Abs material, its preparation method and application

Abstract

The application discloses an ABS material, which comprises the following components in parts by weight: ABS resin 100 parts; bromine flame retardant 18-24 parts; magnesium-aluminum hydrotalcite 3-8 parts; polypropylene resin 30-60 parts; supporting filler 10-25 parts; compatibilizer 10-20 parts; and char-forming agent 5-10 parts; wherein the compatibilizer is selected from a complex of a styrene copolymer, PS-g-PP and PP-g-MAH, and the weight ratio is (1-2)(1-3):1. The ABS material has UL 94 5VA level flame retardancy and good heat deformation resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to an ABS material and a preparation method and application thereof. BACKGROUND

[0002] Acrylonitrile-butadiene-styrene copolymer (ABS) is widely used in the fields of automobiles, electronics, electrical appliances, textiles, utensils and building materials due to its excellent mechanical properties and good processing properties. In recent years, with the development of electronic appliances, communication, household appliances and electromechanical equipment towards high performance and miniaturization, the requirements for the flame retardant properties of materials are becoming higher and higher. Most of the conventional commercial flame-retardant ABS materials can meet the UL94 V-0, but there are few commercial ABS materials that can meet the UL94 5VA level, and it is even more difficult to meet the demand for thin-walled products.

[0003] Chinese patent application CN118146611A discloses a thin-walled 5VA flame-retardant ABS composition, which comprises 100 parts of ABS resin, 12-20 parts of bromine-based flame retardant, 1-4 parts of flame-retardant synergist, 7-13 parts of organic heat-resistant agent, 5-10 parts of inorganic heat-resistant agent and 5-10 parts of olefin grafting. The thin-walled 5VA flame-retardant ABS composition has the characteristics of thin-walled 5VA flame retardation, good tensile strength and good drop ball impact performance. However, the heat distortion resistance of the patent solution still needs to be further improved.

[0004] Therefore, there is a need in the market for an ABS material with UL94 5VA level flame retardation, good thin-walled performance and good heat distortion resistance. SUMMARY

[0005] The present application aims to provide an ABS material with UL94 5VA level flame retardation, good thin-walled performance and good heat distortion resistance, as well as a preparation method and application thereof.

[0006] The present application is achieved by the following technical solutions:

[0007] An ABS material, by weight, comprises the following components:

[0008] ABS resin 100 parts;

[0009] Polypropylene resin 30-60 parts;

[0010] Bromine-based flame retardant 18-24 parts;

[0011] Magnesium-aluminum hydrotalcite 3-8 parts;

[0012] Supporting filler 10-25 parts;

[0013] Compatibilizer 10-20 parts;

[0014] Char former 5-10 parts;

[0015] The compatibilizer is selected from a complex of styrene copolymer, polystyrene grafted polypropylene and polypropylene grafted maleic anhydride, with a weight ratio of (1-2):(1-3):1.

[0016] The bromine-based flame retardant is selected from at least one of decabromodiphenyl ethane, brominated triazine and brominated epoxy.

[0017] The self-supporting filler is selected from at least one of whisker, wollastonite and glass fiber.

[0018] Preferably, the compatibilizer is selected from a complex of styrene copolymer, polystyrene grafted polypropylene and polypropylene grafted maleic anhydride, with a weight ratio of (1.3-1.8):(1.5-2.5):1.

[0019] The styrene copolymer is selected from styrene grafted maleic anhydride, styrene-acrylonitrile-maleic anhydride copolymer and the like.

[0020] The char former is a polyhydric alcohol selected from at least one of pentaerythritol, dipentaerythritol, starch, sorbitol and tri-pentaerythritol.

[0021] The ABS resin has no particular limitation, and preferably has a melt index in the range of 20-60 g / 10 min under the test conditions of 220 DEG C / 10 KG.

[0022] The polypropylene resin has no particular limitation, and preferably has a melt index in the range of 2-10 g / 10 min under the test conditions of 230 DEG C / 2.16 KG.

[0023] 0-4 parts of an auxiliary agent can be added or not according to actual conditions, the auxiliary agent is selected from at least one of an antioxidant and a lubricant, wherein the antioxidant is one or a composite of hindered phenol and phosphite, and the lubricant is ethylene bis-stearamide.

[0024] The preparation method of the ABS material comprises the following steps: uniformly mixing components according to a proportion, and extruding and granulating through a double-screw extruder to obtain the ABS material.

[0025] The ABS material is used for preparing UL94 5VA level flame-retardant products, such as electric control boxes and electric meter boxes.

[0026] The ABS material has the following beneficial effects:

[0027] The application can form a continuous rigid skeleton structure by supporting filler and the compounding compatibilizer of the application, and contains a specific content of polypropylene resin to improve heat resistance, provide sufficient rigidity to cause the material to be less likely to deform when heated, so that the flame escapes. At the same time, by taking advantage of the poor compatibility of polypropylene and ABS, by adding specific compatibilizers and suitable proportions to regulate the PP and ABS resin to form a co-continuous phase structure, and by adjusting the supporting material and brominated flame retardant to be dispersed at the phase interface of PP and ABS phase, a continuous phase flame retardant system can be formed, which greatly improves the fire resistance of the material by the mechanism of gas phase free radical capture and condensed phase carbon formation to form a protective layer. Provide a strong defense line for the material; at the same time, in the traditional bromine-antimony flame retardant system, magnesium-aluminum hydrotalcite is used to replace antimony white, which can further improve the heat deformation resistance while reducing the amount of antimony white. At the same time, the ABS material of the application has good fluidity (≥18 g / 10 min, 220℃ / 10 kg), which is suitable for injection molding of thin-walled parts. DETAILED DESCRIPTION

[0028] The application will be described in detail below in conjunction with specific examples. The following examples will help those skilled in the art to further understand the application, but do not limit the application in any form. It should be pointed out that for those skilled in the art, without departing from the concept of the application, a number of modifications and improvements can be made. These all belong to the protection scope of the application.

[0029] The raw materials used in the application are as follows:

[0030] ABS resin: ABS KF-730, melt index 22 g / 10 min, Liaoning Jinfa Technology Co., Ltd.; ABS 0215H, melt index 20 g / 10 min, China Petroleum and Natural Gas Co., Ltd.;

[0031] Polypropylene resin: KF-K8003, melt index 2.26 g / 10 min; Ningbo Jinfa New Material Co., Ltd.; PPBX3500 (ZHONGHAN), melt index 8.7 g / 10 min, China Petrochemical Chemical Sales Co., Ltd. Central Branch;

[0032] Decabromodiphenyl ethane: SAYTEX 8010, Albemarle Management (Shanghai) Co., Ltd.

[0033] Brominated triazine: FR-245, ICL TRADING (HK) LTD. Israel Chemical Industry;

[0034] Brominated epoxy: F-3014, Bromine Compounds Marketing;

[0035] Mg-Al hydrotalcite: HT-88F, Shanghai Yunhe Material Science and Technology Co., Ltd.

[0036] Whisker: ABcx-2, Changzhou Aobang Material Science and Technology Co., Ltd.

[0037] Wollastonite: WFC5-2101, Hubei Fengjiashan Silicon Fiber Co., Ltd.

[0038] Glass fiber: ECS13-4.5-534AFF, China Jushi Co., Ltd.

[0039] Styrene grafted maleic anhydride: SMA-700, Jiaxing Huawen Chemical Co., Ltd.

[0040] Styrene-acrylonitrile-maleic anhydride copolymer: SMA-800, Jiaxing Huawen Chemical Co., Ltd.

[0041] Polystyrene grafted polypropylene: BP-1310, Jia Yirong Polymer (Shanghai) Co., Ltd.

[0042] Polypropylene grafted maleic anhydride: PC-1, Foshan Nanhai Baimen High Polymer New Material Co., Ltd.

[0043] Pentaerythritol: Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0044] Dipentaerythritol: Wuhan Kemik Biological Medicine Co., Ltd.

[0045] Starch: corn starch, Shandong Fuyang Biological Starch Co., Ltd.

[0046] Sorbitol: D-sorbitol, Shanghai Aladdin Bio-Chem Technology Co., Ltd.

[0047] Antioxidant: RIANOX 1076, Tianjin Li'anlong New Material Co., Ltd.

[0048] Preparation method of ABS material of examples and comparative examples: according to the ratio, mix each component uniformly, and extrude and granulate through a double screw extruder, the temperature of the screw is set to 190-230°C, and the rotation speed is 800 revolutions / minute, to obtain the ABS material.

[0049] Each test method:

[0050] (1) Flame retardant grade: tested according to standard UL94-2009, tested 1.5 mm, 2.0 mm, 2.5 mm, and 3.0 mm thickness. Only the thickness reaching 5VA is recorded in the table, and the thinner the thickness reaching 5VA, the better the fire resistance.

[0051] (2) Melt flow rate: measured according to ISO 1133-2011 standard, test condition: 220℃ / 10kg.

[0052] (3) Heat deflection temperature: HDT (℃): tested according to ISO 75-2 standard, load: 0.45MPa.

[0053] Table 1: Component content (parts by weight) and test results of ABS materials of Examples 1-6

[0054] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 ABS resin 100 100 100 100 100 100 Polypropylene resin 30 45 60 45 45 45 decabromodiphenyl ethane 18 Bromotriazine 20 20 20 20 Brominated epoxy 24 Magnesium aluminum hydrotalcite 3 6 8 6 6 6 whiskers 10 Wollastonite 18 18 18 18 Fiberglass 25 Styrene grafted with maleic anhydride 5.1 6.6 5 6 3 Styrene-acrylonitrile-maleic anhydride copolymer 3.4 Polystyrene grafted polypropylene 4.4 6.6 8.8 5 6 9 Polypropylene grafted with maleic anhydride 2.2 3.3 4.4 5 3 3 Pentaerythritol 5 8 10 8 8 8 antioxidants 0.2 0.2 0.2 0.2 0.2 0.2 Flame retardancy 1.5mm 5VA 1.5mm 5VA 2.0mm 5VA 1.5mm 5VA 1.5mm 5VA 1.5mm 5VA Melt flow rate g / 10min 18 31 40 28 29 35 Heat distortion temperature (°C) 82 79 75 78 79 76

[0055] Table 2: Component content (parts by weight) and test results of ABS materials of Examples 7-12

[0056] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 ABS resin 100 100 100 100 100 100 Polypropylene resin 45 45 45 45 45 45 Bromotriazine 20 20 20 20 20 20 Magnesium aluminum hydrotalcite 6 6 6 6 6 6 Wollastonite 18 18 18 18 18 18 Styrene grafted with maleic anhydride 5 5.2 5.1 5.1 5.1 5.1 Polystyrene grafted polypropylene 7.5 5.9 7.1 6.6 6.6 6.6 Polypropylene grafted with maleic anhydride 2.5 3.9 2.8 3.3 3.3 3.3 Pentaerythritol 8 8 8 Dipentaerythritol 8 starch 8 Sorbitol 8 antioxidants 0.2 0.2 0.2 0.2 0.2 0.2 Flame retardancy 1.5mm 5VA 1.5mm 5VA 1.5mm 5VA 1.5mm 5VA 1.5mm 5VA 1.5mm 5VA Melt flow rate g / 10min 33 38 40 31 32 34 Heat distortion temperature (°C) 77 80 81 79 78 75

[0057] From Examples 4-9, it can be seen that the weight ratio of styrene copolymer, polystyrene grafted polypropylene and polypropylene grafted maleic anhydride (1.3-1.8) (1.5-2.5): 1 is preferred.

[0058] Table 3: Component content (parts by weight) and test results of ABS materials of Comparative Examples 1-4

[0059] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 ABS resin 100 100 100 100 Polypropylene resin 15 80 45 45 Bromotriazine 20 20 20 20 Magnesium aluminum hydrotalcite 6 6 6 6 Wollastonite 18 18 18 18 Styrene grafted with maleic anhydride 5.1 5.1 5.1 5.1 Polystyrene grafted polypropylene 6.6 6.6 6.6 6.6 Polypropylene grafted with maleic anhydride 3.3 3.3 3.3 3.3 Pentaerythritol 8 8 2 15 antioxidants 0.2 0.2 0.2 0.2 Flame retardancy 3.0mm 5VA 3.0mm 5VA 3.0mm 5VA 3.0mm V-0 Melt flow rate g / 10min 25 40 22 33 Heat distortion temperature (°C) 70 74 73 68

[0060] From Comparative Examples 1 / 2, it can be seen that when the content of polypropylene is too low or too high, it is impossible to achieve thin-wall flame retardation, and when the content of polypropylene is too low, it is insufficient to improve the heat deflection temperature of the ABS material, and when the content of polypropylene is too high, the heat deflection temperature is also reduced due to compatibility problems.

[0061] From Comparative Examples 3 / 4, it can be seen that if the content of charring agent is too low or too high, it is impossible to achieve thin-wall flame retardation, and the heat deflection temperature is also low. Specifically, when the content of charring agent is too low, the carbon layer is not dense enough, and only 3.0mm 5VA can be achieved; when the content of charring agent is too high, the generated carbon layer has no ductility and is easy to crack, losing the protective layer effect.

[0062] Table 4: Component content (parts by weight) and test results of ABS materials of Comparative Examples 5-9

[0063] Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 ABS resin 100 100 100 100 100 Polypropylene resin 45 45 45 45 45 Bromotriazine 20 20 20 20 20 Magnesium aluminum hydrotalcite 6 6 6 6 6 Wollastonite 18 18 18 18 18 Styrene grafted with maleic anhydride 0 2.2 10 10 5 Polystyrene grafted polypropylene 10 10.7 2.5 0 10 Polypropylene grafted with maleic anhydride 5 2.1 2.5 5 0 Pentaerythritol 8 8 8 8 8 antioxidants 0.2 0.2 0.2 0.2 0.2 Flame retardancy 3.0mm V-0 3.0mm V-0 3.0mm V-0 3.0mm V-0 3.0mm V-0 Melt flow rate g / 10min 20 23 17 12 16 Heat distortion temperature (°C) 72 74 74 74 73

[0064] From Comparative Examples 5-9, it can be seen that if the ratio of styrene copolymer, polystyrene grafted polypropylene and polypropylene grafted maleic anhydride is not within the scope of the present application, the grafting reaction degree of wollastonite, magnesium-aluminum hydrotalcite, etc. is different, resulting in material aggregation and other phenomena, which cannot achieve thin-wall flame retardation, and the melt index also decreases significantly.

Claims

1. An ABS material, characterized in that, By weight parts, including the following components: ABS resin 100 parts; Polypropylene resin 30-60 parts; Bromine flame retardant 18-24 parts; Magnesium aluminum hydrotalcite 3-8 parts; Supporting filler 10-25 parts; Compatibilizer 10-20 parts; Char former 5-10 parts; The compatibilizer is selected from the compounding of styrene copolymer, PS-g-PP and PP-g-MAH, the weight ratio is (1-2):(1-3):

1. The styrene copolymer is selected from at least one of PS-g-MAH, styrene-acrylonitrile-maleic anhydride copolymer.

2. The ABS material according to claim 1, characterized in that, The bromine flame retardant is selected from at least one of decabromodiphenyl ethane, bromine triazine, brominated epoxy.

3. The ABS material of claim 1, wherein, The supporting filler is selected from at least one of whisker, wollastonite, glass fiber.

4. The ABS material of claim 1, wherein, The compatibilizer is selected from the compounding of styrene copolymer, PS-g-PP and PP-g-MAH, the weight ratio is (1-2):(1-3):

1.

5. The ABS material of claim 1, wherein, The char former is selected from polyhydric alcohol, the polyhydric alcohol is selected from at least one of pentaerythritol, dipentaerythritol, starch, sorbitol, tri-pentaerythritol.

6. The ABS material of claim 1, wherein, The ABS resin is selected from the range of melt index 30-60 g / 10 min.

7. The ABS material of claim 1, wherein, By weight parts, also including 0-4 parts of auxiliary, the auxiliary is selected from at least one of antioxidant, lubricant.

8. A process for the production of the ABS material according to any one of claims 1 to 7, characterized in that, Including the following steps: according to the proportion, mix each component uniformly, extrude and granulate through double screw extruder, get ABS material.

9. Use of the ABS material according to any one of claims 1 to 7, characterized in that For preparing UL94 5VA level flame retardant parts.