HIPS alloy material and preparation method and application thereof

Abstract

The application discloses a HIPS alloy material and a preparation method and application thereof, and belongs to the technical field of high polymer engineering plastics. The HIPS alloy material comprises the following components in parts by mass: 58-82 parts of HIPS resin, 18-42 parts of ASA glue powder, 10-18 parts of phosphorus flame retardant, 3-9 parts of nitrogen flame retardant, 4-12 parts of hollow glass microbead and 1-9 parts of compatibility agent. The mass content of acrylate in the ASA glue powder is 53-66%. The average particle size of the hollow glass microbead is 38-82 mu m. The HIPS alloy material provided by the application has excellent flame retardance and mechanical properties. The preparation method is simple and is beneficial to actual production.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer engineering plastics, and in particular relates to a HIPS alloy material and a preparation method and application thereof. Background Art

[0002] GPPS, or general-purpose polystyrene, is a general-purpose plastic with advantages such as high rigidity, high gloss, high fluidity and dimensional stability. It is widely used in fields such as home appliances, office equipment and automobiles. However, its poor toughness limits its application in fields with high toughness requirements. At present, the most common way to improve the defect of poor impact performance of general-purpose polystyrene is to modify general-purpose polystyrene by adding polybutadiene rubber to form high-impact polystyrene (HIPS). The improvement in toughness has greatly broadened the application range of PS materials, but HIPS itself is a flammable material and is prone to dripping and burning through during the combustion process, thus failing to meet the 5VA flame retardant rating. Usually, a considerable proportion of bromine antimony flame retardants and anti-drip agents must be added to achieve a 5VA flame retardant rating. However, brominated flame retardants and anti-drip agents (commonly used polytetrafluoroethylene) have two major problems: high price and environmental pollution.

[0003] At present, thin-walled products (thickness ≤ 2mm) have become a development trend for many products, such as televisions, printers, and car interiors, which has led to increasingly higher requirements for flame retardant properties. Since 5VA flame retardancy is higher than V-0 flame retardancy, meeting 5VA flame retardancy has also become an important development direction for many materials to meet the requirements for high flame retardancy after thin-walled products. A Chinese patent (CN112745591B) discloses a flame-retardant, high-rigidity PS / PPE composite material and its preparation. The solution uses a brominated flame retardant and glass fiber compound to achieve a 5VA flame retardant grade, but the use of brominated flame retardants cannot meet halogen-free environmental protection requirements, and the patent does not explore whether the thin-walled product can still meet the 5VA flame retardant grade. A Chinese patent (CN117757208A) discloses a polystyrene material. Although it can achieve a 5VA flame retardant grade for products with a thickness of 2mm, an anti-dripping agent is added to the formula, which not only poses a threat to the environment, but also damages the mechanical properties to a certain extent. Summary of the Invention

[0004] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a HIPS alloy material that can meet the 5VA flame retardancy rating in a thin-walled state (thickness ≤ 2 mm) and has good strength and toughness, as well as a preparation method and application thereof.

[0005] To achieve the above objectives, in a first aspect of the present invention, a HIPS alloy material is provided, comprising the following components in parts by mass: 58-82 parts of HIPS resin, 18-42 parts of ASA rubber powder, 10-18 parts of phosphorus-based flame retardant, 3-9 parts of nitrogen-based flame retardant, 4-12 parts of hollow glass microspheres, and 1-9 parts of compatibilizer;

[0006] The mass content of acrylate in the ASA rubber powder is 53-66%;

[0007] The average particle size of the hollow glass microspheres is 38-82 μm.

[0008] The HIPS alloy material provided by the present invention is prepared by selectively adding hollow glass microspheres within a specific average particle size range, selecting ASA rubber powder with a specific acrylate mass content range, and combining other components in appropriate mass proportions. The obtained product can meet the halogen-free 5VA flame retardant grade when prepared into a thin-walled product (thickness ≤ 2 mm), and achieves the 5VA flame retardant grade without adding an anti-dripping agent. At the same time, the obtained product has good toughness and rigidity.

[0009] Specifically, the addition of ASA rubber powder within a specific acrylate mass content range can fully utilize its polar and non-polar properties, acting as a bridge between the polar hollow glass microsphere surface and the non-polar HIPS resin, effectively strengthening the bonding between the two and improving the material's melt strength, thereby enhancing the product's flame retardancy and mechanical properties. The addition of hollow glass microspheres within a specific average particle size range not only provides insulation and slows heat transfer, but also acts as a network of nodes, enhancing the material's melt strength and preventing burn-through, further helping to improve the product's flame retardancy and mechanical properties. Furthermore, hollow glass microspheres are low-density materials, and as components of HIPS alloy materials, they can reduce the density of the HIPS alloy material, thereby reducing production costs. Furthermore, the addition of a compatibilizer within a specific mass range can effectively enhance the compatibility of HIPS and ASA rubber powder, thereby improving the overall compatibility of the system and improving the overall product performance.

[0010] The mass content of acrylate in the ASA rubber powder is calculated by gas chromatography. This method is based on the separation characteristics of acrylate in a gas chromatographic column, utilizing the volatility of acrylate in the sample and performing quantitative analysis using the detector of a gas chromatograph. The specific steps are as follows: First, prepare the sample. Dissolve the sample to be tested in a suitable solvent to prepare a sample solution of a certain concentration. Simultaneously, add an internal standard for calibration during quantitative analysis. Then, inject the sample into the gas chromatograph for testing, and perform quantitative analysis based on the results.

[0011] The average particle size of the hollow glass microspheres is obtained by testing with a laser particle size analyzer.

[0012] For example, the mass content of the HIPS resin may be any value between 58 and 82 parts or any two-point range values, such as 60-80 parts, or 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, 82 parts, etc.; the mass content of the ASA rubber powder may be any value between 18 and 42 parts or any two-point range values, such as 20-40 parts, or 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, etc.; the mass content of the phosphorus-based flame retardant may be any value between 10 and 18 parts or any two-point range values, such as 12-16 parts. , or it can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, etc.; the nitrogen-based flame retardant can be any point value between 3-9 parts or any two-point range value, such as 5-7 parts, or it can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, etc.; the hollow glass microspheres can be any point value between 4-12 parts or any two-point range value, such as 6-10 parts, or it can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, etc.; the compatibilizer can be any point value between 1-9 parts or any two-point range value, such as 3-7 parts, or it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, etc.

[0013] Exemplarily, in the ASA rubber powder, the mass content of acrylate can be any point value or any two point range values ​​between 53-66%, for example, it can be 55-64%, or it can be 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, etc.

[0014] Exemplarily, the average particle size of the hollow glass microspheres can be any point value or any two point range values ​​between 38-82 μm, for example, 40-80 μm, or 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, etc.

[0015] Preferably, the mass content of acrylate in the ASA rubber powder is 56-60%.

[0016] Preferably, the average particle size of the hollow glass microspheres is 55-65 μm.

[0017] Preferably, in the HIPS alloy material, the mass percentage of ASA rubber powder is 12-38%, and the mass percentage of hollow glass microspheres is 2-12%.

[0018] As a preferred embodiment of the HIPS alloy material of the present invention, the HIPS alloy material comprises the following components in parts by mass: 25-32 parts of ASA rubber powder, 8-9 parts of hollow glass microspheres, and 5-6 parts of a compatibilizer.

[0019] The present invention has found that the addition amount of ASA rubber powder, hollow glass microspheres and compatibilizer will affect the performance of the product. When the mass parts of the three are further selected to be within the above range, the comprehensive performance of the obtained product is better.

[0020] As a preferred embodiment of the HIPS alloy material of the present invention, the rubber mass content of the HIPS resin is 15-28%.

[0021] Specifically, the rubber content of HIPS resin refers to the mass content of butadiene. The rubber content of HIPS resin is determined by solvent extraction. First, a HIPS sample is thoroughly mixed with a suitable solvent (such as benzene or xylene) to dissolve the butadiene rubber in the solvent to form a solution. The solvent is then evaporated to obtain a rubber residue. Finally, the mass of the rubber residue is compared with the mass of the initial HIPS sample to determine the rubber content.

[0022] For example, the rubber mass content of the HIPS resin can be any point value or any two point range values ​​between 15-28%, such as 18-25%, or 15%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 28%, etc.

[0023] Preferably, the rubber mass content of the HIPS resin may be 20-22%.

[0024] The present invention has found that the rubber content of HIPS resin affects the mechanical properties of the product and also has a certain impact on the flame retardant properties of the product. When the rubber content of HIPS resin is further selected to be 15-28%, especially 20-22%, the overall effect of the obtained product is better.

[0025] As a preferred embodiment of the HIPS alloy material of the present invention, the compatibilizer includes at least one of styrene-maleic anhydride copolymer, maleic anhydride grafted SEBS, silicone, and maleic anhydride grafted ABS.

[0026] Preferably, the compatibilizer includes at least one of styrene-maleic anhydride copolymer and maleic anhydride grafted SEBS.

[0027] The present invention has found that the selection of a compatibilizer affects the compatibility between the components, thereby affecting the melt strength of the product and further affecting the overall performance of the product. When the compatibilizer is further selected as a substance of the above category, the overall performance of the obtained product is better.

[0028] As a preferred embodiment of the HIPS alloy material of the present invention, the phosphorus-based flame retardant includes at least one of bisphenol A-bis(diphenyl phosphate) and triphenyl phosphate.

[0029] As a preferred embodiment of the HIPS alloy material of the present invention, the nitrogen-based flame retardant includes at least one of melamine cyanurate and dicyandiamide.

[0030] As a preferred embodiment of the HIPS alloy material of the present invention, the HIPS alloy material further comprises 0.1-1 parts of a processing aid.

[0031] Preferably, the processing aid includes at least one of an antioxidant and a lubricant.

[0032] Illustratively, the antioxidant includes at least one of a hindered phenol antioxidant, a hindered amine antioxidant, and a phosphite antioxidant.

[0033] Illustratively, the lubricant includes at least one of a stearamide lubricant and a zinc stearate lubricant.

[0034] In the second aspect of the present invention, the present invention also provides a method for preparing the HIPS alloy material, which comprises the following steps: weighing the dried raw materials, mixing them, and feeding them into a twin-screw extruder, extruding, drawing, cooling, pelletizing, and drying to obtain the HIPS alloy material.

[0035] As a preferred embodiment of the preparation method of the present invention, the parameters of the twin-screw extruder are: the aspect ratio of the twin-screw extruder is (40-36):1, the screw speed is 250-300 rpm, and the extrusion temperature is 190-200°C.

[0036] In the third aspect of the present invention, the present invention also provides the use of the HIPS alloy material in preparing flame-retardant ultra-thin materials.

[0037] For example, HIPS alloy materials are used in the preparation of various home appliance housings, printer panels, automobile interiors and other materials.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The HIPS alloy material provided by the present invention is prepared by adding hollow glass microspheres within a specific average particle size range, selecting ASA rubber powder with a specific acrylate mass content range, and combining other components in appropriate mass parts. The obtained product can meet the halogen-free 5VA flame retardant grade when prepared into a thin-walled product (thickness ≤ 2 mm) without adding an anti-dripping agent, and the obtained product has good toughness and strength. Specifically, the obtained HIPS alloy material has an Izod notched impact strength of 18.3 kJ / m 2 The above-mentioned properties have a bending strength of more than 27.5 MPa and a flame retardant performance that meets the 2.0 mm 5VA grade. In addition, the preparation method of the HIPS alloy material provided by the present invention is simple and is conducive to actual production. DETAILED DESCRIPTION

[0040] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0041] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0042] HIPS-1: PS1180, rubber content 21.4wt%, Trinseo, USA;

[0043] HIPS-2: PS HI-425TVL, rubber content 18.1wt%, Kumho Petrochemical Co., Ltd., South Korea;

[0044] HIPS-3: PS PH-888G, rubber content 25.0wt%, Chi Mei Chemical Co., Ltd., Taiwan, China;

[0045] HIPS-4: PS 514P, rubber content 15.3 wt%, Shanghai Secco Petrochemical Co., Ltd.

[0046] HIPS-5: PS1110, rubber content 27.2wt%, Trinseo, USA;

[0047] ASA rubber powder 1: M800, acrylate content 58w.t.%, Zhejiang Suqi New Materials Co., Ltd.;

[0048] ASA rubber powder 2: A600N, acrylate content 55w.t.%, Zhejiang Changhong Plastic Raw Materials Co., Ltd.

[0049] ASA rubber powder 3: Q350KL, acrylate content 64w.t.%, Zhejiang Suqi New Materials Co., Ltd.

[0050] ASA rubber powder 4: XC-500A, acrylate content 50wt%, Kumho Petrochemical Co., Ltd., South Korea;

[0051] ASA rubber powder 5: EM500, acrylate content 70wt%. Dongguan Huiyi Chemical Materials Co., Ltd.

[0052] Hollow glass microspheres 1: HN20, average particle size 60 μm, Shanxi Hainuo Technology Co., Ltd.

[0053] Hollow glass microspheres 2: 320#, average particle size 40 μm, Lingshou Baiyi Mineral Products Co., Ltd.

[0054] Hollow glass microspheres 3: 220#, average particle size 80 μm, Lingshou Baiyi Mineral Products Co., Ltd.

[0055] Hollow glass microspheres 4: HN16K, average particle size 30 μm, Shanxi Hainuo Technology Co., Ltd.

[0056] Hollow glass microspheres 5:180#, average particle size 90μm, Lingshou Baiyi Mineral Products Co., Ltd.

[0057] Solid glass microspheres 6: 220 mesh glass microspheres, average particle size 50 μm, Okey Minerals Company;

[0058] Compatibilizer 1: SEBS FG1901GT, maleic anhydride grafted SEBS, Kraton, USA;

[0059] Compatibilizer 2: SMA 700, styrene-maleic anhydride copolymer, Shanghai Huawen Electronic New Materials Co., Ltd.

[0060] Compatibilizer 3: KT-2, maleic anhydride grafted ABS, Shenyang Ketong Plastic Technology Co., Ltd.

[0061] Compatibilizer 4: MB50-002, silicone, Dow Corning;

[0062] Phosphorus flame retardant: bisphenol A-bis(diphenyl phosphate), commercially available;

[0063] Nitrogen flame retardant: melamine cyanurate, commercially available;

[0064] Antioxidant: hindered amine antioxidant, commercially available;

[0065] Lubricant: Stearic acid amide lubricant, commercially available.

[0066] The antioxidants and lubricants used in the parallel experiments of the examples and comparative examples were consistent.

[0067] Examples 1-16 and Comparative Examples 1-9

[0068] The embodiments and comparative examples of the present invention provide a HIPS alloy material, and the component contents (parts by weight) of the HIPS alloy material are shown in Tables 1-3;

[0069] Table 1

[0070]

[0071] Table 2

[0072]

[0073]

[0074] Table 3

[0075]

[0076] The preparation method of the HIPS alloy material provided in Example 1 is:

[0077] The dried raw materials are weighed, mixed and fed into a twin-screw extruder, and subjected to extrusion, strand drawing, cooling, pelletizing and drying to obtain a HIPS alloy material;

[0078] The parameters of the twin-screw extruder are as follows: the aspect ratio of the twin-screw extruder is 40:1, the screw speed is 280 rpm, and the extrusion temperature is 195°C.

[0079] The preparation methods of the HIPS alloy materials provided in Examples 2-16 and Comparative Examples 1-9 are consistent with that in Example 1, except that no relevant components are added.

[0080] Effect Examples

[0081] The effectiveness examples of the present invention verify the performance of the products prepared in the examples and comparative examples; the test items include the following aspects:

[0082] 1. Bending strength test: The test standard refers to ISO 178-2010 Plastics - Determination of flexural properties;

[0083] 2. Izod notched impact strength test: The test standard refers to ISO 180-2000 Plastics - Determination of Izod impact strength, and the notch type is Type A;

[0084] 3. 5VA flame retardancy test: The test standard refers to "UL 94-2018 Tests for Flammability of Materials for Equipment and Appliance Components", sample thickness 1.5 / 2.0mm;

[0085] The test results are shown in Table 4;

[0086] Table 4

[0087]

[0088] It can be seen from Table 4 that when the technical solution of the present invention is adopted, the obtained product has excellent mechanical properties and flame retardant properties; specifically, the obtained product has an Izod notched impact strength of 18.3 kJ / m 2 Above, the bending strength is above 27.5MPa, and all have 2.0mm 5VA flame retardant grade;

[0089] It can be seen from Examples 1-4 and Comparative Examples 1-3 that the quality of the components has a significant impact on the overall performance of the product. When the mass fractions of the components in Comparative Examples 1-3 are not within the ranges given in the present invention, the flame retardant properties of the resulting products are significantly reduced and cannot meet the 2.0 mm 5VA flame retardant rating. However, when the mass fractions of the components are further selected to be within the preferred ranges of the present invention, the resulting products can meet the 1.5 mm 5VA flame retardant rating.

[0090] It can be seen from Example 1, Examples 10-11 and Comparative Examples 8-9 that the mass content of acrylate in ASA rubber powder also affects the performance of the product. When the mass content of acrylate in the ASA rubber powder in Comparative Examples 8-9 is not within the given range, the obtained product cannot meet the thin-wall (thickness ≤ 2.00 mm) 5VA flame retardant grade.

[0091] It can be seen from Example 1, Examples 12-13 and Comparative Examples 5-6 that the average particle size of the hollow glass microspheres will also affect the flame retardant properties of the product. When the average particle size of the hollow glass microspheres in Comparative Examples 5-6 is not within the range given in the present invention, the obtained product cannot meet the thin-walled (thickness ≤ 2.00 mm) 5VA flame retardant grade; it can be seen from Example 1 and Comparative Example 4 that when the hollow glass microspheres are not added, the obtained product not only fails to meet the 5VA flame retardant grade, but also shows a certain downward trend in bending strength; it can be seen from Example 1 and Comparative Example 7 that when solid glass microspheres are used instead of hollow glass microspheres, the obtained product also fails to meet the thin-walled (thickness ≤ 2.00 mm) 5VA flame retardant grade.

[0092] Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention rather than 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 the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A HIPS alloy material, characterized in that: The HIPS alloy material comprises the following components in parts by mass: 58-82 parts of HIPS resin, 18-42 parts of ASA rubber powder, 10-18 parts of phosphorus flame retardant, 3-9 parts of nitrogen flame retardant, 4-12 parts of hollow glass microspheres, and 1-9 parts of compatibilizer; The mass content of acrylate in the ASA rubber powder is 53-66%; The average particle size of the hollow glass microspheres is 38-82 μm.

2. The HIPS alloy material according to claim 1, characterized in that The HIPS alloy material comprises the following components in parts by mass: 25-32 parts of ASA rubber powder, 8-9 parts of hollow glass microspheres, and 5-6 parts of a compatibilizer.

3. The HIPS alloy material according to claim 1, characterized in that The rubber mass content of the HIPS resin is 15-28%.

4. The HIPS alloy material according to claim 1, characterized in that The compatibilizer includes at least one of styrene-maleic anhydride copolymer, maleic anhydride grafted SEBS, silicone, and maleic anhydride grafted ABS.

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

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

7. The HIPS alloy material according to claim 1, characterized in that: The HIPS alloy material further includes 0.1-1 parts of a processing aid.

8. The method for preparing the HIPS alloy material according to any one of claims 1 to 7, wherein: The preparation method comprises the following steps: weighing the dried raw materials, mixing them and feeding them into a twin-screw extruder, and performing extrusion, strip drawing, cooling, pelletizing and drying to obtain a HIPS alloy material.

9. Use of the HIPS alloy material according to any one of claims 1 to 7 in the preparation of flame-retardant ultra-thin materials.

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