaneously, the unbroken disulfide bonds limit the excessive movement of the ASA molecular chains, preventing pigment aggregation. When there is no ultraviolet radiation, the thiol groups can recombine into disulfide bonds, "locking" the repaired polarized structure and forming a dynamic cycle of "damage-repair-lock". By solving the polarity problem of ASA resin, its compatibility with pigments can be improved, thereby improving color saturation and color fastness. It still has the characteristics of low fading and low discoloration after long-term use.

[0049] The present invention also provides a method for preparing the above-mentioned ASA-based composite material, the method comprising the following steps: 1) mixing the ASA preform with optional matrix resin, optional antioxidant, optional lubricant, optional UV stabilizer, optional flame retardant, and optional filler additives; 2) feeding the mixture obtained in step 1) into a reactive twin-screw extruder for extrusion granulation, and then subjecting it to cooling, pelletizing, and drying to obtain the ASA-based composite material.

[0050] According to an embodiment of the present invention, in step 1), the mixing time is 1-10 min, for example, 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min or 10 min; the mixing is carried out under stirring conditions, and the stirring speed is 100-500 rpm, for example, 100 rpm, 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm or 500 rpm.

[0051] According to an embodiment of the present invention, in step 2), the extrusion granulation temperature is 200-250°C, for example, 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, or 250°C; the screw speed of the reactive twin-screw extruder is 300-600 rpm, for example, 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm, or 600 rpm.

[0052] The present invention also provides the application of the above-mentioned ASA-based composite material in household appliances, automotive parts and building materials.

[0053] The beneficial effects of this invention are as follows: This invention provides a long-lasting, high-color-saturation ASA preform, its preparation method, and its uses; this invention also provides a long-lasting, high-color-saturation ASA-based composite material, its preparation method, and its uses. The ASA preform and ASA-based composite material can effectively improve the compatibility of ASA resin and pigments, increase their color saturation, making blacks deeper and whites whiter, while also enhancing the purity of colored products. Simultaneously, it can improve the color fastness of ASA resin, resulting in a longer color retention time compared to existing technologies, which greatly expands the application range of ASA preforms and ASA resin products. Specifically, the ASA preforms and ASA-based composite materials of the present invention have the following effects: 1) Achieving purer colors on plastic products, broadening the range of color expression, and enabling wider applications; 2) Achieving long-lasting color retention, reducing color fading and discoloration of plastic products, and extending service life; 3) Improved compatibility leads to increased color saturation, allowing the use of less pigment to achieve the same effect; 4) The synergistic use of photosensitive dynamic covalent bonds and UV stabilizers can greatly improve the weather resistance of the ASA resin matrix and delay the photodecomposition of the ASA resin matrix. Detailed Implementation

[0054] The technical solution 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 merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection 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.

[0055] Unless otherwise specified, the experimental methods used in the following examples are conventional methods; unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0056] The components and contents used in Examples 1-4 and Comparative Examples 1-4 are shown in Tables 1 and 2 below (by weight).

[0057] Table 1. Composition of ASA-based composite materials prepared in the examples and comparative examples.

[0058] Table 2 Composition of ASA preforms in Examples 1-4

[0059] The preparation method of ASA preforms in Examples 1-4 includes the following steps: (1) By weight, ASA resin, initiator, photosensitive dynamic covalent bond donor, antioxidant, lubricant and color powder in Table 2 are placed in a high-speed stirrer and mixed at a stirring speed of 200 rpm for 3 min; (2) The mixture is fed into a reactive twin-screw extruder for extrusion granulation at a temperature of 230°C and a screw speed of 350 rpm; (3) The extruded material is cooled, granulated and dried; (4) The product obtained in step (3) is pre-polarized under 365 nm ultraviolet light for 5 min to obtain ASA preforms.

[0060] The preparation methods of ASA-based composite materials in Examples 1-4 and Comparative Examples 1-4 include the following steps: (1) According to the weight parts, the materials in Table 1 are placed in a high-speed mixer for mixing at a speed of 200 rpm for 3 min; (2) The mixture is fed into a reactive twin-screw extruder for extrusion granulation at a temperature of 230°C and a screw speed of 350 rpm; (3) The extruded material is cooled, pelletized, and dried to prepare ASA-based composite materials.

[0061] The prepared ASA-based composite material was subjected to the following performance tests, and the test results are shown in Table 3.

[0062] Table 3 Performance test results of the examples and comparative examples

[0063] Test conditions: UV aging conditions were performed according to ISO 4892-3 requirements, using UV light with a wavelength of 340 nm and an irradiance of 0.71 W / (m²). 2 ×nm), with a cycle of 24 hours (16 hours of irradiation + 8 hours of condensation), and a total test duration (including irradiation time and condensation time) of 500 hours.

[0064] The results show that, compared to Comparative Examples 1-4, under the same pigment addition amount, Examples 1-4 exhibited a purer blue, a lower L value for black, and a higher L value for white, with the red-green and yellow-blue hues approaching 0 values. After UV aging, Examples 1-4 showed less color change compared to Comparative Examples 1-4, with color difference values ​​ΔE significantly lower than those of Comparative Examples 1-4. Furthermore, the results of Examples 1-4 were at the same level, and the comparison with Comparative Example 1 also ruled out the influence of pre-dispersion on pigment saturation.

[0065] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An ASA prefabrication, wherein, The raw materials for preparing the ASA preform include the following components: ASA resin; photosensitive dynamic covalent bond donor; wherein the photosensitive dynamic covalent bond donor is a compound containing disulfide bonds.

2. The ASA prefabricated structure according to claim 1, wherein, The raw materials for preparing the ASA preform include the following components in parts by weight: ASA resin; 100 parts by weight; photosensitive dynamic covalent bond donor; 0.5-15 parts by weight.

3. The ASA prefabrication according to claim 1 or 2, wherein, The raw materials for preparing the ASA preform further include at least one of an initiator, an antioxidant, a lubricant, and a UV stabilizer; and / or, relative to 100 parts by weight of ASA resin, the raw materials for preparing the ASA preform include 0.1-5 parts by weight of an initiator; and / or, relative to 100 parts by weight of ASA resin, the raw materials for preparing the ASA preform include 0.2-2 parts by weight of an antioxidant; and / or, relative to 100 parts by weight of ASA resin, the raw materials for preparing the ASA preform include 0.2-2 parts by weight of a lubricant; and / or, relative to 100 parts by weight of ASA resin, the raw materials for preparing the ASA preform include 0.2-2 parts by weight of a UV stabilizer. Preferably, the raw materials for preparing the ASA preform further include colorant; and / or, relative to 100 parts by weight of ASA resin, the raw materials for preparing the ASA preform include 0-30 parts by weight of colorant. Preferably, the photosensitive dynamic covalent bond donor is selected from at least one of ethylene glycol dithiodiacrylate, dithiodiallylamine, dithiodiethanol, dithiobis(2-hydroxyethyl) ether, dithiobis(3-mercaptopropionic acid), 3,3'-dithiodipropionic anhydride, and cyclic dithio compounds.

4. A method for preparing the ASA preform according to any one of claims 1-3, the method comprising the following steps: (1) mixing ASA resin, photosensitive dynamic covalent bond donor, optional initiator, optional antioxidant, optional lubricant, optional UV stabilizer; (2) feeding the mixture obtained in step (1) into a reactive twin-screw extruder for extrusion granulation, and then subjecting it to cooling, pelletizing and drying; (3) pre-polarizing the material obtained in step (2) under ultraviolet irradiation with a wavelength of 365 nm to prepare the ASA preform. Preferably, in step (1), the mixing time is 1-10 min; the mixing is carried out under stirring conditions, and the stirring speed is 100-500 rpm; and / or, in step (2), the extrusion granulation temperature is 200-250℃; the screw speed of the reactive twin-screw extruder is 300-600 rpm; and / or, in step (3), the pre-polarization time is 2-30 min.

5. An ASA preform, said ASA preform being prepared by the method of claim 4.

6. The use of the ASA preform according to any one of claims 1-3 and 5 in the preparation of ASA-based composite materials.

7. An ASA-based composite material, wherein, The raw materials for preparing the ASA-based composite material include the ASA preforms as described in any one of claims 1-3 and 5.

8. The ASA-based composite material according to claim 7, wherein, The raw materials for preparing the ASA-based composite material further include at least one of a matrix resin, an antioxidant, a lubricant, a UV stabilizer, a flame retardant, and fillers; and / or, relative to 100 parts by weight of the ASA-based composite material, the raw materials for preparing the ASA-based composite material include 4-100 parts by weight of ASA preforms; and / or, relative to 100 parts by weight of the ASA-based composite material, the raw materials for preparing the ASA-based composite material include 0-96 parts by weight of a matrix resin; and / or, relative to 100 parts by weight of the ASA-based composite material, the raw materials for preparing the ASA-based composite material include 0-0.5 parts by weight of an antioxidant. The raw materials for preparing the ASA-based composite material include, relative to 100 parts by weight, 0-0.5 parts by weight of a lubricant; and / or, relative to 100 parts by weight of the ASA-based composite material, 0-1 parts by weight of a UV stabilizer; and / or, relative to 100 parts by weight of the ASA-based composite material, 0-20 parts by weight of a flame retardant; and / or, relative to 100 parts by weight of the ASA-based composite material, 0-15 parts by weight of filler.

9. A method for preparing the ASA-based composite material according to claim 7 or 8, the method comprising the following steps: 1) Mix the ASA preform with optional matrix resin, optional antioxidant, optional lubricant, optional UV stabilizer, optional flame retardant, and optional filler additives; 2) Feed the mixture obtained in step 1) into a reactive twin-screw extruder for extrusion granulation, followed by cooling, pelletizing, and drying to obtain the ASA-based composite material. Preferably, in step 1), the mixing time is 1-10 min; the mixing is carried out under stirring conditions at a stirring speed of 100-500 rpm; and / or, in step 2), the extrusion granulation temperature is 200-250°C; and the screw speed of the reactive twin-screw extruder is 300-600 rpm.

10. The application of the ASA-based composite material according to claim 7 or 8 in household appliances, automotive parts and building materials.

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