Flame-retardant ABS (Acrylonitrile Butadiene Styrene) composition and preparation method and application thereof

Abstract

The flame-retardant ABS composition is prepared from the following components in parts by weight: 70 to 80 parts of ABS resin; 16 to 20 parts of brominated flame retardant; 3-5 parts of an aluminum phosphate flame retardant; and 1-2 parts of a guanidine phosphate flame retardant. Through compounding of the brominated flame retardant, the aluminum phosphate flame retardant and the guanidine phosphate flame retardant, 1.5 mmV-0 flame retardance can be achieved on the premise that antimony trioxide is not added, and the flame retardant has the advantages of being high in melt fluidity, low in density and good in toughness and is suitable for preparing light-weight vehicle-mounted parts.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a flame retardant ABS composition and a preparation method and application thereof. Background Art

[0002] ABS resin contains butadiene rubber components, which play a toughening role and are flammable, resulting in an oxygen index of only 18%, which is a flammable material. In the field of home appliances and electrical applications, in order to improve its flame retardant properties, flame retardant modification must be carried out to meet application requirements. Currently, mature flame-retardant ABS on the market all belong to the bromine-antimony flame retardant system, which is mature and widely used in commercial applications. However, these two flame retardants are heavily dependent on bromine and antimony resources, especially the limited reserves of antimony resources. Therefore, the cost of flame-retardant ABS products fluctuates greatly due to the influence of resource supply, which has caused great concern among market users.

[0003] In the prior art, CN113549312A records a PC / ABS flame retardant system, which is mainly composed of aluminum hypophosphite flame retardants and melamine hydrobromide. Among them, on the one hand, although the patent records that the flame retardant and antibacterial microspheres containing guanidine salts have both flame retardancy and antibacterial properties, it also records that guanidine salts are specifically small molecule guanidine salts, guanidine phosphate, guanidine hydrochloride, etc., but in the patent, guanidine salts mainly play an antibacterial effect, which is due to the low content of guanidine salts and cannot achieve flame retardant effect. On the other hand, the system is not a brominated flame retardant as the main flame retardant. Although antimony-free is achieved, the system has poor melt fluidity, resulting in a decrease in processing performance, and PC resin is easily degraded, resulting in a very obvious decrease in toughness, which has a negative impact on industrial applications.

[0004] In the prior art, it is difficult to achieve antimony-free in a bromine-based flame retardant system. This is because bromine-based flame retardants must be under the action of antimony white and achieve a barrier effect through the generation of high-density antimony bromide during the combustion process, so that they can play a good flame retardant synergistic and complementary role and achieve a high flame retardant effect with a low addition amount.

[0005] At the same time, the bromine antimony flame retardant system in the prior art has a high density, which makes it difficult to achieve the requirement of lightweight vehicle parts. Summary of the invention

[0006] The object of the present invention is to overcome the above technical defects and provide a flame retardant ABS composition with 1.5 mm V-0 flame retardancy and good melt fluidity.

[0007] The present invention is achieved through the following technical solutions: A flame retardant ABS composition, comprising the following components in parts by weight: ABS resin 70-80 parts; 16-20 parts of brominated flame retardant; 3-5 parts of aluminum phosphonate flame retardant; 1-2 parts of guanidine phosphate flame retardant.

[0008] In the flame retardant ABS composition of the present invention, the ABS resin accounts for no less than 63wt% of the total weight. The melt index range of the ABS resin of the present invention is 25-40 g / 10min, and the test condition is 220°C / 10kg.

[0009] The brominated flame retardant is selected from at least one of decabromodiphenylethane, octabromoether, bromotriazine, brominated epoxy and brominated polystyrene.

[0010] Preferably, the brominated flame retardant is selected from brominated triazines.

[0011] The structure of the aluminum phosphonate flame retardant is as follows:

[0012] Wherein, R1, R2, R3, R4, R5, and R6 are independently selected from -OH, -C2H5, -C6H 13 、-C8H 17 Any one of .

[0013] In the aluminum phosphonate flame retardant, R1, R2, R3, R4, R5, and R6 are all -OH, or R1, R2, R3, R4, R5, and R6 are all -C2H5, or R1, R2, R3, R4, R5, and R6 are all -C6H 13 , or R1, R2, R3, R4, R5, R6 are all -C8H 17 ; Preferably, in the aluminum phosphonate flame retardant, R1, R2, R3, R4, R5, and R6 are all -C2H5.

[0014] The average particle size range of aluminum phosphonate flame retardant is D50=40-55μm. The average particle size is tested by a laser particle size analyzer.

[0015] Specifically, the aluminum phosphonate flame retardant can be selected from diethyl aluminum phosphinate, dihydrogen aluminum phosphonate, and the like.

[0016] The structural formula of the guanidine phosphate flame retardant is as follows: When m=1, n=4; when m=2, n=3; when m=3, n=2.

[0017] Those skilled in the art can choose whether to add 0-1 parts of lubricant according to actual needs. The lubricant can be a stearate lubricant, a stearic acid amide lubricant, etc., such as pentaerythritol stearate, ethylene bis stearic acid amide, etc., preferably pentaerythritol stearate lubricant.

[0018] The preparation method of the flame retardant ABS composition comprises the following steps: mixing the components uniformly according to the proportion, and extruding and granulating the components through a twin-screw extruder to obtain the flame retardant ABS composition.

[0019] The flame retardant ABS composition is used to prepare lightweight vehicle parts.

[0020] The present invention has the following beneficial effects: The present invention effectively replaces the antimony-based flame retardant synergist by compounding the aluminum phosphate flame retardant and the guanidine phosphate flame retardant, which not only enables the flame retardant ABS composition of the present invention to have a flame retardancy of 1.5 mmV-0, but also significantly reduces the density of the composition (density <1.17 g / cm 3 ), and good toughness (notch impact strength> 13kJ / m 2 ), good melt fluidity (melt index > 30g / 10min, 220℃ / 10kg), suitable for lightweight automotive parts. DETAILED DESCRIPTION

[0021] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0022] The sources of raw materials used in the present invention are as follows: ABS resin-1: melt index 33g / 10min, 220℃ / 10kg, ABS GP-35, INEOS Styrolution; ABS resin-2: melt index is 22g / 10min, 220℃ / 10kg, ABS PA-757, Taiwan Chimei, Taiwan Province of China; Bromotriazine: FR-245, Israel Chemical Company; Decabromodiphenylethane: SAYTEX 8010, Albemarle Corporation, USA; Octabromoether: XZ-6800, Shandong Brothers Company; Brominated epoxy: F-3014, Israel Chemical Company; Brominated polystyrene: SAYTEX 621, Albemarle Corporation, USA; Aluminum diethylphosphinate: average particle size 31 μm, EXOLIT OP 1230, Clariant; Guanidine phosphate flame retardant A: m=2, n=3, diguanidine phosphate, Hubei Siweitu New Material Technology Co., Ltd.; Guanidine phosphate flame retardant B: m=1, n=4, diguanidine hydrogen phosphate, Hangzhou Xiangshun Chemical Co., Ltd.; Melamine hydrobromide: Guangdong Wengjiang Chemical Reagent Co., Ltd.; Antimony trioxide: S-05N, Changde Chenzhou Antimony Products Company; Lubricant A: pentaerythritol stearate, PETS-AP, Fage, Italy; Lubricant B: ethylene bis stearamide, EBS B50, Guangzhou Runfeng Chemical Company; Embodiment and comparative example Preparation method of flame retardant ABS composition: according to the ratio, each component is mixed evenly, and extruded and granulated by a twin-screw extruder to obtain a flame retardant ABS composition, wherein the barrel temperature range is 200-220°C, and the screw speed is 300-500 rpm.

[0023] Various test methods: (1) Flame retardant: According to UL-94-2021 test, thickness 1.5mm; (2) Density: ISO 1183-1:2019, 23°C; (3) Melt flow rate: ISO 1133-1:2022, 220°C, 10kg; (4) Notched impact strength: ISO 180 / 1A-2023, 23°C.

[0024] Table 1: Weight content of each component of flame retardant ABS composition and test results Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 ABS resin-1 70 80 70 70 70 70 70 ABS resin-2 75 Bromotriazine 18 16 20 18 Decabromodiphenylethane 18 Octabromoether 18 Epoxy Bromide 18 Brominated polystyrene 18 Aluminum diethylphosphinate 4 3 5 4 4 4 4 4 Guanidine phosphate flame retardant A 1 1.5 1 1 1 1 1 Guanidine phosphate flame retardant B 2 Lubricant A 0.3 0.5 0.3 0.3 0.3 0.3 Lubricant B 0.8 0.3 Flame retardant V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 <![CDATA[Density, g / cm 3 > 1.13 1.12 1.14 1.15 1.14 1.14 1.13 1.13 MFI, g / 10min 45 41 39 38 42 44 40 40 <![CDATA[Notched impact strength, kJ / m 2 > 17 17 15 14 17 16 17 15 It can be seen from Examples 1 / 4 / 5 / 6 / 7 that the brominated flame retardant is preferably brominated triazine.

[0025] It can be seen from Examples 1 / 8 that pentaerythritol stearate lubricant is preferred.

[0026] Table 2: Weight content of each component in the flame retardant ABS composition of the comparative example and test results Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 ABS resin-1 70 70 70 70 70 Bromotriazine 18 18 14 21.5 Aluminum diethylphosphinate 4 13 2 1 Guanidine phosphate flame retardant A 0 1 0.5 0.5 Melamine hydrobromide 9 Antimony trioxide 5 Lubricant A 0.3 0.3 0.3 0.3 0.3 Flame retardant V-0 V-1 V-2 V-1 V-1 <![CDATA[Density, g / cm 3 > 1.18 1.13 1.11 1.12 1.18 MFI, g / 10min 28 29 31 26 25 <![CDATA[Notched impact strength, kJ / m 2 > 17 16 12 18 14 It can be seen from Comparative Example 1 that the bromine antimony flame retardant system has a higher density and a lower melt index under the same content conditions.

[0027] It can be seen from Comparative Example 2 that if the guanidine phosphate flame retardant is not contained, the flame retardancy cannot reach V-0 and the melt index is low.

[0028] It can be seen from Comparative Example 3 that the flame retardancy of the compound of diethylaluminum hypophosphite / melamine hydrobromide / guanidine phosphate flame retardant is poor.

[0029] It can be seen from Comparative Example 4 that if the content of the flame retardant is too low, the flame retardancy cannot reach V-0.

[0030] It can be seen from Comparative Example 5 that if the content of the flame retardant is not within the range of the present invention, the flame retardancy of V-0 cannot be achieved.

Claims

1. A flame retardant ABS composition, characterized in that: By weight, it includes the following components: ABS resin 70-80 parts; 16-20 parts of brominated flame retardant; 3-5 parts of aluminum phosphonate flame retardant; 1-2 parts of guanidine phosphate flame retardant.

2. The flame retardant ABS composition according to claim 1, characterized in that: The brominated flame retardant is selected from at least one of decabromodiphenylethane, octabromoether, brominated triazine, brominated epoxy and brominated polystyrene.

3. The flame retardant ABS composition according to claim 2, characterized in that: The brominated flame retardant is selected from brominated triazines.

4. The flame retardant ABS composition according to claim 1, characterized in that: The structure of the aluminum phosphonate flame retardant is as follows: Wherein, R1, R2, R3, R4, R5, and R6 are independently selected from -OH, -C2H5, -C6H 13 、-C8H 17 Any one of .

5. The flame retardant ABS composition according to claim 4, characterized in that: In the aluminum phosphonate flame retardant, R1, R2, R3, R4, R5, and R6 are all -OH, or R1, R2, R3, R4, R5, and R6 are all -C2H5, or R1, R2, R3, R4, R5, and R6 are all -C6H 13 , or R1, R2, R3, R4, R5, R6 are all -C8H 17 .

6. The flame retardant ABS composition according to claim 5, characterized in that: In the aluminum phosphonate flame retardant, R1, R2, R3, R4, R5 and R6 are all -C2H5.

7. The flame retardant ABS composition according to claim 1, characterized in that: The structural formula of the guanidine phosphate flame retardant is as follows: When m=1, n=4; when m=2, n=3; when m=3, n=2.

8. The flame retardant ABS composition according to claim 1, characterized in that: By weight, 0-1 part of pentaerythritol stearate lubricant is also included.

9. The method for preparing the flame retardant ABS composition according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing the components uniformly according to the proportion, extruding and granulating through a twin-screw extruder to obtain a flame-retardant ABS composition.

10. Use of the flame retardant ABS composition according to any one of claims 1 to 8, characterized in that: Used to prepare lightweight vehicle parts.

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