Brominated flame retardant, flame-retardant ABS (Acrylonitrile Butadiene Styrene) resin composition as well as preparation method and application thereof

Abstract

The invention provides a brominated flame retardant, a flame-retardant ABS resin composition and a preparation method and application of the brominated flame retardant, the brominated flame retardant has large molecular weight, high heat-resistant temperature and excellent flame retardant property, has excellent compatibility with ABS resin, and has excellent flame retardant property after being added into the ABS resin. The flame-retardant ABS resin composition can be ensured to have high heat resistance, low precipitation characteristic and excellent mechanical property on the premise of having excellent flame retardant property.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a brominated flame retardant, a flame-retardant ABS resin composition, its preparation method, and its application. Background Technology

[0002] Styrene-butadiene-styrene copolymer (ABS) resin is widely used in appearance parts of home appliances, cleaning appliances and office equipment due to its excellent comprehensive properties, such as high gloss, excellent mechanical properties and good processing performance. However, ABS resin has a low oxygen index and is a flammable material, which limits its application in some occasions that require strict fire resistance.

[0003] To improve the flame retardant properties of ABS resin, flame retardants are typically added for modification. Currently, brominated flame retardants are the most commonly used flame retardants for ABS resin, mainly including brominated triazine and brominated epoxy. These flame retardants achieve their flame-retardant effect by inhibiting chemical reactions during combustion and increasing the limiting oxygen index of the material. However, these flame retardants have small molecular weights and low polarity, resulting in poor compatibility with ABS resin. They are prone to precipitating in flame-retardant ABS products, thus affecting the product's appearance and mechanical properties. In addition, low molecular weight brominated triazine and brominated epoxy act as plasticizers in ABS resin, significantly reducing the material's heat resistance temperature. This means that the heat distortion temperature of flame-retardant ABS is generally below 80°C, limiting its application range in high-temperature environments.

[0004] Therefore, to improve the heat resistance temperature of flame-retardant ABS, the commonly used method is to add heat-resistant modifiers or blend it with other polymers with good heat resistance, which can significantly improve the heat resistance of flame-retardant ABS. For example, adding heat-resistant modifiers such as α-methylstyrene (MS) or maleimide (MI) to ABS can increase its glass transition temperature, thereby enhancing its heat resistance. However, the introduction of heat-resistant agents greatly reduces the mechanical properties of ABS materials, especially its impact resistance.

[0005] Therefore, it is of great significance to develop a brominated flame retardant with low exudation, excellent flame retardant properties, and without affecting the mechanical properties and heat resistance of ABS resin. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the purpose of this invention is to provide a brominated flame retardant, a flame-retardant ABS resin composition, a preparation method thereof, and its application. The flame-retardant ABS resin composition prepared by the brominated flame retardant has excellent flame retardant properties, as well as high heat resistance, low exudation characteristics, and excellent mechanical properties.

[0007] To achieve this objective, the present invention employs the following technical solution: In a first aspect, the present invention provides a brominated flame retardant having the structure shown in Formula I: Formula I; Where x is an integer from 66 to 80 (e.g., 67, 68, 69, 70, 72, 74, 76, 78, 80 or any of the above values); y is an integer from 20 to 34 (e.g., 20, 22, 24, 26, 28, 30, 32, 33 or any of the above values), more preferably x is from 67 to 75 and y is from 23 to 33.

[0008] The structure of the brominated flame retardant provided by this invention is shown in Formula I above. It has a relatively large molecular weight, a high heat resistance temperature and excellent flame retardant properties, and has excellent compatibility with ABS resin. Therefore, when added to ABS resin, it can ensure that the resulting flame-retardant ABS resin composition has excellent flame retardant properties, as well as high heat resistance, low exudation characteristics and excellent mechanical properties.

[0009] In a second aspect, the present invention provides a method for preparing a brominated flame retardant as described in the first aspect, the method comprising: carrying out a bromination reaction of a styrene-acrylonitrile copolymer and bromine in the presence of a catalyst to obtain the brominated flame retardant.

[0010] The reaction equation for the above bromination reaction is as follows: ; Where x and y have the same range of values ​​as x and y in Equation I.

[0011] Preferably, the molar ratio of the styrene-acrylonitrile copolymer to bromine is 1:(3.1~3.3), for example 1:3.1, 1:3.15, 1:3.2, 1:3.25 or 1:3.3, etc.

[0012] Preferably, the styrene-acrylonitrile copolymer has the following structural formula II: Formula II; Where x and y have the same range of values ​​as x and y in Equation I.

[0013] Preferably, the catalyst includes at least one of AlCl3, FeCl3, or ZnCl2.

[0014] Preferably, based on 1 g of the styrene-acrylonitrile copolymer, the amount of the catalyst is 0.001~0.1 g, for example 0.001 g, 0.002 g, 0.004 g, 0.006 g, 0.008 g, 0.01 g, 0.02 g, 0.04 g, 0.06 g, 0.08 g, or 0.1 g, etc.

[0015] Preferably, the bromination reaction is carried out at a temperature of 30~60℃, such as 30℃, 35℃, 40℃, 45℃, 50℃, 55℃ or 60℃.

[0016] Preferably, the bromination reaction time is 0.5 to 6 h, for example, 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 5 h or 6 h.

[0017] Thirdly, the present invention provides a flame-retardant ABS resin composition, wherein the flame-retardant ABS resin composition comprises the following components in parts by weight: 55-90 parts by weight of ABS resin; 15-25 parts by weight of the brominated flame retardant as described in the first aspect; The first synergistic flame retardant is 0.8 to 7.2 parts by weight.

[0018] The flame-retardant ABS resin composition provided by the present invention uses a brominated flame retardant as described in the first aspect and a first synergistic flame retardant to achieve highly efficient flame retardancy of ABS resin without affecting the excellent mechanical properties of ABS resin itself, and also enables the obtained flame-retardant ASB resin composition to have both high heat resistance and low exudation characteristics.

[0019] The amount of ABS resin used can be 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, or any of the above values; preferably, the mass percentage of ABS resin in the flame-retardant ABS resin composition is not less than 55%.

[0020] The amount of the brominated flame retardant can be 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, or any of the above values.

[0021] The amount of the first synergistic flame retardant can be 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, or any of the above values.

[0022] The melt flow index of the ABS resin at 220°C and 10 kg is 5~45 g / 10min, for example 5 g / 10min, 10 g / 10min, 15 g / 10min, 20 g / 10min, 30 g / 10min, 40 g / 10min, 45 g / 10min or any of the above values.

[0023] In this invention, the melt flow index of the ABS resin can be tested according to the method provided in ASTM D1238-2010.

[0024] Preferably, the first synergistic flame retardant includes at least one of antimony trioxide, zinc borate, zinc oxide, and sodium antimonate, more preferably antimony trioxide.

[0025] In this invention, the D50 of the first synergistic flame retardant is 0.1~20μm, for example, it can be 0.1μm, 0.2μm, 0.5μm, 1μm, 2μm, 4μm, 6μm, 8μm, 10μm, 15μm, 18μm or any of the above values.

[0026] In this invention, the D50 of the first synergistic flame retardant can be obtained by testing with a laser particle size analyzer.

[0027] Preferably, the flame-retardant ABS resin composition further includes a second flame-retardant synergist.

[0028] Preferably, the content of the second flame retardant synergist in the flame retardant ABS resin composition is not higher than 10 parts by weight, for example, 9 parts by weight, 8 parts by weight, 7 parts by weight, 6 parts by weight, 5 parts by weight, 4 parts by weight, 3 parts by weight, 2 parts by weight, 1 part by weight or any of the above values, more preferably 2 to 5 parts by weight.

[0029] Preferably, the second flame retardant synergist includes at least one of barium sulfate, titanium dioxide, talc, and montmorillonite, more preferably talc and / or montmorillonite.

[0030] In this invention, the D50 of the second synergistic flame retardant is 0.1~20μm, for example, it can be 0.1μm, 0.2μm, 0.5μm, 1μm, 2μm, 4μm, 6μm, 8μm, 10μm, 15μm, 18μm or any of the above values.

[0031] In this invention, the D50 of the second synergistic flame retardant can be obtained by testing with a laser particle size analyzer.

[0032] Preferably, the flame-retardant ABS resin composition also includes other additives.

[0033] Preferably, the content of other additives in the flame-retardant ABS resin composition is not higher than 2 parts by weight, for example 2 parts by weight, 1.8 parts by weight, 1.6 parts by weight, 1.4 parts by weight, 1.2 parts by weight, 1 part by weight, 0.8 parts by weight, 0.6 parts by weight, 0.4 parts by weight, or any of the above values.

[0034] In this invention, the other additives can be selectively added as needed. For example, antioxidants, lubricants, and other conventional additives in the art can be selectively added. There are no special requirements for the specific types of antioxidants and lubricants. For example, the antioxidants can be antioxidant 1010, antioxidant 168, antioxidant TNPP, etc., and the lubricants can be vinyl bis-stearamide (EBS), erucamide, polyethylene wax, pentaerythritol stearate, pentaerythritol oleate, etc.

[0035] Fourthly, the present invention provides a method for preparing a flame-retardant ABS resin composition as described in the second aspect, the method comprising: mixing the various components and extruding and granulating them to obtain the flame-retardant ABS resin composition.

[0036] Preferably, the mixing time is 3 to 5 minutes, such as 3 minutes, 3.2 minutes, 3.4 minutes, 3.6 minutes, 3.8 minutes, 4 minutes, 4.2 minutes, 4.4 minutes, 4.6 minutes, 4.8 minutes, or 5 minutes.

[0037] Preferably, the extrusion granulation temperature is 150~230℃, such as 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃ or 230℃.

[0038] Preferably, the extrusion granulation is carried out in a twin-screw extruder.

[0039] Preferably, the temperature ranges of the twin-screw extruder are as follows: Zone 1: 150~180℃ (e.g., 150℃, 160℃, 170℃, or 180℃); Zone 2: 180~200℃ (e.g., 180℃, 185℃, 190℃, 195℃, or 200℃); Zone 3: 180~200℃ (e.g., 180℃, 185℃, 190℃, 195℃, or 200℃); Zone 4: 190~210℃ (e.g., 190℃, 195℃, 200℃, 205℃, or 210℃); Zone 5: 200~220℃ (e.g., 200℃, 205℃, 210℃, 215℃, or 220℃); Zone 6: 200~220℃ (e.g., 150℃, 160℃, 170℃, or 180℃); Zone 6: 200~220℃ (e.g., 180℃, 160℃, 170℃, or 180℃); Zone 7: 180~200℃ (e.g., 180℃, 160℃, 170℃, or 180℃); Zone 8: 180~200℃ (e.g., 180℃, 160℃, 170℃, or 180℃); Zone 9: 180~200℃ (e.g., 180℃, 160℃, 170℃, or 180℃); Zone 100~220℃ (e.g., 180℃, 160℃ Zones 7, 8, 9, 10, and 11 are 200℃, 205℃, 210℃, 215℃, or 220℃, respectively. The temperature ranges for each zone are as follows: Zone 7: 200℃, 205℃, 210℃, 215℃, or 220℃, respectively. The temperature ranges for each zone are as follows: Zone 8: 200℃, 205℃, 210℃, 215℃, 220℃, 225℃, or 230℃, respectively. The temperature ranges for each zone are as follows: Zone 9: 210℃, 215℃, 220℃, 225℃, or 230℃, respectively. The temperature ranges for each zone are as follows: Zone 1: 210℃, 215℃, 220℃, 225℃, or 230℃, respectively. The temperature ranges for each zone are as follows: Zone 1: 210℃, 215℃, 220℃, 225℃, or 230℃, respectively.

[0040] Preferably, the rotational speed of the twin-screw extruder is 300~600 rpm, such as 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm or 600 rpm.

[0041] Preferably, the length-to-diameter ratio of the twin-screw extruder is 40 to 44:1, such as 40:1, 41:1, 42:1, 43:1, or 44:1.

[0042] Fifthly, the present invention provides a component comprising the flame-retardant ABS resin composition as described in the third aspect.

[0043] Preferably, the component includes at least one of household goods, electronic components, household appliance parts, gardening equipment parts, medical technology equipment parts, or motor vehicle parts.

[0044] Specifically, the aforementioned components include television casings or charger casings.

[0045] Compared with the prior art, the present invention has the following beneficial effects: The brominated flame retardant provided by this invention has a large molecular weight, a high heat resistance temperature, and excellent flame retardant properties. It also has excellent compatibility with ABS resin. When added to ABS resin, it can ensure that the resulting flame-retardant ABS resin composition has excellent flame retardant properties, as well as high heat resistance, low exudation characteristics, and excellent mechanical properties, resulting in excellent overall performance. Attached Figure Description

[0046] Figure 1 The carbon NMR spectrum of the brominated flame retardant provided in Example 1; Figure 2 The infrared spectrum of the brominated flame retardant provided in Example 1. Detailed Implementation

[0047] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0048] Unless otherwise specified, all materials used in this invention are commercially available or prepared using conventional methods; in particular, detailed information on some of the materials used in this invention is as follows: (1) Styrene-acrylonitrile copolymer (AS): AS-1: Its structural formula is x is 74, y is 26, Liaoning Jinfeng KFA-130; AS-2; its structural formula is: x is 79, y is 21, Liaoning Jinfeng KFA-130B; AS-3; its structural formula is: x is 68, y is 32, Liaoning Jinfeng KFA-180.

[0049] (2) ABS resin: ABS-1: Melt flow index of 22 g / 10min (220℃ / 10 kg), purchased from Liaoning Jinfeng, model KF-730; ABS-2: Melt flow index of 35-40 g / 10min (220℃ / 10 kg), purchased from Liaoning Jinfeng, model KF-740; ABS-3: Melt flow index of 8 g / 10min (220℃ / 10 kg), purchased from Liaoning Jinfeng, model KF-718.

[0050] (3) Synergistic flame retardants: Antimony trioxide: Commercially available.

[0051] Zinc borate: Commercially available.

[0052] Talc, montmorillonite, and barium sulfate are all sourced from commercially available products.

[0053] (4) Bromotriazine: purchased from ICL Dead Sea, model FR-245.

[0054] (5) Brominated epoxy: purchased from ICL Dead Sea, model F-3014.

[0055] Example 1 A brominated flame retardant, the structural formula of which is shown below: ; Where x is 76 and y is 24; The preparation method of the brominated flame retardant provided in this embodiment includes: taking 20 g of styrene-acrylonitrile copolymer (AS-1) and placing it in a 1000 mL four-necked flask equipped with a mechanical stirrer, a constant pressure dropping funnel, a thermometer, and a tail gas receiving device; adding 300 mL of dichloromethane; heating and stirring in a water bath to dissolve the copolymer; after the styrene-acrylonitrile copolymer is completely dissolved; adding 0.1 g of AlCl3 catalyst to the four-necked flask and stirring to fully disperse it in the solvent; then adding 150 g of bromine dropwise to the reaction flask at a constant pressure dropping funnel, maintaining the dropping temperature at 25°C; after the dropping is complete, raising the temperature to 50°C and holding for 5 hours to ensure complete bromination; after the reaction is complete, slowly adding a 10% sodium metabisulfite aqueous solution to the four-necked flask, stirring until the solution color changes from reddish-brown to pale yellow or colorless; removing any unreacted bromine; and then transferring the mixture to a 1000 mL four-necked flask. The organic phase was separated in a separatory funnel of mL, and a saturated sodium bicarbonate solution was added to the organic phase to adjust the pH to neutral. The mixture was washed three times with water to obtain the organic phase. The solvent was removed by a rotary evaporator to obtain the bromine-based flame retardant.

[0056] Structural characterization: (1) The brominated flame retardant provided in Example 1 was tested using a nuclear magnetic resonance spectrometer (Brook, AVANCE NEO 400M). The carbon NMR spectrum of the brominated flame retardant provided in Example 1 is shown below. Figure 1 As shown; from Figure 1It can be seen that: 120.2 ppm is the sequence structure peak of AAA, 120.8 ppm is the sequence structure peak of AAS and SAA, 122 ppm is the sequence structure peak of SAS, 142.3 ppm is the sequence structure peak of ASA, 143.7 ppm is the sequence structure peak of SSA or ASS, and 145.9 ppm is the sequence structure peak of SSS; where AAA represents acrylonitrile-acrylonitrile-acrylonitrile sequence; AAS represents acrylonitrile-acrylonitrile-styrene sequence; SAA represents styrene-acrylonitrile-acrylonitrile sequence; SAS represents styrene-acrylonitrile-styrene sequence; ASA represents acrylonitrile-styrene-acrylonitrile sequence; SSA represents styrene-styrene-acrylonitrile sequence; ASS represents acrylonitrile-styrene-styrene sequence; and SSS represents styrene-styrene-styrene sequence.

[0057] (2) The brominated flame retardant provided in Example 1 was tested using an infrared spectrometer (Thermo Fisher Scientific, Nicolet iS50). The infrared spectrum of the brominated flame retardant provided in Example 1 is shown below. Figure 2 As shown; from Figure 2 It can be seen that: 567cm -1 The peak at this point represents the stretching vibration of the carbon-bromine bond, indicating that bromine is effectively introduced into the SAN structure.

[0058] Examples 2-3 Examples 2 and 3 respectively provide a brominated flame retardant. The difference between them and Example 1 is that in the preparation method, AS-1 is replaced with AS-2 and AS-3 of equal mass, respectively. All other steps are the same as in Example 1.

[0059] Application Examples 1-11 and Comparative Application Examples 1-5 Application Examples 1-11 and Comparative Application Examples 1-5 each provide a flame-retardant ABS resin composition, the components and amounts of which are shown in Table 1. In Table 1, the amount of each component is in parts by weight.

[0060] Table 1 The preparation method of the flame-retardant ABS resin composite material provided in Application Examples 1-11 and Comparative Application Examples 1-5 includes: placing each component in Table 1 according to its respective weight parts into a mixer with a rotation speed of about 100 rpm and mixing for 5 min; then, melting and granulating the mixture in a twin-screw extruder with an aspect ratio of 40:1, a temperature range of 160℃, 190℃, 190℃, 200℃, 210℃, 210℃, 220℃, 220℃, and 220℃, and a rotation speed of 450 rpm to obtain the flame-retardant ABS resin composition.

[0061] Performance testing: (1) Flame retardancy rating: Tested according to UL94-2018 standard, the thickness of the test sample is 2~3 mm.

[0062] (2) Notched impact strength: The test shall be conducted in accordance with the method provided in the test standard GB-T1843-1996.

[0063] (3) Heat distortion temperature: The test was conducted with a load of 1.8 MPa, referring to ISO75-2004 standard.

[0064] (4) Mold scale: 304 stainless steel with a size of 30×30 mm was used as the mold. Samples were continuously injected into the mold. Mold scale such as gas generated during the injection process was deposited on the surface. The precipitates on the mold surface within 2 hours were collected and weighed.

[0065] Flame-retardant ABS resin compositions were tested according to the test methods described above, corresponding to test cases 1-11 and comparative application examples 1-5. The test results are shown in Table 2. Table 2 According to the data in Table 2: Application Examples 1-5 provide flame-retardant ABS resin compositions with a flame retardant rating of V-0, a heat distortion temperature of not less than 78°C, and a notched impact strength of not less than 15 kJ / m². -2 The amount of scale is only about 2 mg. It has excellent flame retardant properties, high heat resistance, low precipitation characteristics and excellent mechanical properties, and its overall performance is excellent.

[0066] As can be seen from the comparison between Application Example 1 and Application Example 11, and Comparative Application Example 5, the combination of the second synergistic flame retardant and the first synergistic flame retardant is beneficial to further improve the flame retardant performance while ensuring good impact performance.

[0067] Comparing the data from Application Example 1 and Comparative Application Examples 1-2, it can be seen that when the brominated flame retardant is brominated triazine or brominated epoxy, the resulting flame-retardant ABS resin composition has a lower flame retardant rating and a higher amount of mold residue, resulting in poor flame retardant performance and exudation characteristics.

[0068] Comparing the data from Application Example 1 and Comparative Application Examples 3-4, it can be seen that when the amount of brominated flame retardant provided in Example 1 is too high, the notched impact strength of the resulting flame-retardant ABS resin composition will decrease and the mechanical properties will deteriorate; while when the amount of brominated flame retardant provided in Example 1 is too low, the flame retardant rating of the resulting flame-retardant ABS resin composition will only be V-1, and the flame retardant performance will decrease.

[0069] The applicant declares that this invention illustrates a brominated flame retardant, a flame-retardant ABS resin composition, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above process steps, meaning that this invention does not necessarily rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of the raw materials used in this invention, additions of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this invention.

Claims

1. A brominated flame retardant, characterized in that, The brominated flame retardant has the structure shown in Formula I: Formula I; Where x is an integer between 66 and 80, and y is an integer between 20 and 34.

2. A method for preparing the brominated flame retardant as described in claim 1, characterized in that, The preparation method includes: brominating styrene-acrylonitrile copolymer and bromine in the presence of a catalyst to obtain the bromine-based flame retardant having the structure shown in Formula I.

3. The preparation method according to claim 2, characterized in that, The molar ratio of the styrene-acrylonitrile copolymer to bromine is 1:(3.1~3.3); Preferably, the catalyst comprises at least one of AlCl3, FeCl3, or ZnCl2; Preferably, the bromination reaction is carried out at a temperature of 30-60°C for 3-6 hours.

4. A flame-retardant ABS resin composition, characterized in that, The flame-retardant ABS resin composition comprises the following components in parts by weight: 55-90 parts by weight of ABS resin; 15-25 parts by weight of the brominated flame retardant as described in claim 1; The first synergistic flame retardant is 0.8 to 7.2 parts by weight.

5. The flame-retardant ABS resin composition according to claim 4, characterized in that, The melt index of the ABS resin at 220°C and 10 kg is 5~45 g / 10min.

6. The flame-retardant ABS resin composition according to claim 4, characterized in that, The first synergistic flame retardant includes at least one of antimony trioxide, zinc borate, zinc oxide, and sodium antimonate, more preferably antimony trioxide.

7. The flame-retardant ABS resin composition according to claim 4, characterized in that, The flame-retardant ABS resin composition also includes a second flame-retardant synergist; Preferably, the content of the second flame retardant synergist in the flame retardant ABS resin composition is not more than 10 parts by weight, and more preferably 2 to 5 parts by weight. Preferably, the second flame retardant synergist includes at least one of barium sulfate, titanium dioxide, talc, and montmorillonite, more preferably talc and / or montmorillonite; Preferably, the flame-retardant ABS resin composition further includes other additives; Preferably, the content of other additives in the flame-retardant ABS resin composition is no more than 2 parts by weight.

8. A method for preparing the flame-retardant ABS resin composition according to any one of claims 4 to 7, characterized in that, The preparation method includes: mixing the various components and extruding and granulating them to obtain the flame-retardant ABS resin composition.

9. A component, characterized in that, The component comprises the flame-retardant ABS resin composition as described in any one of claims 4 to 7.

10. The part according to claim 9, characterized in that, The components include at least one of the following: household goods, electronic components, household appliance parts, gardening equipment parts, medical technology equipment parts, or motor vehicle parts.

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