Abs alloy material, preparation method and application thereof

Abstract

The application discloses an ABS alloy material and a preparation method and application thereof, and belongs to the technical field of high polymer materials; the ABS alloy material provided by the application comprises the following components in parts by mass: 58-82 parts of ABS resin, 18-42 parts of ASA glue powder, 6-14 parts of a phosphorus flame retardant, 5-11 parts of a nitrogen flame retardant, 5-11 parts of a heteropolyacid salt and 2-8 parts of a compatilizer. The ABS alloy material provided by the application has good rigidity and toughness balance and excellent solvent resistance on the basis of realizing V0 flame retardant grade of the thin-wall product prepared from the ABS alloy material by selecting appropriate parts by mass of the components to cooperate with each other. Moreover, the preparation method of the ABS alloy provided by the application is simple in operation and is beneficial to actual production.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and particularly relates to an ABS alloy material, its preparation method and application. Background Technology

[0002] ABS, or acrylonitrile-butadiene-styrene terpolymer, is a general-purpose plastic that combines rigidity and toughness, high gloss, ease of processing, and dimensional stability. It is widely used in home appliances, office equipment, and the electronics and electrical industries. However, ABS resin has an oxygen index of only around 18, classifying it as a flammable material. It requires flame-retardant modification before it can be used in products involving electricity, which significantly limits its applications.

[0003] Currently, flame-retardant modification technology for ABS is quite mature. The most common method is to add bromine-antimony flame retardants to ABS to prepare flame-retardant ABS; however, this method involves halogen-containing flame retardants, which is an environmentally unfriendly approach and does not align with the development trend of ABS. Chinese patent (CN 118406345 A) discloses a flame-retardant ABS composite material and its preparation method. This method uses a coated modified phosphorus-nitrogen compound flame retardant to achieve a V0 halogen-free flame retardant rating. However, the red phosphorus flame retardant used has a certain degree of toxicity, and the production process poses a fire risk. Alternatively, blending PC and ABS with the addition of phosphate ester flame retardants can also achieve halogen-free V0 flame retardancy. However, halogen-free flame-retardant PC / ABS has poor solvent resistance and cannot be used in products requiring solvent resistance.

[0004] In summary, flame-retardant ABS still has shortcomings such as environmental friendliness and solvent resistance. Therefore, it is of great significance to develop environmentally friendly and solvent-resistant halogen-free V0 flame-retardant ABS materials. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide an environmentally friendly ABS alloy material that exhibits excellent flame retardancy, excellent solvent resistance, and good mechanical properties when used in the preparation of thin-walled products (wall thickness ≤ 2 mm), as well as its preparation method and application.

[0006] To achieve the above objectives, in a first aspect, the present invention provides an ABS alloy material comprising the following components in parts by weight:

[0007] 58-82 parts ABS resin, 18-42 parts ASA adhesive powder, 6-14 parts phosphorus-based flame retardant, 5-11 parts nitrogen-based flame retardant, 5-11 parts heteropoly acid salt, 2-8 parts compatibilizer.

[0008] The present invention provides an ABS alloy material that, by selecting appropriate mass proportions of components and combining them together, achieves a V0 flame retardant rating in the preparation of thin-walled ABS alloy products, while also possessing good rigidity-toughness balance and excellent solvent resistance.

[0009] Specifically, this invention selects to add ASA adhesive powder, which not only provides a halogen-free flame-retardant carbon source, but also works with flame retardants and heteropolyacid salts to improve the flame retardancy of the product. Furthermore, it interacts with ABS resin to effectively toughen the system, improving the product's mechanical properties and solvent resistance. The addition of heteropolyacid salts has several advantages. First, as an acid source, it has strong dehydration capabilities, allowing it to coat the surface of burning materials and enhance the product's flame retardant effect. Simultaneously, it can work with phosphorus-based and nitrogen-based flame retardants to further improve the halogen-free flame retardant effect, enabling the product to achieve a halogen-free V0 flame retardant rating even in thin-walled states. Moreover, the addition of heteropolyacid salts does not damage the product's mechanical properties while improving flame retardancy, thus ensuring good mechanical properties. Second, because heteropolyacid salts have a large number of anions and cations, they can strongly interact with solvents, adsorbing solvents and weakening the interaction between solvents and the resin matrix, preventing solvent-induced cracking and thus improving overall solvent resistance.

[0010] For example, the solvent in the solvent resistance property includes at least one of acetic acid, ethanol, and edible oil.

[0011] For example, the ABS resin can be any point value or any two-point range between 58 and 82 parts, such as 60-80 parts, or 58, 60, 62, 65, 68, 70, 72, 75, 78, 80, 82, etc.; the ASA adhesive powder can be any point value or any two-point range between 18 and 42 parts, such as 20-40 parts, or 18, 20, 23, 25, 28, 30, 32, 35, 38, 40, 42, etc.; the phosphorus-based flame retardant can be any point value or any two-point range between 6 and 14 parts, such as 7-13 parts. Alternatively, the amount can be 6, 7, 8, 9, 10, 11, 12, or 13 parts, etc.; the nitrogen-based flame retardant can be any point value or any two-point range value between 5 and 11 parts, for example, 6-10 parts, or 5, 6, 7, 8, 9, 10, or 11 parts, etc.; the heteropolyacid salt can be any point value or any two-point range value between 5 and 11 parts, for example, 6-10 parts, or 5, 6, 7, 8, 9, 10, or 11 parts, etc.; the compatibilizer can be any point value or any two-point range value between 2 and 8 parts, for example, 3-7 parts, or 2, 3, 4, 5, 6, 7, or 8 parts, etc.

[0012] In the ABS alloy material, the mass percentage of ABS resin is ≥40%.

[0013] Preferably, the ABS alloy material contains 48-60% ABS resin by mass.

[0014] In a preferred embodiment of the ABS alloy material of the present invention, the mass ratio of the ABS resin to the ASA adhesive powder is 1:(0.2-0.7).

[0015] For example, the mass ratio of ABS resin to ASA adhesive powder can be any point value or any two points between 1:(0.2-0.7), such as 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, etc.

[0016] This invention has found that the mass ratio between ABS resin and ASA powder affects the mechanical properties, flame retardant properties, and solvent resistance of the product. When the mass ratio of ABS resin to ASA powder is further selected to be 1:(0.2-0.7), the overall performance of the product is better.

[0017] Preferably, the mass ratio of the ABS resin to the ASA adhesive powder is 1:(0.33-0.5).

[0018] As a preferred embodiment of the ABS alloy material of the present invention, the heteropolyacid salt includes at least one of dodecyl molybdenum phosphate, dodecyl tungsten phosphate, dodecyl molybdenum silicate, and dodecyl tungsten silicate.

[0019] Preferably, the heteropolyacid salt includes dodecyltungsten phosphate and dodecylmolybdenum phosphate.

[0020] More preferably, the heteropolyacid salt includes dodecyl tungstate phosphate.

[0021] For example, the dodecyltungsten phosphate includes at least one of sodium dodecyltungsten phosphate, magnesium dodecyltungsten phosphate, iron dodecyltungsten phosphate, aluminum dodecyltungsten phosphate, chromium dodecyltungsten phosphate, zinc dodecyltungsten phosphate, rhodium dodecyltungsten phosphate, and copper dodecyltungsten phosphate.

[0022] This invention has found that there are differences in the types of heteropoly acid salts themselves and their interactions with phosphorus-based and nitrogen-based flame retardants. When the types of heteropoly acid salts are further selected to be those mentioned above, especially dodecyltungsten phosphate, the resulting products have better flame retardancy, can achieve a V0 flame retardancy rating for thin-walled products (thickness ≤2mm), and have a more superior flame retardant effect. Furthermore, the resulting products have better mechanical properties and solvent resistance.

[0023] As a preferred embodiment of the ABS alloy material of the present invention, the compatibilizer includes at least one of ABS grafted maleic anhydride, styrene-maleic anhydride graft, maleic anhydride grafted SEBS, and stearic acid alcohol ester.

[0024] Preferably, the compatibilizer comprises ABS grafted with maleic anhydride.

[0025] This invention has found that the type of compatibilizer affects the compatibility between components, thereby affecting the product's performance. When the compatibilizer is further selected to be of the type mentioned above, especially ABS grafted with maleic anhydride, the overall performance of the obtained product is better.

[0026] In a preferred embodiment of the ABS alloy material of the present invention, the rubber mass percentage of the ABS resin is 15-30%.

[0027] It should be noted that the rubber mass percentage of ABS resin is determined by the dissolution-precipitation method. Specifically, the dissolution-precipitation method involves dissolving the styrene and styrene phases in an organic solvent (such as dichloromethane), while butadiene, as the rubber phase, is insoluble in the organic solvent, thus achieving phase separation. After drying, the butadiene (rubber) content is calculated.

[0028] For example, the rubber mass percentage of the ABS resin can be any point value or any two points between 15% and 30%, such as 18%-28%, or 15%, 17%, 19%, 20%, 22%, 24%, 26%, 28%, 30%, etc.

[0029] Preferably, the rubber mass percentage of the ABS resin is 22-24%.

[0030] The present invention has found that when the rubber mass percentage of ABS resin is selected to be 15-30%, especially 22-24%, the overall effect of the product is better.

[0031] As a preferred embodiment of the ABS alloy material of the present invention, the phosphorus-based flame retardant includes at least one of bisphenol A-bis(diphenyl phosphate), triphenyl phosphate, and tetraphenylethylene bisphosphate.

[0032] As a preferred embodiment of the ABS alloy material of the present invention, the nitrogen-based flame retardant includes at least one of melamine urate and dicyandiamide.

[0033] This invention does not have any special requirements for ASA adhesive powder, nor for the acrylate content in the ASA adhesive powder. For example, the acrylate content in the ASA adhesive powder can be any point value or any two points between 50-70 wt.%.

[0034] As a preferred embodiment of the ABS alloy material of the present invention, the ABS alloy material further includes 0.1-1 parts of antioxidant and 0.1-1 parts of lubricant.

[0035] For example, the antioxidant includes at least one of hindered phenolic antioxidants, hindered amine antioxidants, and phosphite antioxidants.

[0036] For example, the lubricant includes at least one of stearamide lubricant and zinc stearate lubricant.

[0037] In a second aspect, the present invention also provides a method for preparing the ABS alloy material, the method comprising the following steps: mixing and melting the components and extruding them to obtain the ABS alloy material.

[0038] As a preferred embodiment of the preparation method of the present invention, the parameters of the twin-screw extruder are as follows: the length-to-diameter ratio of the twin-screw extruder is (36-40):1, the screw speed is 250-300 rpm, and the extrusion temperature is 190-200℃.

[0039] In a third aspect, the present invention also provides the application of the ABS alloy material in the fields of household appliances or automobiles.

[0040] Examples include the application of ABS alloy materials in the manufacture of materials for kitchen appliances, medical devices, and bathroom fixtures.

[0041] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0042] This invention provides an ABS alloy material that, through the selection and appropriate combination of its components by mass ratio, achieves a V0 flame retardant rating in thin-walled ABS alloy products, while also exhibiting good rigidity-toughness balance and excellent solvent resistance. Specifically, the resulting products all meet a 2.0mm V0 flame retardant rating, have a modulus above 1623MPa, and an impact strength of 14.2kJ / m. 2 The above-mentioned product exhibits a cracking resistance time of over 17 minutes against glacial acetic acid. Furthermore, the preparation method of the product provided by this invention is simple to operate and beneficial for practical production. Detailed Implementation

[0043] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0044] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in the field; and unless otherwise specified, the raw materials used in parallel experiments are from the same batch.

[0045] ABS-1: ABS HS3302, with a rubber content of 23%, manufactured by Mitsubishi Chemical Corporation, Japan;

[0046] ABS-2: ABSDG-417, with a rubber content of 18%, manufactured by Tianjin Dagu Chemical Co., Ltd.

[0047] ABS-3: ABS 745N, with a rubber content of 28%, manufactured by Kumho Petrochemical Co., Ltd., South Korea;

[0048] ASA adhesive powder 1: XC-500A, acrylate content 50w.t.%, Kumho Petrochemical Co., Ltd., South Korea;

[0049] ASA adhesive powder 2: EM500, acrylate content 70w.t.%, Dongguan Huiyi Chemical Materials Co., Ltd.;

[0050] Phosphorus-based flame retardant 1: Bisphenol A-bis(diphenyl phosphate), commercially available;

[0051] Phosphorus-based flame retardant 2: Triphenyl phosphate, commercially available;

[0052] Nitrogen-based flame retardant 1: Melamine cyanurate, commercially available;

[0053] Nitrogen-based flame retardant 2: Dicyandiamide, commercially available;

[0054] Heteropolyacid salt 1: Sodium dodecyltungstate phosphate, commercially available;

[0055] Heteropolyacid salt 2: Sodium dodecylmolybdate phosphate, commercially available;

[0056] Heteropolyacid salt 3: Sodium dodecylmolybdate, commercially available;

[0057] Compatibilizer 1: KT-2, maleic anhydride-grafted ABS, Shenyang Ketong Plastics Technology Co., Ltd.;

[0058] Compatibilizer 2: SMA 700, styrene-maleic anhydride copolymer, Shanghai Huawen Electronic New Materials Co., Ltd.;

[0059] Compatibilizer 3: Pentaerythritol monostearate, commercially available;

[0060] Antioxidants: Hindered amine antioxidants, commercially available;

[0061] Lubricant: Stearamide lubricant, commercially available.

[0062] The antioxidants and lubricants used in the parallel experiments of the examples and comparative examples were consistent.

[0063] Examples 1-13 and Comparative Examples 1-8

[0064] The present invention provides an ABS alloy material in the embodiments and comparative examples, wherein the component content (parts by weight) of the ABS alloy material is shown in Table 1-2;

[0065] Table 1

[0066]

[0067]

[0068] Table 2

[0069]

[0070] The preparation method of the ABS alloy material provided in Example 1 is as follows:

[0071] After drying, the raw materials are weighed and mixed, then fed into a twin-screw extruder. After extrusion, drawing, cooling, pelletizing, and drying, ABS alloy material is obtained.

[0072] The parameters of the twin-screw extruder are as follows: the length-to-diameter ratio of the twin-screw extruder is 40:1, the screw speed is 280 rpm, and the temperatures of each screw section from the feed port to the die head are 190℃, 190℃, 195℃, 195℃, 195℃, 200℃, and 200℃, respectively.

[0073] The preparation methods of the ABS alloy materials provided in Examples 2-13 and Comparative Examples 1-8 are consistent with those in Example 1, except that the relevant components are not added.

[0074] Example of effect

[0075] The performance of the products prepared in the embodiments and comparative examples of this invention is verified by the following test items:

[0076] 1. Flame retardant performance: The test standard is in accordance with "UL 94-2018 Test for flammability of materials for equipment and appliance components", with a sample thickness of 2.0 mm;

[0077] 2. Cantilever beam notched impact strength: The test standard refers to "ISO 180-2000 Plastics - Determination of IZOD impact strength";

[0078] 3. Flexural modulus: The test standard is in accordance with ISO 178-2010 "Determination of Flexural Properties of Plastics";

[0079] 4. Solvent resistance: The mold used for solvent resistance testing is a steel mold with an inner length of 165 mm; Sample: A tensile specimen made according to ISO 527-1:2019 standard, with a length of 169 mm and a curvature of 0.5%; Chemical reagent: glacial acetic acid; Evaluation method: The chemical reagent is evenly coated on the upper surface of the specimen, at the highest point of the specimen's bending, and then the time of specimen breakage is recorded as the evaluation standard for the material's chemical resistance.

[0080] The test results are shown in Table 3.

[0081] Table 3

[0082]

[0083]

[0084] As can be seen from Table 3, when the technical solution of this invention is adopted, the obtained product has excellent mechanical properties, flame retardant properties, and solvent resistance; specifically, the obtained products can all meet the 2.0mm V0 flame retardant rating, the modulus of the products is above 1623MPa, and the impact strength is above 14.2kJ / m. 2 The above-mentioned resistance to glacial acetic acid cracking time is above 17 minutes;

[0085] As can be seen from Examples 1-3, Comparative Examples 2 and 7-8, the mass fraction of the components has a significant impact on the performance of the products. When the amount of ASA adhesive powder added in Comparative Example 2 is too large, the flame retardant performance of the product decreases significantly, the 2.0mm flame retardant V0 is not reached, and the modulus of the product also shows a significant downward trend. When the amount of heteropoly acid salt added in Comparative Example 7 is too large, the impact strength of the product shows a significant downward trend. When the amount of compatibilizer added in Comparative Example 8 is too large, the flame retardancy of the product decreases significantly, and the modulus and impact strength of the product also show a certain downward trend.

[0086] As can be seen from Examples 1, 6-7, and Comparative Example 1, the mass ratio of ASA adhesive powder to ABS resin affects the product performance. When no ASA adhesive powder is added in Comparative Example 1, the resulting product not only exhibits reduced flame retardancy, failing to meet the 2.0mmV0 flame retardancy rating, but also shows a significant decrease in impact strength. When the mass ratio of ABS resin to ASA adhesive powder is further selected within the preferred range of this invention, the resulting product exhibits superior overall performance. Specifically, the resulting product meets the 2.0mmV0 flame retardancy rating, has an acetic acid cracking resistance time of over 20 minutes, a modulus of over 2013 MPa, and an impact strength of 15.7 kJ / m². 2 above;

[0087] As can be seen from Examples 1 and Comparative Examples 3-6, the heteropoly acid salts, phosphorus-based flame retardants and nitrogen-based flame retardants added in this invention have a certain compounding effect. When any one of them is not added, the flame retardant performance of the obtained product decreases significantly.

[0088] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An ABS alloy material, characterized in that, The ABS alloy material comprises the following components in parts by weight: 58-82 parts ABS resin, 18-42 parts ASA adhesive powder, 6-14 parts phosphorus-based flame retardant, 5-11 parts nitrogen-based flame retardant, 6-10 parts heteropoly acid salt, 2-8 parts compatibilizer; The compatibilizer comprises ABS grafted with maleic anhydride.

2. The ABS alloy material according to claim 1, characterized in that, The mass ratio of ABS resin to ASA adhesive powder is 1:(0.2-0.7).

3. The ABS alloy material according to claim 1, characterized in that, The heteropolyacid salts include at least one of dodecyl molybdenum phosphate, dodecyl tungsten phosphate, dodecyl molybdenum silicate, and dodecyl tungsten silicate.

4. The ABS alloy material according to claim 1, characterized in that, The rubber mass percentage of the ABS resin is 15-30%.

5. The ABS alloy material according to claim 1, characterized in that, The phosphorus-based flame retardant includes at least one of bisphenol A-bis(diphenyl phosphate), triphenyl phosphate, and tetraphenyl phenylene diphosphate.

6. The ABS alloy material according to claim 1, characterized in that, The nitrogen-based flame retardant includes at least one of melamine urate and dicyandiamide.

7. The ABS alloy material according to claim 1, characterized in that, The ABS alloy material also includes 0.1-1 parts antioxidant and 0.1-1 parts lubricant.

8. The method for preparing the ABS alloy material according to any one of claims 1-7, characterized in that, The preparation method includes the following steps: mixing and melting the components and extruding them to obtain ABS alloy material.

9. The application of the ABS alloy material as described in any one of claims 1-7 in the fields of household appliances or automobiles.

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