A flame-retardant ABS composite material and its preparation and application

Abstract

This invention relates to a flame-retardant ABS composite material, its preparation, and its application. The components include ABS resin, SAS resin, PBAT resin, flame retardant, hydroxyapatite, and additives. The ABS composite material of this invention exhibits high flame retardancy, high toughness, and ease of processing.

Description

Technical Field

[0001] This invention belongs to the field of modified plastics, and specifically relates to a flame-retardant ABS composite material and its preparation and application. Background Technology

[0002] ABS resin is a copolymer of styrene, butadiene, and acrylonitrile. ABS has excellent mechanical properties, especially due to the presence of tough butadiene, resulting in good impact strength. However, while ABS material possesses high toughness, the presence of substituted tertiary carbon atoms in the polybutadiene phase facilitates hydrogen abstraction from butadiene, initiating oxidation and accelerating ABS degradation, making it highly flammable. Ordinary ABS resin cannot achieve fire resistance and requires flame retardant modification. The conventional method of adding brominated flame retardants can achieve flame retardancy in ABS material, but this significantly reduces the material's toughness and melt flow, increasing processing difficulty. Injection molding of larger parts with high fire resistance requirements can lead to molding difficulties, especially in winter, where insufficient toughness can cause cracking. Summary of the Invention

[0003] In view of the shortcomings of the prior art, the technical problem to be solved by the present invention is to provide a high-efficiency flame-retardant, high-toughness, and easy-to-process ABS composite material, as well as its preparation and application.

[0004] An ABS composite material of the present invention comprises, by weight, the following components:

[0005]

[0006] The melt flow rate of the ABS resin at 220°C and 10kg is 7-20g / 10min, as measured according to the test standard GB / T 3682-2000.

[0007] The intrinsic viscosity of the PBAT resin is 1.8-2.6 dl / g, and the intrinsic viscosity number conforms to standard GB / T 1632.5-2008.

[0008] Choosing a suitable viscosity of PBAT results in a more stable melt and more uniform dispersion of components during composite material processing. ABS resin is a copolymer of styrene, butadiene, and acrylonitrile.

[0009] SAS is a styrene-acrylonitrile-organosilicon copolymer;

[0010] PBAT resin is a copolymer of butylene adipate and butylene terephthalate.

[0011] Preferably, the melt flow rate of the ABS resin at 220°C and 10 kg is 8-13 g / 10 min, as measured according to test standard GB / T 3682-2000.

[0012] Preferably, the intrinsic viscosity of the PBAT resin is 2.0-2.5 dl / g.

[0013] The intrinsic viscosity of PBAT resin was tested according to standard GB / T 1632.5-2008.

[0014] Preferably, the acrylonitrile content in the SAS resin is 20-33%. The nitrogen content is tested using an elemental analyzer, and the acrylonitrile content is calculated.

[0015] Preferably, the flame retardant is one or more of the following: brominated flame retardants (such as brominated triazine, tetrabromobisphenol A) and antimony white (antimony trioxide).

[0016] Preferably, the D50 particle size of the hydroxyapatite is ≤100nm.

[0017] Preferably, the additive is one or more of antioxidants, lubricants, and anti-dripping agents.

[0018] More preferably, the antioxidant is one or more of the following: hindered phenolic antioxidants (such as pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, etc.), phosphite antioxidants (such as tris(2,4-di-tert-butyl)phosphite, cyclic pentapentanetetrayl di(2,6-di-tert-butyl-4-methylphenyl phosphite), etc.); the lubricant is one or more of the following: stearic acid lubricants (such as calcium stearate, zinc stearate, etc.), polyethylene lubricants (such as polyethylene wax), ester lubricants (such as montanyl ester, stearate ester), paraffin lubricants, amide lubricants (such as EBS, erucamide); and the anti-dripping agent is a polytetrafluoroethylene substance.

[0019] Preferably, the components, by weight, include:

[0020]

[0021] A method for preparing the ABS composite material of the present invention includes:

[0022] Weigh each component according to the weight ratio, mix them, and then feed them into the main feed port of the extruder. After melting, extrusion, and granulation, ABS composite material is obtained.

[0023] Preferably, the melting temperature is 150-230°C.

[0024] More preferably, the temperatures in zones 1, 2, 3, 4, 5, 6, 7, 8, and 9 are 190-225℃, and the main unit speed is 250-360 rpm.

[0025] This invention relates to the application of the ABS composite material in the field of mining equipment, such as electrical control boxes for northern mining equipment.

[0026] The ABS composite material of this invention preferably consists of a blend of SAS resin with a suitable acrylonitrile content, PBAT resin with a suitable viscosity, and ABS resin. Due to the good polarity matching of the chain segments, the melt is more stable during shear blending. The SAS resin contains organosilicon, which promotes flame retardancy. Hydroxyapatite with abundant hydroxyl groups on its surface is selected as a core agent. Because it is weakly alkaline, it can accelerate the decomposition of the flame retardant during combustion and accelerate the formation of the carbon layer, thereby better improving the flame retardant performance.

[0027] Beneficial effects

[0028] The ABS composite material of this invention exhibits superior flame retardancy and high toughness, meeting the requirements for long-term outdoor fire resistance and high toughness in this product. Simultaneously, the lower processing temperature facilitates easy processing and low energy consumption, enhancing product competitiveness. Furthermore, the composite material possesses good toughness, ensuring that the product components are less prone to cracking in low-temperature environments. This composite material is suitable for outdoor low-temperature and fire-resistant applications. Detailed Implementation

[0029] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0030] I. Source of Raw Materials

[0031] ABS resin-1: D-120A, Guoqiao Chemical Co., Ltd., melt flow rate is 12g / 10min (220℃, 10kg);

[0032] ABS resin-2: MG29, SABIC, melt flow rate of 8 g / 10 min (220 °C, 10 kg);

[0033] ABS Resin-3: PA-709, Chi Mei Chemical Co., Ltd., melt flow rate is 5g / 10min (220℃, 10kg);

[0034] ABS resin-4: 0215A, Jilin Chemical Company, melt flow rate is 22g / 10min (220℃, 10kg);

[0035] PBAT Resin-1: A400, Zhuhai Wantong Chemical Co., Ltd., intrinsic viscosity is 2.0 dl / g;

[0036] PBAT Resin-2: A401, Zhuhai Wantong Chemical Co., Ltd., intrinsic viscosity is 2.5 dl / g;

[0037] PBAT resin-3: A402, Zhuhai Wantong Chemical Co., Ltd., intrinsic viscosity is 2.8 dl / g;

[0038] PBAT resin-4: A500, Zhuhai Wantong Chemical Co., Ltd., intrinsic viscosity is 1.6 dl / g;

[0039] SAS Resin-1: TW-21H, UMG, acrylonitrile content 33%;

[0040] SAS Resin-2: S351, UMG, acrylonitrile content 20%;

[0041] Flame retardant: The mass ratio of brominated triazine, tetrabromobisphenol A, and antimony trioxide is 1.5:1.5:1;

[0042] Hydroxyapatite: Aladdin Chemicals, Nano HAP: D50 particle size is 80nm;

[0043] Nano talc: HTP Ultra 5L, Liaoning Aihai Yimi Mining Co., Ltd.;

[0044] Additives: antioxidants, lubricants and anti-dripping agents, in a mass ratio of 3:3:2, wherein the mass ratio of primary antioxidant to secondary antioxidant is 1:1.

[0045] The main antioxidant, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)phenylpropionate, is commercially available.

[0046] Tris(2,4-di-tert-butyl)phosphite, an auxiliary antioxidant, is commercially available.

[0047] The lubricant, an amide-based lubricant EBS EB-FF, is commercially available.

[0048] The anti-dripping agent is a polytetrafluoroethylene-based substance SN80-SA7, which is commercially available.

[0049] The antioxidants, lubricants, and anti-dripping agents used in the parallel examples and comparative examples are the same commercially available products.

[0050] II. Preparation methods of the examples and comparative examples

[0051] Weigh each component according to the weight ratio, mix them, and then feed them into the main feed port of the extruder. After melting, extrusion, and granulation, ABS composite material is obtained. The processing conditions for melt extrusion in the extruder are as follows: Zone 1 temperature 190-205℃, Zone 2 temperature 190-205℃, Zone 3 temperature 195-215℃, Zone 4 temperature 195-220℃, Zone 5 temperature 195-220℃, Zone 6 temperature 195-225℃, Zone 7 temperature 195-225℃, Zone 8 temperature 190-225℃, Zone 9 temperature 190-225℃, and main machine speed 250-360 rpm.

[0052] III. Testing Standards and Methods

[0053] Flame retardant performance evaluation method: Injection-molded 2.0mm thick flame retardant specimens, test the vertical burning time, and determine the flame retardant level according to standard GB / T2408-2021.

[0054] Toughness Quantitative Characterization Method: The notched impact strength of the cantilever beam was tested according to ISO 180-2000. The notch type was Type A, and the test temperature was -10℃. The higher the impact strength value, the better the toughness.

[0055] Ease of processing assessment method: Using an injection molding machine at an injection speed of 45 mm / s and an injection pressure of 65 MPa, a holding speed of 45 mm / s and a holding pressure of 65 MPa, and a holding time of 8 seconds, a 100*100*0.8 mm square plate (with a 1.5 mm wide side gate) was injection molded. The lowest processing temperature was set for the injection molding machine. After demolding, the sample was observed to be full and without deformation. This molding temperature was recorded. The lower the temperature, the easier it is to process and mold.

[0056] Table 1. Formulation ratios (parts by weight) of the embodiments.

[0057]

[0058]

[0059] Table 2 Comparative Example Proportions (parts by weight)

[0060] Raw material name Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 ABS Resin-1 50 50 50 50 50 50 ABS Resin-3 50 ABS Resin-4 50 PBAT Resin-1 15 15 15 15 15 PBAT Resin-3 15 PBAT Resin-4 15 SAS Resin-1 15 15 15 15 15 15 15 Flame retardant 15 15 15 15 15 15 15 15 Hydroxyapatite 0.5 0.5 0.5 0.5 0.5 0.5 2 Nano talc 0.5 Additives 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7

[0061] Table 3 Performance data of the embodiments and comparative examples

[0062] Testing items Flame retardant rating Impact strength Minimum molding temperature unit UL94 KJ / m2 ℃ Example 1 5VA 16.6 180 Example 2 5VB 11.8 190 Example 3 5VB 13.9 185 Example 4 5VB 14.5 195 Example 5 5VB 12.6 200 Example 6 5VB 13.4 200 Example 7 5VA 10.2 205 Example 8 5VB 12.3 205 Comparative Example 1 V-0 9.9 210 Comparative Example 2 V-0 9.6 205 Comparative Example 3 V-0 9.3 205 Comparative Example 4 V-0 8.4 210 Comparative Example 5 V-0 11.1 205 Comparative Example 6 V-1 7.8 215 Comparative Example 7 V-1 6.5 210 Comparative Example 8 5VB 9.7 210

[0063] Analysis and Explanation:

[0064] The data in Table 3 show that the flame-retardant ABS composite materials prepared in the various embodiments of the present invention have a flame retardant rating of 5VA to 5VB and an impact strength of 10.2-16.6 KJ / m. 2 The minimum molding temperature is 180-205℃, and it also has the characteristics of high flame retardancy, high toughness and easy processing.

[0065] Examples 1-6 show that after adding PBAT resin, SAS resin, and a suitable nucleating agent, the composite material exhibits better processing characteristics and a lower processing temperature. The SAS resin, containing organosilicon, promotes flame retardancy. The prepared flame-retardant ABS composite material has good flame retardant properties, toughness, and processability. Example 1 shows the best ratio effect, and Examples 7-8 are also quite good. The results of comparing Example 1 with Comparative Example 5 indicate that using hydroxyapatite with abundant hydroxyl groups on its surface as a nucleating agent, due to its weak alkalinity, can accelerate the decomposition of the flame retardant during combustion and accelerate the formation of the carbon layer, thus better improving the flame retardant properties. The results of Comparative Examples 1-4 show that using ABS resin with a higher or lower melt index to blend with PBAT resin, or using PBAT resin with a higher or lower intrinsic viscosity to blend with ABS resin, results in unstable phase state during shear blending due to viscosity mismatch. Even with the addition of SAS resin, the performance of the prepared flame-retardant ABS composite material is not optimal. The results of Comparative Examples 6-7 show that adding only one of PBAT and SAS resins in the formulation results in poor flame retardant properties, toughness, and poor processing characteristics. The flame-retardant ABS composite materials prepared by adding too much nucleating agent hydroxyapatite to Comparative Example 8 all had poor toughness and poor processing characteristics.

Claims

1. An ABS composite material, characterized in that, By weight, the components include: The ABS resin has a melt flow rate of 7-20 g / 10 min at 220°C and 10 kg. The intrinsic viscosity of the PBAT resin is 1.8-2.6 dl / g; The acrylonitrile content in the SAS resin is 20-33%.

2. The ABS composite material according to claim 1, characterized in that, The melt flow rate of the ABS resin at 220°C and 10 kg is 8-13 g / 10 min.

3. The ABS composite material according to claim 1, characterized in that, The intrinsic viscosity of the PBAT resin is 2.0-2.5 dl / g.

4. The ABS composite material according to claim 1, characterized in that, The flame retardant is one or more of the following: bromine-based flame retardants and antimony white.

5. The ABS composite material according to claim 1, characterized in that, The additive is one or more of antioxidants, lubricants, and anti-dripping agents.

6. The ABS composite material according to claim 1, characterized in that, By weight, the components include:

7. A method for preparing the ABS composite material according to claim 1, comprising: Weigh each component according to the weight ratio, mix them, and then feed them into the main feed port of the extruder. After melting, extrusion, and granulation, ABS composite material is obtained.

8. The application of the ABS composite material according to any one of claims 1-6 in the field of mining equipment.

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