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

Abstract

The invention relates to the technical field of new materials, in particular to a high-performance flame-retardant ABS composite material and a preparation method thereof.The high-performance flame-retardant ABS composite material is prepared from, by mass, 60-80 parts of ABS resin, 10-30 parts of PC resin, 1-5 parts of a flame retardant A, 3-7 parts of a flame retardant B and 1-5 parts of a processing aid. Compared with the prior art, the invention has the following beneficial effects: the flame retardant A and the flame retardant B developed and designed by the invention are compounded for use and have synergistic interaction, the UL94 test reaches V-0 level, and the flame retardant has very excellent flame retardant property.

Description

Technical Field

[0001] The invention relates to the technical field of new materials, and in particular to a high-performance flame-retardant ABS composite material and a preparation method thereof. Background Art

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

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

[0004] ABS / PC composite materials have excellent room and low temperature toughness, good comprehensive material performance and a wide range of applications. However, since ABS is easy to burn, the flame retardancy of ABS / PC composite materials is not ideal. Summary of the invention

[0005] In order to solve the problems mentioned in the above background technology, the present invention provides a high-performance flame-retardant ABS composite material and a preparation method thereof.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions: The invention provides a high-performance flame-retardant ABS composite material, which 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 aid, calculated by weight.

[0007] Preferably, the flame retardant A is prepared by the following method: The acenaphthenequinone and p-toluenesulfonic acid are dispersed in toluene, biphenylphosphamidate is added, stirred and heated for reaction, and post-processed to obtain flame retardant A; The structural formula of flame retardant A is .

[0008] Preferably, the molar ratio of acenaphthenequinone, biphenylphosphoramidate and p-toluenesulfonic acid is 1:(0.95-1.05):(0.01-0.05).

[0009] Preferably, the flame retardant B is prepared by the following method: Cyanuric chloride and triethylamine are dispersed in N,N-dimethylformamide (DMF), maintained at -5 - 0 °C, ethanolamine is added and stirred for reaction, then heated to 40 - 60 °C, a part of 4,4'-diaminodiphenyl sulfide is added and stirred for reaction, then heated to 90 - 100 °C, the remaining 4,4'-diaminodiphenyl sulfide is added and stirred for reaction, and after post-treatment, flame retardant B is obtained; The structural formula of flame retardant B is .

[0010] 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).

[0011] Preferably, the other additives include any one or several of toughening agents, compatibilizers, antioxidants, and dispersants; Among them, 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.

[0012] The present invention also provides a preparation method of a high-performance flame-retardant ABS composite material, which 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. Add the above mixture into a twin-screw extruder, and through melt extrusion and pelletization, the above high-performance flame-retardant ABS composite material is obtained.

[0013] Preferably, in step S1, the mixing speed is 600 - 900 rpm and the mixing time is 5 - 15 min.

[0014] Preferably, in step S2, the temperatures of each section of the twin-screw extruder are 170 - 180 °C, 185 - 195 °C, 190 - 200 °C, 190 - 200 °C, 205 - 215 °C respectively, and the screw speed is 300 - 600 rpm.

[0015] Compared with the prior art, the beneficial effects of the present invention are: 1. The flame retardant A and flame retardant B developed and designed in the present invention are used in combination, with synergistic effect, and the UL94 test reaches V - 0 level, having very excellent flame retardant performance.

[0016] 2. During the combustion process of the ABS composite material of the present invention, nitrogen, hydrogen, oxygen, sulfur and other elements in flame retardants A and flame retardants B are released in large quantities in the form of non-combustible gases such as NH3, H2O, SO2, etc., diluting the combustible gas and heat around the combustion product, playing a role in gas phase flame retardancy. 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 carbonization. The formation of carbon reduces the heat conduction from the flame to the condensed phase, forms a thin glassy or liquid protective layer on the condensed phase, reduces oxygen diffusion and heat transfer between the gas phase and the solid phase, and finally achieves very excellent flame retardant properties.

[0017] 3. The ABS composite material prepared by the present invention has excellent mechanical properties and good flame retardant effect, and can meet the material technology requirements in the electronic and electrical fields. DETAILED DESCRIPTION

[0018] Unless otherwise specified, the raw materials and reagents used in the present invention are commercially available or can be prepared by known methods.

[0019] ABS resin: 121H, LG Chem PC resin: PC-1100, Lotte Chemical of Korea Toughening agent: EM500, LG Chem Compatibilizer: SAG-002, Jiayirong Antioxidant: 1076, BASF Antioxidant: 168, BASF Dispersant: PETS, Italian hair base The preparation method of flame retardant A is: Disperse 1 mol of acenaphthenequinone and 0.03 mol of p-toluenesulfonic acid in an appropriate amount of toluene, heat with stirring at 75°C for 1 h, add 0.95 mol of biphenyl aminophosphorate, reflux for 5 h, cool to room temperature, filter, wash and dry to obtain flame retardant A.

[0020] The preparation method of flame retardant B is: Disperse 2 mol of cyanuric chloride and 6.8 mol of triethylamine in an appropriate amount of N,N-dimethylformamide (DMF), maintain -5°C, add 2 mol of ethanolamine and stir to react for 2 hours, heat to 50°C, add 1 mol of 4,4'-diaminodiphenyl sulfide and stir to react for 3 hours, heat to 95°C, add 2 mol of 4,4'-diaminodiphenyl sulfide and stir to react for 6 hours, filter, wash and dry to obtain flame retardant B. Example 1

[0021] A method for preparing a high-performance flame-retardant ABS composite material comprises the following steps: S1. Mix 70 parts of ABS resin, 20 parts of PC resin, 3 parts of flame retardant A, 5 parts of flame retardant B, 2 parts of toughening agent, 2 parts of compatibilizer, 0.3 part of antioxidant 168, 0.2 part of antioxidant 1076, and 0.3 part of dispersant at 750 rpm for 10 min to obtain a mixture; S2. Add the above mixture to a twin-screw extruder and perform melt extrusion granulation to obtain the above high-performance flame-retardant ABS composite material.

[0022] The temperatures of each section of the twin-screw extruder are 175 °C, 190 °C, 195 °C, 195 °C, and 210 °C respectively, and the screw speed is 450 rpm. Example 2

[0023] The difference between this example and Example 1 is: 60 parts of ABS resin, and the rest is exactly the same as in Example 1. Example 3

[0024] The difference between this example and Example 1 is: 80 parts of ABS resin, and the rest is exactly the same as in Example 1. Example 4

[0025] The difference between this example and Example 1 is: 1 part of flame retardant A, and the rest is exactly the same as in Example 1. Example 5

[0026] The difference between this example and Example 1 is: 5 parts of flame retardant A, and the rest is exactly the same as in Example 1. Example 6

[0027] The difference between this example and Example 1 is: 3 parts of flame retardant B, and the rest is exactly the same as in Example 1. Example 7

[0028] The difference between this example and Example 1 is: 7 parts of flame retardant B, and the rest is exactly the same as in Example 1.

[0029] Comparative Example 1 The difference between this comparative example and Example 1 is: 0 part of flame retardant A, 0 part of flame retardant B, and the rest is exactly the same as in Example 1.

[0030] Comparative Example 2 The difference between this comparative example and Example 1 is: 0 part of flame retardant A, and the rest is exactly the same as in Example 1.

[0031] Comparative Example 3 The difference between this comparative example and Example 1 is: 0 part of flame retardant B, and the rest is exactly the same as in Example 1.

[0032] Results and Tests Tensile strength and elongation at break: Tested in accordance with GB / T 1040.1-2018, test condition: 50 mm / min; Flexural strength: Refer to GB / T 9341-2008, test condition: 2 mm / min; Impact strength: Tested in accordance with GB / T 1843-2008, test condition: 5.5 J; Flame retardant performance: Tested in accordance with the UL94 vertical burning test standard; Table 1

[0033] From the data of Examples 1-7 in Table 1, it can be seen that the flame-retardant ABS composite material prepared by the present invention has excellent performance in terms of tensile strength, elongation at break, flexural strength, impact strength and flame retardant performance.

[0034] Comparing Example 1 with Comparative Example 1, it can be seen that in the absence of flame retardant A and flame retardant B (Comparative Example 1), the flame retardant effect is very poor. By adding flame retardant A and flame retardant B (Example 1), the flame retardant performance is significantly improved, and at the same time, it does not affect the mechanical properties of the material. Even due to the rigid spatial structure of flame retardants A and B, a certain enhancing effect on the mechanical properties is produced, such as the tensile strength increasing from 57.31 to 61.95.

[0035] Comparing Example 1 with Comparative Examples 2 and 3, it can be seen that using a single flame retardant does not give satisfactory results. When using a single flame retardant A (Comparative Example 3), the flame retardant effect is at the V-2 level, and when using a single flame retardant B (Comparative Example 2), the flame retardant effect is at the V-1 level. However, when the two are compounded, an obvious enhancing effect is produced, and the flame retardant effect reaches the V-0 level.

[0036] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and should be covered by the protection scope of the present invention.

Claims

1. A high-performance flame-retardant ABS composite material, characterized in that: Calculated by weight, 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 aid.

2. A high performance flame retardant ABS composite material according to claim 1, characterized in that: The flame retardant A is prepared by the following method: Acenaphthenequinone and p-toluenesulfonic acid are dispersed in toluene, biphenylphosphamidate is added, stirred and heated for reaction, and post-processed to obtain flame retardant A.

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

4. The high performance flame retardant ABS composite material according to claim 1, characterized in that: The flame retardant B is prepared by the following method: Disperse cyanuric chloride and triethylamine in N,N-dimethylformamide (DMF), maintain -5-0°C, add ethanolamine and stir to react, heat to 40-60°C, add part of 4,4'-diaminodiphenyl sulfide and stir to react, heat to 90-100°C, add the remaining 4,4'-diaminodiphenyl sulfide and stir to react, post-treat to obtain flame retardant B.

5. A high performance flame retardant ABS composite material according to claim 4, 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).

6. The high performance flame retardant ABS composite material according to claim 1, characterized in that: The other additives include any one or more of toughening agents, compatibilizers, antioxidants, and dispersants; Wherein, the toughening agent is EM500; The compatibilizer is SAG-002; The antioxidant is any one or both of antioxidant 168 and antioxidant 1076; The dispersant is pentaerythritol stearate.

7. A method for preparing a high-performance flame-retardant ABS composite material as claimed in claim 1, characterized in that: The steps include: S1. The ABS resin, PC resin, flame retardant A, flame retardant B, and processing aid are uniformly mixed to obtain a mixture; S2. The mixture is added into a twin-screw extruder, and the mixture is melt-extruded and granulated to obtain the high-performance flame-retardant ABS composite material.

8. The method for preparing a high-performance flame-retardant ABS composite material according to claim 7, characterized in that: In step S1, the mixing speed is 600-900 rpm, and the mixing time is 5-15 min.

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

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