High-performance flame-retardant ABS composite material and preparation method thereof

Abstract

The application relates to the technical field of new materials, in particular to a high-performance flame-retardant ABS composite material and a preparation method thereof, which comprises the following components in parts by mass: ABS resin 60-80 parts, PC resin 10-30 parts, flame retardant A 1-5 parts, flame retardant B 3-7 parts and processing aid 1-5 parts. Compared with the prior art, the application has the beneficial effect that the flame retardant A and the flame retardant B are used in combination, synergistic effect is achieved, UL94 testing reaches V-0 level, and the flame-retardant performance is very excellent.

Description

Technical Field

[0001] This invention relates to the field of new materials technology, and in particular to a high-performance flame-retardant ABS composite material and its preparation method. Background Technology

[0002] ABS resin is an acrylonitrile-butadiene-styrene terpolymer. It has good surface gloss, excellent mechanical properties, cold resistance, impact resistance, dimensional stability, and easy molding. It is widely used in automobiles, home appliances, transportation, and packaging.

[0003] Polycarbonate (PC) and ABS resin are blended to obtain ABS / PC composite materials, which can complement each other in terms of performance. On the one hand, the heat resistance, impact strength and tensile strength of the composite material are better than those of ABS, and on the other hand, its melt viscosity is lower than that of PC and its processing performance is better than that of PC.

[0004] ABS / PC composites have excellent toughness at room temperature and low temperature, good overall material properties, and a wide range of applications. However, due to the flammability of ABS, the flame retardancy of ABS / PC composites is not ideal. Summary of the Invention

[0005] To address the problems mentioned in the background section, this invention provides a high-performance flame-retardant ABS composite material and its preparation method.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] This invention provides a high-performance flame-retardant ABS composite material, which, by weight, comprises 60-80 parts of ABS resin, 10-30 parts of PC resin, 1-5 parts of flame retardant A, 3-7 parts of flame retardant B, and 1-5 parts of processing aids.

[0008] Preferably, the flame retardant A is prepared by the following method:

[0009] Acenathoquinone and p-toluenesulfonic acid were dispersed in toluene, biphenylaminophosphate was added, the mixture was stirred and heated to react, and then post-treated to obtain flame retardant A.

[0010] The structural formula of flame retardant A is:

[0011] .

[0012] Preferably, the molar ratio of acenaphthene, biphenylaminophosphate, and p-toluenesulfonic acid is 1:(0.95-1.05):(0.01-0.05).

[0013] Preferably, the flame retardant B is prepared by the following method:

[0014] Cyanuric chloride and triethylamine were dispersed in N,N-dimethylformamide (DMF) and kept at -5 to 0°C. Ethanolamine was added and stirred to react. The temperature was raised to 40 to 60°C. Part of 4,4'-diaminodiphenyl sulfide was added and stirred to react. The temperature was raised to 90 to 100°C. The remaining 4,4'-diaminodiphenyl sulfide was added and stirred to react. After post-treatment, flame retardant B was obtained.

[0015] The structural formula of flame retardant B is:

[0016] .

[0017] Preferably, the molar ratio of cyanuric chloride, ethanolamine, 4,4'-diaminodiphenyl sulfide, and triethylamine is 2:(1.9-2.1):(2.5-3.5):(6-8).

[0018] Preferably, the other additives include any one or more of toughening agents, compatibilizers, antioxidants, and dispersants;

[0019] The toughening agent is EM500;

[0020] The compatibilizer is SAG-002;

[0021] The antioxidant is any one or two of antioxidant 168 and antioxidant 1076;

[0022] The dispersant is pentaerythritol stearate.

[0023] This invention also provides a method for preparing a high-performance flame-retardant ABS composite material, comprising the following steps:

[0024] S1. Mix ABS resin, PC resin, flame retardant A, flame retardant B, and processing aids evenly to obtain a mixture;

[0025] S2. The above mixture is added to a twin-screw extruder and melt-extruded and granulated to obtain the above high-performance flame-retardant ABS composite material.

[0026] Preferably, in step S1, the mixing speed is 600-900 rpm and the mixing time is 5-15 min.

[0027] Preferably, in step S2, the temperatures of each section of the twin-screw extruder are 170-180℃, 185-195℃, 190-200℃, 190-200℃, and 205-215℃, respectively, and the screw speed is 300-600 rpm.

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] 1. The flame retardant A and flame retardant B developed in this invention are used in combination for synergistic effect, achieving a V-0 rating in UL94 testing, and have excellent flame retardant performance.

[0030] 2. During the combustion process, the nitrogen, hydrogen, oxygen, sulfur and other elements in flame retardants A and B of the ABS composite material of the present invention are released in large quantities in the form of non-combustible gases such as NH3, H2O and SO2, which dilute the combustible gases and heat around the burning material and play a gas-phase flame retardant role. At the same time, phosphorus and oxygen form phosphoric acid as a dehydrating agent, which isolates the air on the polymer surface. The released water vapor absorbs a large amount of heat and promotes char formation. The formation of char reduces the heat conduction from the flame to the condensed phase and forms a thin glassy or liquid protective layer on the condensed phase, which reduces oxygen diffusion and heat transfer between the gas phase and the solid phase, ultimately achieving excellent flame retardant performance.

[0031] 3. The ABS composite material prepared by this invention has excellent mechanical properties and good flame retardant effect, which can meet the material technology requirements of the electronic and electrical fields. Detailed Implementation

[0032] Unless otherwise stated, all raw materials and reagents used in this invention are commercially available or can be prepared by known methods.

[0033] ABS resin: 121H, LG Chem

[0034] PC resin: PC-1100, Lotte Chemicals, South Korea

[0035] Toughening agent: EM500, LG Chem

[0036] Compatibilizer: SAG-002, Jia Yi Rong

[0037] Antioxidant: 1076, BASF

[0038] Antioxidant: 168, BASF

[0039] Dispersant: PETS, Italian brand Fat

[0040] The preparation method of flame retardant A is as follows:

[0041] 1 mol of acenaphthene and 0.03 mol of p-toluenesulfonic acid were dispersed in an appropriate amount of toluene, stirred and heated at 75°C for 1 h, 0.95 mol of biphenylaminophosphate was added, and the mixture was refluxed for 5 h. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain flame retardant A.

[0042] The preparation method of flame retardant B is as follows:

[0043] 2 mol of cyanuric chloride and 6.8 mol of triethylamine were dispersed in an appropriate amount of N,N-dimethylformamide (DMF). The mixture was kept at -5°C, and 2 mol of ethanolamine was added and stirred for 2 h. The temperature was raised to 50°C, and 1 mol of 4,4'-diaminodiphenyl sulfide was added and stirred for 3 h. The temperature was raised to 95°C, and 2 mol of 4,4'-diaminodiphenyl sulfide was added and stirred for 6 h. The mixture was then filtered, washed, and dried to obtain flame retardant B. Example 1

[0044] A method for preparing a high-performance flame-retardant ABS composite material includes the following steps:

[0045] S1. Mix 70 parts ABS resin, 20 parts PC resin, 3 parts flame retardant A, 5 parts flame retardant B, 2 parts toughening agent, 2 parts compatibilizer, 0.3 parts antioxidant 168, 0.2 parts antioxidant 1076, and 0.3 parts dispersant, and mix at 750 rpm for 10 min to obtain a mixture;

[0046] S2. The above mixture is added to a twin-screw extruder and melt-extruded and granulated to obtain the above high-performance flame-retardant ABS composite material.

[0047] The temperatures of each section of the twin-screw extruder are 175℃, 190℃, 195℃, 195℃, and 210℃, and the screw speed is 450 rpm. Example 2

[0048] The difference between this embodiment and Embodiment 1 is that 60 parts of ABS resin are used, while the rest of the components are exactly the same as in Embodiment 1. Example 3

[0049] The difference between this embodiment and Embodiment 1 is that 80 parts of ABS resin are used, while the rest of the components are exactly the same as in Embodiment 1. Example 4

[0050] The difference between this embodiment and embodiment 1 is that: 1 part of flame retardant A, and the rest of the parts are exactly the same as in embodiment 1. Example 5

[0051] The difference between this embodiment and Embodiment 1 is that: 5 parts of flame retardant A are used, while the rest of the contents are exactly the same as in Embodiment 1. Example 6

[0052] The difference between this embodiment and Embodiment 1 is that: 3 parts of flame retardant B are used, while the rest of the components are exactly the same as in Embodiment 1. Example 7

[0053] The difference between this embodiment and Embodiment 1 is that 7 parts of flame retardant B are used, while the rest are exactly the same as in Embodiment 1.

[0054] Comparative Example 1

[0055] The difference between this comparative example and Example 1 is that there are 0 parts of flame retardant A and 0 parts of flame retardant B, while the rest are exactly the same as in Example 1.

[0056] Comparative Example 2

[0057] The difference between this comparative example and Example 1 is that there are 0 parts of flame retardant A, and the rest are exactly the same as in Example 1.

[0058] Comparative Example 3

[0059] The difference between this comparative example and Example 1 is that there are 0 parts of flame retardant B, and the rest is exactly the same as in Example 1.

[0060] Results and Detection

[0061] Tensile strength and elongation at break: tested according to GB / T1040.1-2018, test conditions: 50 mm / min;

[0062] Bending strength: Refer to GB / T9341-2008, test conditions: 2mm / min;

[0063] Impact strength: Tested according to GB / T 1843-2008, test conditions: 5.5J;

[0064] Flame retardant performance: Tested according to UL94 vertical burning test standard;

[0065] Table 1

[0066]

[0067] As can be seen from the data in Examples 1-7 in Table 1, the flame-retardant ABS composite material prepared by the present invention has excellent performance in tensile strength, elongation at break, flexural strength, impact strength and flame retardant properties.

[0068] Comparing Example 1 and Comparative Example 1, it can be seen that the lack of flame retardant A and flame retardant B (Comparative Example 1) results in a very poor flame retardant effect. Adding flame retardant A and flame retardant B (Example 1) significantly improves the flame retardant performance without affecting the mechanical properties of the material. In fact, due to the rigid spatial structure of flame retardants A and B, they even enhance the mechanical properties to a certain extent, such as increasing the tensile strength from 57.31 to 61.95.

[0069] Comparing Example 1 with Comparative Examples 2 and 3, it can be seen that using a single flame retardant does not produce satisfactory results. Using a single flame retardant A (Comparative Example 3), the flame retardant effect is at level V-2, and using a single flame retardant B (Comparative Example 2), the flame retardant effect is at level V-1. However, when the two are used in combination, a significant enhancement effect is produced, and the flame retardant effect reaches level V-0.

[0070] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A high-performance flame-retardant ABS composite material, characterized in that, Calculated by weight parts, it includes 60-80 parts of ABS resin, 10-30 parts of PC resin, 1-5 parts of flame retardant A, 3-7 parts of flame retardant B, and 1-5 parts of processing aids; The flame retardant A is prepared by the following method: Acenathoquinone and p-toluenesulfonic acid were dispersed in toluene, biphenylaminophosphate was added, the mixture was stirred and heated to react, and then post-treated to obtain flame retardant A. The flame retardant B is prepared by the following method: Cyanuric chloride and triethylamine were dispersed in N,N-dimethylformamide (DMF) and kept at -5 to 0°C. Ethanolamine was added and stirred to react. The temperature was raised to 40 to 60°C. Part of 4,4'-diaminodiphenyl sulfide was added and stirred to react. The temperature was raised to 90 to 100°C. The remaining 4,4'-diaminodiphenyl sulfide was added and stirred to react. After post-treatment, flame retardant B was obtained.

2. The high-performance flame-retardant ABS composite material according to claim 1, characterized in that, The molar ratio of acenaphthene, biphenylaminophosphate, and p-toluenesulfonic acid is 1:(0.95-1.05):(0.01-0.05).

3. The high-performance flame-retardant ABS composite material according to claim 1, characterized in that, The molar ratio of cyanuric chloride, ethanolamine, 4,4'-diaminodiphenyl sulfide, and triethylamine is 2:(1.9-2.1):(2.5-3.5):(6-8).

4. The high-performance flame-retardant ABS composite material according to claim 1, characterized in that, The processing aids include any one or more of toughening agents, compatibilizers, antioxidants, and dispersants; The toughening agent is EM500; The compatibilizer is SAG-002; The antioxidant is any one or two of antioxidant 168 and antioxidant 1076; The dispersant is pentaerythritol stearate.

5. A method for preparing a high-performance flame-retardant ABS composite material as described in claim 1, characterized in that, Includes the following steps: S1. Mix ABS resin, PC resin, flame retardant A, flame retardant B, and processing aids evenly to obtain a mixture; S2. The above mixture is added to a twin-screw extruder and melt-extruded and granulated to obtain the above high-performance flame-retardant ABS composite material.

6. The method for preparing a high-performance flame-retardant ABS composite material according to claim 5, characterized in that, In step S1, the mixing speed is 600-900 rpm and the mixing time is 5-15 min.

7. The method for preparing a high-performance flame-retardant ABS composite material according to claim 5, characterized in that, In step S2, the temperatures of each section of the twin-screw extruder are 170-180℃, 185-195℃, 190-200℃, 190-200℃, and 205-215℃, respectively, and the screw speed is 300-600 rpm.

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