Abs composite and method for producing the same

Abstract

The application discloses an ABS composite material and a preparation method thereof, and belongs to the technical field of extruded sheets; the ABS composite material comprises the following raw materials in parts by mass: ABS resin 59-79 parts, a flame retardant 15-25 parts, a synergistic flame retardant 5 parts, mineral powder 5-15 parts and a processing aid 1 part. The ABS composite material has the performances of flame retardation, high toughness and high oxygen index, the preparation method is simple and easy to implement, and the ABS composite material is easy to process, and is very suitable for popularization and application in the fields of household appliances, electrical instruments, the building industry, the transportation industry, the security industry and the like.

Description

Technical Field

[0001] This invention belongs to the field of extruded sheet technology, specifically relating to an ABS composite material and its preparation method. Background Technology

[0002] Styrene-butadiene-acrylonitrile (ABS) resin combines the rigidity and heat resistance of acrylonitrile, the gloss and processability of polystyrene, and the impact resistance of polybutadiene. It is widely used in household appliances, office equipment, instruments, transportation, building materials, daily necessities, and packaging materials. However, the limiting oxygen index (LOI) of ordinary ABS resin is only around 18. According to the "Code for Fire Protection Design of Buildings," emergency light housings in the field of security electrical appliances require an OX of greater than 28, necessitating flame-retardant modification of the ABS resin before its use. Furthermore, modified high-oxygen-index flame-retardant ABS is typically limited by its toughness and has poor impact resistance.

[0003] To effectively improve the high oxygen index (HOI) of flame-retardant ABS materials, a common method is to add different mineral fillers to the brominated flame retardant system to increase the OOI. However, these methods have a problem: the flame retardant and the mineral filler have an antagonistic effect on the flame-retardant effect of the material. In the market, high OOI flame-retardant ABS is generally limited by its material formulation system, resulting in relatively low material toughness. Currently, commonly available flame-retardant ABS materials often only achieve some of the properties of flame retardancy, high toughness, and high OOI, making it difficult to meet the application requirements of such products. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide an ABS composite material and its preparation method, thereby solving the problems in the prior art.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] An ABS composite material comprises the following raw materials in parts by weight:

[0007]

[0008] Furthermore, the flame retardant is at least one of decabromodiphenyl ethane, bromotriazine, and chlorinated polyethylene.

[0009] Furthermore, the synergistic flame retardant is at least one of molybdenum trioxide and antimony trioxide.

[0010] Furthermore, the mineral powder is at least one of precipitated barium sulfate and calcium carbonate.

[0011] Furthermore, the processing aid is a combination of a lubricant and an antioxidant.

[0012] Furthermore, the antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant.

[0013] Furthermore, the lubricant is one or more combinations of pentaerythritol stearate, silicone powder, and ethylene bis-stearamide.

[0014] A method for preparing the above-mentioned ABS composite material includes the following steps:

[0015] S1, ABS resin, flame retardant, mineral powder, synergistic flame retardant and processing aids are added into a high-speed mixer according to the mass proportions to obtain a premix;

[0016] S2 involves feeding the premixed material into the main feed port of a twin-screw extruder for melt extrusion, followed by plasticizing, extrusion, and granulation to obtain a high oxygen index and high toughness ABS composite material.

[0017] Furthermore, the screw length-to-diameter ratio of the twin-screw extruder is 48:1. The melt extrusion conditions of the twin-screw extruder are as follows: Zone 1 temperature 190℃, Zone 2 temperature 210℃, Zone 3 temperature 215℃, Zone 4 temperature 215℃, Zone 5 temperature 215℃, Zone 6 temperature 215℃, Zone 7 temperature 220℃, Zone 8 temperature 220℃, Zone 9 temperature 220℃, Zone 10 temperature 210℃, Zone 11 temperature 210℃, main feed rate 350kg / h, screw speed 800rpm.

[0018] The above-mentioned ABS composite material is used in the manufacture of electronic and automotive parts.

[0019] The beneficial effects of this invention are:

[0020] 1. The flame retardant used in this invention is decabromodiphenyl ethane with a high bromine content of about 84%, which can reduce the impact on the impact and maintain good toughness under good high oxygen index conditions.

[0021] 2. The synergistic flame retardant molybdenum trioxide selected in this invention, similar to conventional antimony trioxide, significantly improves the oxygen index. Chlorinated polyethylene is the preferred synergistic catalyst primarily because, as a saturated rubber, it possesses excellent resistance to heat and oxygen aging, ozone aging, acids and alkalis, and chemicals. The addition of chlorinated polyethylene to the composite material prepared in this invention utilizes these properties to give the composite flame-retardant ABS material good toughening properties. Furthermore, CPE contains chlorine, which gives it excellent flame-retardant properties and anti-dripping properties during combustion, further improving the material's safety. Through its synergistic flame retardant effect with molybdenum trioxide, it can effectively improve the oxygen index of the material.

[0022] 3. This invention uses a screened mineral powder filler, specifically precipitated barium sulfate, which is added to flame-retardant ABS. On the one hand, this helps to improve the oxygen index test data; on the other hand, because barium sulfate has a spherical structure, it can minimize the impact on the impact performance of flame-retardant ABS. While meeting the requirements of high oxygen index and high toughness, the cost is also significantly reduced compared to conventional materials.

[0023] 4. The high oxygen index, high toughness, and flame retardant ABS material of the present invention has a simple and easy preparation method and is easy to process, making it very suitable for promotion and application in the fields of household appliances, electrical instruments, construction industry, transportation industry, and security industry. Detailed Implementation

[0024] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] An ABS composite material comprises the following raw materials in parts by weight:

[0026]

[0027] Among them, ABS resin is a high-viscosity ABS resin prepared by low melt index emulsion method;

[0028] The flame retardant is at least one of decabromodiphenyl ethane with high bromine content, bromotriazine, and chlorinated polyethylene;

[0029] The synergistic flame retardant is at least one of molybdenum trioxide and antimony trioxide;

[0030] The mineral powder is at least one of precipitated barium sulfate and calcium carbonate;

[0031] The processing aid is a mixture of antioxidants and lubricants;

[0032] The lubricant is selected from at least one of internal lubricants and external lubricants. The internal lubricant is selected from ethylene bis-stearamides (ethylene bis-stearamide EBS, modified ethylene bis-stearamide TAF, etc.), and the external lubricant can be selected from stearic acids (barium stearate, calcium stearate, etc.). Specifically, the lubricant can be selected from one or more of pentaerythritol stearate, silicone powder, and ethylene bis-stearamide.

[0033] The antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant, such as antioxidant 1010 or antioxidant 168.

[0034] The preparation process of ABS composite material is described in detail below through the following examples and comparative examples. The raw materials used in the examples and comparative examples are as follows, and the parts mentioned in the examples and comparative examples are all parts by mass.

[0035] ABS resin: Low melt index emulsion polymerized ABS, ABS AG10NP, Formosa Plastics, melt index is 0.6 g / 10 min at 200℃ and 5 kg, commercially available;

[0036] Flame retardant A: A flame retardant with a high bromine content of approximately 84%, using decabromodiphenyl ethane, brand name SAYTEX4010, from Dead Sea Bromine Company, Israel.

[0037] Flame retardant B: A flame retardant with a bromine content of approximately 64%, brominated triazine, model FR-245, produced by Shandong Shouguang Co., Ltd., and commercially available.

[0038] Flame retardant C: Chlorinated polyethylene, model CPE135C, produced by Shouguang Hongchuang Environmental Protection Technology Co., Ltd., commercially available;

[0039] Synergistic flame retardants: Antimony trioxide (Sb2O3), available commercially from Changde Chenzhou Antimony Products Co., Ltd.; Molybdenum trioxide (MoO3), from Xingbang Molybdenum Industry.

[0040] Mineral filler: Precipitated barium sulfate, 2000 mesh, Shenzhen Ruixing Radiation Protection Engineering Co., Ltd. Calcium carbonate, CaCO3, 1500 mesh, Omia (USA). Commercially available.

[0041] Antioxidants: Antioxidant 1010, Antioxidant 168, and Leylan are commercially available.

[0042] Lubricant: Pentaerythritol stearate, PETS-AP, Italian brand, commercially available.

[0043] Example 1

[0044] 79 parts of ABS resin, 15 parts of decabromodiphenyl ethane, 5 parts of antimony trioxide, 0.5 parts of antioxidant 1010 and 0.5 parts of pentaerythritol stearate were added to a high-speed mixer and mixed at 500 rpm for 3 minutes to obtain a premix.

[0045] The premix is ​​fed into the melt extrusion through the main feed port of a twin-screw extruder, and then plasticized, extruded, and granulated to obtain a high oxygen index, high toughness, and flame retardant ABS composite material.

[0046] The twin-screw extruder has a screw length-to-diameter ratio of 48:1. The melt extrusion conditions of the twin-screw extruder are as follows: zone 1 temperature 190℃, zone 2 temperature 210℃, zone 3 temperature 215℃, zone 4 temperature 215℃, zone 5 temperature 215℃, zone 6 temperature 215℃, zone 7 temperature 220℃, zone 8 temperature 220℃, zone 9 temperature 220℃, zone 10 temperature 210℃, zone 11 temperature 210℃, main feed rate 350kg / h, and screw speed 800rpm.

[0047] Example 2

[0048] The preparation method is the same as in Example 1, except for the raw materials. The raw materials in this example are: 79 parts ABS resin, 15 parts bromotriazine, 5 parts antimony trioxide, 0.5 parts antioxidant 1010 and 0.5 parts pentaerythritol stearate.

[0049] Example 3

[0050] The preparation method is the same as in Example 1, except for the raw materials. The flame retardant is decabromodiphenyl ethane, and the synergist is molybdenum trioxide. The raw materials in this example are: 79 parts ABS resin, 15 parts decabromodiphenyl ethane, 5 parts molybdenum trioxide, 0.5 parts antioxidant 1010, and 0.5 parts pentaerythritol stearate.

[0051] Comparative Example 1

[0052] The preparation method is the same as in Example 1, except for the raw materials: flame retardant decabromodiphenyl ethane, chlorinated polyethylene; synergist molybdenum trioxide. The raw materials in this comparative example are: 69 parts ABS resin, 15 parts decabromodiphenyl ethane, 5 parts molybdenum trioxide, 5 parts chlorinated polyethylene, 0.5 parts antioxidant 1010 and 0.5 parts pentaerythritol stearate.

[0053] Comparative Example 2

[0054] The preparation method is the same as in Example 1, except for the raw materials: flame retardant decabromodiphenyl ethane, chlorinated polyethylene; synergist molybdenum trioxide, mineral powder calcium carbonate. The raw materials in this comparative example are: 69 parts ABS resin, 15 parts decabromodiphenyl ethane, 5 parts molybdenum trioxide, 5 parts chlorinated polyethylene, 5 parts calcium carbonate, 0.5 parts antioxidant 1010 and 0.5 parts pentaerythritol stearate.

[0055] Comparative Example 3

[0056] The preparation method is the same as in Example 1, except for the raw materials: flame retardant decabromodiphenyl ethane, chlorinated polyethylene; synergist molybdenum trioxide, mineral powder barium sulfate. The raw materials in this comparative example are: 69 parts ABS resin, 15 parts decabromodiphenyl ethane, 5 parts molybdenum trioxide, 5 parts chlorinated polyethylene, 5 parts barium sulfate, 0.5 parts antioxidant 1010 and 0.5 parts pentaerythritol stearate.

[0057] Comparative Example 4

[0058] The preparation method is the same as in Example 1, except for the raw materials: flame retardant decabromodiphenyl ethane, chlorinated polyethylene; synergist molybdenum trioxide, mineral powder barium sulfate. The raw materials in this comparative example are: 64 parts ABS resin, 15 parts decabromodiphenyl ethane, 5 parts molybdenum trioxide, 5 parts chlorinated polyethylene, 10 parts barium sulfate, 0.5 parts antioxidant 1010 and 0.5 parts pentaerythritol stearate.

[0059] Comparative Example 5

[0060] The preparation method is the same as in Example 1, except for the raw materials: flame retardant decabromodiphenyl ethane, chlorinated polyethylene; synergist molybdenum trioxide, mineral powder barium sulfate. The raw materials in this comparative example are: 59 parts ABS resin, 15 parts decabromodiphenyl ethane, 5 parts molybdenum trioxide, 5 parts chlorinated polyethylene, 15 parts barium sulfate, 0.5 parts antioxidant 1010 and 0.5 parts pentaerythritol stearate.

[0061] Experimental testing;

[0062] The ABS composite materials prepared in Examples 1-3 and Comparative Examples 1-5 were simultaneously prepared with ABS raw materials to prepare standard samples for testing. The specific steps included the following:

[0063] The flame-retardant ABS materials prepared in Examples 1-3 and Comparative Examples 1-5 were dried in an oven at 80°C for 4 hours. National standard notched impact test specimens, national standard bending test specimens, and flame-retardant 2.0mm test specimens were then injection molded. The test specimens for oxygen index testing were national standard bending test specimens.

[0064] The standards and methods referenced in the test are as follows:

[0065] The melt flow index test conditions are: GB / T 3682, 220℃ / 10kg;

[0066] Impact strength: GB / T 1843, sample size 80mm×10mm×4mm;

[0067] Flame retardant: UL-94, sample size 128mm×12.8mm×2.0mm;

[0068] Oxygen index determination: Following the method provided in GB / T2406.2-2009, pretreatment was performed at 25℃ and 50% RH for 88 hours. Ignition method: A-top surface ignition method.

[0069] The test results are shown in Table 1 below;

[0070] Table 1. Experimental results of Examples 1-8 and Comparative Examples 1-5

[0071]

[0072] According to the data from Examples 1-3, flame retardants with different bromine contents combined with different synergists show significant differences in oxygen index and impact resistance of flame-retardant ABS. Among them, the decabromodiphenyl ethane combined with molybdenum trioxide as a synergist in Example 3 showed the best effect. The high-bromine-content decabromodiphenyl ethane was selected mainly because it can provide as much bromine as possible while maintaining impact and flame retardant properties, which is beneficial for oxygen index testing.

[0073] According to Examples 1, 2, and 3, and the data from Comparative Example 1, in the brominated flame retardant system, the chlorinated polyethylene synergist effectively improves the oxygen index, increasing it from 23 to 27, a year-on-year increase of 17%; the impact index increases from 17.3 to 28.4, a significant improvement of approximately 50%. Simultaneously, the melt index is also enhanced, which is beneficial for the processability of the material. This is mainly because chlorinated polyethylene, as a saturated rubber, possesses excellent resistance to heat and oxygen aging, ozone aging, acids and alkalis, and chemicals. In the composite material prepared by this patent, the addition of chlorinated polyethylene utilizes these properties to give the composite flame-retardant ABS material good toughening properties. Furthermore, the presence of chlorine in CPE gives it excellent flame retardant properties, along with anti-dripping properties during combustion, further improving the material's safety performance. By combining with molybdenum trioxide as a synergistic flame retardant, the oxygen index of the material can also be effectively improved.

[0074] Based on the data from Comparative Examples 1, 2, and 3, it can be seen that by selecting different fillers, the oxygen index of the material can be increased from 27 to 29. Comparative Examples 2 and 3 show that the selected barium sulfate not only effectively improves the oxygen index of the material but also maintains the impact index at around 26, which is approximately 25% higher than the 21 performance of the calcium carbonate-filled system. This is mainly because the barium sulfate filler has a spherical structure, resulting in a relatively smaller impact effect on the material; simultaneously, it alters the proportions of different components in the material, reducing flammability and thus increasing the oxygen index.

[0075] Based on the data from Examples 1, 2, and 3, and Comparative Examples 1, 2, 3, 4, and 5, it is evident that, considering the oxygen index and overall impact, Example 4 in the brominated flame retardant system not only maintains a high toughness impact rating of 24.3 but also possesses a high oxygen index of 32. Both are significantly higher than conventional flame retardant formulations with antimony, molybdenum, and other synergistic flame retardants. Furthermore, this system, due to the use of a high proportion of 10 parts barium sulfate filler, offers a significant cost advantage and has broad market prospects.

[0076] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0077] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. An ABS composite material, characterized in that, It consists of the following raw materials in parts by weight: 59-79 parts of ABS resin; 15-25 parts flame retardant; Five parts of synergistic flame retardant; 5-15 parts mineral powder; 1 part processing aid; The synergistic flame retardant is molybdenum trioxide; The mineral powder is precipitated barium sulfate with a spherical structure; The melt flow index of ABS resin at 200℃ and 5kg is 0.6g / 10min; The flame retardant comprises chlorinated polyethylene.

2. The ABS composite material according to claim 1, characterized in that, The processing aid is a combination of a lubricant and an antioxidant.

3. The ABS composite material according to claim 2, characterized in that, The antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant.

4. An ABS composite material according to claim 2, characterized in that, The lubricant is one or more of pentaerythritol stearate, silicone powder, and ethylene bis-stearamide.

5. A method for preparing the ABS composite material according to any one of claims 1-4, characterized in that, Includes the following steps: S1, ABS resin, flame retardant, mineral powder, synergistic flame retardant and processing aids are added into a high-speed mixer according to the mass proportions to obtain a premix; S2 involves feeding the premixed material into the main feed port of a twin-screw extruder for melt extrusion, followed by plasticizing, extrusion, and granulation to obtain a high oxygen index and high toughness ABS composite material.

6. The method for preparing ABS composite material according to claim 5, characterized in that, The twin-screw extruder has a screw length-to-diameter ratio of 48:

1. The melt extrusion conditions for the twin-screw extruder are as follows: Zone 1 temperature 190℃, Zone 2 temperature 210℃, Zone 3 temperature 215℃, Zone 4 temperature 215℃, Zone 5 temperature 215℃, Zone 6 temperature 215℃, Zone 7 temperature 220℃, Zone 8 temperature 220℃, Zone 9 temperature 220℃, Zone 10 temperature 210℃, Zone 11 temperature 210℃, main feed rate 350kg / h, and screw speed 800rpm.

7. The application of the ABS composite material according to any one of claims 1-4 in the manufacture of electronic and automotive parts.

Images