Flame-retardant abs composition, its preparation method and application

Abstract

The application discloses a kind of flame-retardant ABS compositions, by parts by weight, including the following components: ABS resin 70-80 parts;Bromine flame retardant 16-20 parts;Aluminum phosphonate flame retardant 3-5 parts;Guanyl phosphate flame retardant 1-2 parts.The application can achieve 1.5mm V-0 flame retardation without adding antimony trioxide by compounding bromine flame retardant, aluminum phosphonate flame retardant, guanyl phosphate flame retardant, and has the advantages of high melt flowability, low density, good toughness, suitable for preparing lightweight vehicle parts.

Description

TECHNICAL FIELD

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

[0002] ABS resin contains butadiene rubber component, which plays a toughening role and has flammability, resulting in an oxygen index of only 18%, belonging to flammable materials. In the field of household appliances and electrical applications, in order to improve the flame retardant performance, flame retardant modification must be carried out to meet the application requirements. The mature flame-retardant ABS on the market belongs to bromine-antimony flame-retardant system, which is mature and widely commercialized, but these two flame retardants are severely dependent on bromine and antimony resources, especially the limited reserves of antimony resources. Therefore, the cost of flame-retardant ABS products is greatly affected by the supply of resources, causing great concern of market users.

[0003] In the prior art, CN113549312A discloses a PC / ABS flame-retardant system, which is mainly composed of aluminum hypophosphite flame retardant and melamine hydrobromide. On the one hand, the patent discloses that the flame-retardant and antibacterial microspheres containing guanidine salt have flame retardancy and antibacterial property, and also discloses that the guanidine salt is small molecule guanidine salt, guanidine phosphate, guanidine hydrochloride, etc. However, in the patent, the guanidine salt mainly plays an antibacterial effect, because the content of guanidine salt is too low to achieve flame retardant effect. On the other hand, the system does not use bromine-based flame retardant as the main flame retardant, although it realizes antimony-free, but the melt flowability of the system is poor, resulting in poor processing performance, and the PC resin is easy to degrade, resulting in a significant decrease in toughness, which has a negative impact on industrial application.

[0004] In the prior art, it is difficult to realize antimony-free in the bromine-based flame-retardant system, because the bromine-based flame retardant must be used in the presence of antimony white, and high-density antimony bromide is generated in the combustion process to achieve barrier effect, so as to well play the flame-retardant complementary effect and achieve high flame-retardant effect with low addition amount.

[0005] At the same time, the bromine-antimony flame-retardant system in the prior art has high density, and it is difficult to realize the lightweight requirement of vehicle parts. SUMMARY

[0006] The present application aims to overcome the above technical defects, and provides a flame-retardant ABS composition with 1.5mm V-0 flame retardancy and good melt flowability.

[0007] The present application is realized by the following technical scheme:

[0008] A flame-retardant ABS composition, comprising the following components by weight:

[0009] ABS resin 70-80 parts;

[0010] Bromine flame retardant 16-20 parts;

[0011] Aluminum phosphonate flame retardant 3-5 parts;

[0012] Phosphonium guanidine flame retardant 1-2 parts.

[0013] In the flame-retardant ABS composition of the present application, the ABS resin accounts for not less than 63wt% of the total weight. The melt index of the ABS resin of the present application ranges from 25 to 40 g / 10min, under the test condition of 220℃ / 10kg.

[0014] The bromine flame retardant is selected from at least one of decabromobiphenyl ethane, octabromide, bromine triazine, brominated epoxy, and brominated polystyrene.

[0015] Preferably, the bromine flame retardant is selected from bromine triazine.

[0016] The structure of the aluminum phosphonate flame retardant is as follows:

[0017]

[0018] wherein R1, R2, R3, R4, R5, R6 are independently selected from any one of -OH, -C2H5, -C6H 13 , -C8H 17 .

[0019] In the aluminum phosphonate flame retardant, R1, R2, R3, R4, R5, R6 are all -OH, or R1, R2, R3, R4, R5, R6 are all -C2H5, or R1, R2, R3, R4, R5, 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, R6 are all -C2H5.

[0020] The average particle size of the aluminum phosphonate flame retardant ranges from D50=40 to 55μm. The average particle size is tested by a laser particle size instrument.

[0021] Specifically, the aluminum phosphonate flame retardant can be selected from diethyl phosphine aluminum, aluminum dihydrogen phosphonate, etc.

[0022] The structure of the phosphonium guanidine flame retardant is as follows:

[0023]

[0024] m=1, n=4; m=2, n=3; m=3, n=2.

[0025] The skilled in the art can select whether to add 0-1 part of a lubricant according to actual needs, and the lubricant can be a stearate lubricant, a stearic acid amide lubricant, etc., such as pentaerythritol stearate, ethylene bis stearic acid amide, etc., and preferably a pentaerythritol stearate lubricant.

[0026] The application discloses a preparation method of a flame-retardant ABS composition.

[0027] The application discloses a preparation method of a flame-retardant ABS composition.

[0028] The application has the following beneficial effects:

[0029] The application effectively replaces the antimony-based flame-retardant synergist by compounding the aluminum phosphate flame retardant and the guanidine phosphate flame retardant, so that the flame-retardant ABS composition has the flame retardancy of 1.5mm V-0, the density of the composition is obviously reduced (the density is less than 1.17g / cm 3 ), the toughness is good (the notched impact strength is greater than 13kJ / m 2 ), and the melt flowability is good (the melt index is greater than 30g / 10min, 220℃ / 10kg), and the flame-retardant ABS composition is suitable for light-weight vehicle parts. DETAILED DESCRIPTION

[0030] The application will be described in detail below in combination with specific embodiments. The following embodiments will help the 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 the skilled in the art, a number of modifications and improvements can be made without departing from the concept of the application. These all belong to the protection scope of the application.

[0031] The raw materials used in the application are as follows:

[0032] ABS resin-1: the melt index is 33g / 10min, 220℃ / 10kg, ABS GP-35, LyondellBasell Industries N.V.

[0033] ABS resin-2: the melt index is 22g / 10min, 220℃ / 10kg, ABS PA-757, Taiwan Formosa in Taiwan Province, China;

[0034] Brominated triazine: FR-245, Israel Chemicals Limited;

[0035] Decabromodiphenyl ethane: SAYTEX 8010, American Albemarle Corporation;

[0036] Octabromide ether: XZ-6800, Shandong Brothers Company;

[0037] Brominated epoxy: F-3014, Isram Chemical Industries Ltd;

[0038] Brominated polystyrene: SAYTEX 621, Albemarle Corporation;

[0039] Aluminum diethylphosphinate: average particle size 31 microns, EXOLIT OP 1230, Clariant Corporation;

[0040] Guanyl phosphate flame retardant A: m=2, n=3, diguanidine phosphate, Hubei Svituo New Material Technology Co., Ltd;

[0041] Guanyl phosphate flame retardant B: m=1, n=4, hydrogen diguanidine phosphate, Hangzhou Xiangshun Chemical Co., Ltd;

[0042] Melamine hydrobromide: Guangdong Wengjiang Chemical Reagent Co., Ltd;

[0043] Antimony trioxide: S-05N, Changde Chenzhou Antimony Products Co., Ltd;

[0044] Lubricant A: pentaerythritol stearate, PETS-AP, Fagron SpA;

[0045] Lubricant B: ethylene bis-stearamide, EBS B50, Guangzhou Runfeng Chemical Co., Ltd;

[0046] Preparation method of flame-retardant ABS compositions of examples and comparative examples: according to the proportion, the components are uniformly mixed, and then extruded and granulated through a double-screw extruder to obtain the flame-retardant ABS compositions. The screw cylinder temperature range is 200-220°C, and the screw rotation speed is 300-500 revolutions / minute.

[0047] Test methods:

[0048] (1) Flame retardance: according to UL-94-2021 test, thickness 1.5 mm;

[0049] (2) Density: ISO 1183-1:2019, 23°C;

[0050] (3) Melt flow rate: ISO 1133-1:2022, 220°C, 10 kg;

[0051] (4) Notched impact strength: ISO 180 / 1A-2023, 23°C.

[0052] Table 1: Weight content of components of flame-retardant ABS compositions of examples and test results

[0053] 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 Brominated triazine 18 16 20 18 Decabromodiphenyl ethane 18 Octabromodiphenyl ether 18 Brominated epoxy 18 Brominated polystyrene 18 Aluminum diethylphosphinate 4 3 5 4 4 4 4 4 Guanyl phosphate flame retardant A 1 1.5 1 1 1 1 1 Guanyl 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 resistance V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 Density, g / cm 3 ]] 1.13 1.12 1.14 1.15 1.14 1.14 1.13 1.13 MFI, g / 10 min 45 41 39 38 42 44 40 40 Notched Charpy impact strength, kJ / m 2 ]] 17 17 15 14 17 16 17 15

[0054] As can be seen from examples 1 / 4 / 5 / 6 / 7, the bromine-based flame retardant is preferably a brominated triazine.

[0055] From Example 1 / 8, it is known that pentaerythritol stearate lubricant is preferred.

[0056] Table 2: Weight content of each component of the flame-retardant ABS composition of the comparative example and test results

[0057] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 ABS resin-1 70 70 70 70 70 Brominated triazine 18 18 14 21.5 Aluminum diethylphosphinate 4 13 2 1 Guanyl 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 resistance V-0 V-1 V-2 V-1 V-1 Density, g / cm 3 ]] 1.18 1.13 1.11 1.12 1.18 MFI, g / 10 min Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 ABS resin-1 Brominated triazine Aluminum diethylphosphinate Guanyl phosphate flame retardant A Melamine hydrobromide Antimony trioxide Lubricant A Flame resistance MFI, g / 10 min 28 29 31 26 25 Notched Charpy impact strength, kJ / m 2 ]] 17 16 12 18 14

[0058] From Comparative Example 1, it is known that the bromine-antimony flame-retardant system has higher density and lower melt index at the same content.

[0059] From Comparative Example 2, it is known that if the guanidine phosphate flame-retardant is not contained, the flame retardancy cannot reach V-0, and the melt index is lower.

[0060] From Comparative Example 3, it is known that the flame-retardant property is poor when the diethylphosphinic acid aluminum / melamine hydrobromide / guanidine phosphate flame-retardant is selected.

[0061] From Comparative Example 4, it is known that if the content of the flame-retardant is too low, the flame retardancy cannot reach V-0.

[0062] From Comparative Example 5, it is known that if the content of the flame-retardant is not within the range of the present application, the flame retardancy cannot reach V-0.

Claims

1. A flame retardant ABS composition, characterized in that: Calculated by weight, it includes the following components: 70-80 parts of ABS resin; 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, bromotriazine, 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, and 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: uniformly mixing the components according to a proportion, and extruding and granulating the components 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 automotive parts.

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