A weather-resistant and flame-retardant ABS material, its preparation method and application

Abstract

The present invention relates to a weather-resistant flame-retardant ABS material, its preparation method and application, belonging to the technical field of modified plastics. The weather-resistant flame-retardant ABS material of the present invention comprises the following components in parts by weight: 34-42 parts of ABS resin, 15-25 parts of SAN resin, 15-25 parts of CPE resin, 2-4 parts of compatibilizer, 12-18 parts of bromine-based flame retardant, and 3-5 parts of antimony-based flame retardant; the bromine-based flame retardant is a high-molecular brominated epoxy resin. By adding the high-molecular brominated epoxy resin to the ABS material in the present invention, the prepared ABS material has higher photothermal stability performance, greatly improving the overall weather resistance of the material; in the ABS material of the present invention, ABS resin, SAN resin and CPE resin are added simultaneously, and the three resins act together within a specific content range to improve the problem of the above-mentioned decrease in toughness, and at the same time, the weather resistance of the material will not be reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of modified plastics, and particularly relates to a weather-resistant and flame-retardant ABS material, a preparation method thereof, and an application thereof. Background Art

[0002] Acrylonitrile-butadiene-styrene terpolymer (ABS) is a thermoplastic polymer material with high strength, high toughness, and high gloss properties, and is easy to process and form. ABS belongs to flammable resin. In order to meet the fire prevention requirements of general products, bromine-antimony flame retardants need to be added to modify it into a flame-retardant ABS material. However, the butadiene rubber and bromine-based flame retardants contained in the flame-retardant ABS are easily decomposed and aged, resulting in poor weather resistance, which greatly restricts the application of flame-retardant ABS in products such as bathrooms, household appliances, and automobiles that require weather resistance.

[0003] In the prior art, the main ways to prepare weather-resistant and flame-retardant ABS are to add photo-thermal stabilizers or prepare ABS alloy materials. Chinese Patent CN103772882B prepared a weather-resistant and flame-retardant ABS / PET material for extrusion process by an alloy method, but its application scope is limited and it can only be used for extrusion molding products. Chinese Patent CN 111534039A discloses a weather-resistant and flame-retardant ABS material and a preparation method thereof, and its weather resistance is good, but this method first needs to prepare a capsule flame retardant, and the preparation process is numerous and time-consuming. Summary of the Invention

[0004] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a weather-resistant and flame-retardant ABS material, a preparation method thereof, and an application thereof, so as to solve the problem that it is difficult for flame-retardant ABS in the prior art to balance toughness and weather resistance.

[0005] To achieve the above purpose, the technical solution adopted by the present invention is: a weather-resistant and flame-retardant ABS material, comprising the following components in parts by weight: 34-42 parts of ABS resin, 15-25 parts of SAN resin, 15-25 parts of CPE resin, 2-4 parts of compatibilizer, 12-18 parts of bromine-based flame retardant, and 3-5 parts of antimony-based flame retardant; the bromine-based flame retardant is a high molecular weight brominated epoxy resin; the number average molecular weight of the high molecular weight brominated epoxy resin is 10,000-25,000.

[0006] In view of the problem in the prior art that it is difficult for flame-retardant ABS materials to balance toughness and weather resistance, a flame-retardant ABS material is provided by selecting the types and contents of various components in the flame-retardant ABS material. This material has high toughness and weather resistance and is easy to process. Through a large number of experiments, the inventors of this application found that adding high-molecular-weight brominated epoxy resin to the ABS material and compounding it with an antimony-based flame retardant enables the ABS material to achieve a flame-retardant function. At the same time, compared with traditional brominated flame retardants (bromotriazine, tetrabromobisphenol A, and low-molecular-weight brominated epoxy), high-molecular-weight brominated epoxy resin has higher photothermal stability and is not easily migratory and precipitated onto the material surface, which greatly improves the overall weather resistance of the material. The compatibility between high-molecular-weight brominated epoxy resin and the ABS matrix is poor. Direct addition of it to ABS will cause a significant decrease in the toughness of the material. Based on this, the inventors of this application found that by simultaneously using ABS resin, SAN resin, and CPE resin in the ABS material, the three resins act together within a specific content range to improve the above-mentioned problem of decreased toughness without reducing the weather resistance of the material. Through a large number of experiments, the inventors of this application found that the number-average molecular weight of high-molecular-weight brominated epoxy resin has a great influence on the weather resistance of the finally prepared ABS material. Selecting high-molecular-weight brominated epoxy resin within the above-mentioned number-average molecular weight range has higher photothermal stability and can greatly improve the weather resistance of the material. The test method for the number-average molecular weight of the high-molecular-weight brominated epoxy resin of the present invention is the end-group analysis method.

[0007] As a preferred embodiment of the weather-resistant flame-retardant ABS material of the present invention, the high-molecular-weight brominated epoxy resin is EP-type brominated epoxy resin. Brominated epoxy resin can be divided into EP type and EC type according to different end groups. The inventors of this application found that using EP-type brominated epoxy resin to prepare ABS material can significantly improve the weather resistance of the ABS material compared with EC-type brominated epoxy resin.

[0008] As a preferred embodiment of the weather-resistant flame-retardant ABS material of the present invention, the ABS resin is synthesized by the bulk method. The weight percentage of butadiene in the ABS resin is 20-25%. ABS resin is generally produced by two different manufacturing processes: bulk continuous polymerization and batch emulsion method. The industry usually refers to them as emulsion ABS (eABS) and bulk method ABS (mABS). The ABS resin prepared by the emulsion method contains more residual monomers and small molecules, while the residual monomers and small molecules in the ABS resin prepared by the bulk method are less. The weather resistance of the ABS material prepared using the ABS resin prepared by the bulk method is better.

[0009] As a preferred embodiment of the weather-resistant flame-retardant ABS material of the present invention, the compatibilizer is maleic anhydride grafted ABS. The grafting rate of the maleic anhydride grafted ABS is 0.8-1.3%. The inventors of the present application have found through research that maleic anhydride grafted ABS has both a weakly polar ABS part and a strongly polar maleic anhydride part, so it can improve the compatibility between ABS and high molecular brominated epoxy, and further enhance the toughness of the material.

[0010] As a preferred embodiment of the weather-resistant flame-retardant ABS material of the present invention, the antimony-based flame retardant includes at least one of antimony trioxide and antimony pentoxide.

[0011] As a preferred embodiment of the weather-resistant flame-retardant ABS material of the present invention, the mass ratio of the bromine-based flame retardant to the antimony-based flame retardant is 4-6:1.

[0012] As a preferred embodiment of the weather-resistant flame-retardant ABS material of the present invention, the weather-resistant flame-retardant ABS material further includes the following components in parts by weight: 0.5-1 part of a light stabilizer, 0.3-1 part of an antioxidant, and 0.5-1 part of a lubricant.

[0013] As a preferred embodiment of the weather-resistant flame-retardant ABS material of the present invention, it includes at least one of (a)-(b):

[0014] (a) The antioxidant is a hindered phenol antioxidant or a phosphite antioxidant;

[0015] (b) The lubricant is at least one of a silicone lubricant, an amide lubricant, and an ester lubricant;

[0016] (c) The light stabilizer is a benzotriazole light stabilizer or a hindered amine light stabilizer.

[0017] The present invention also provides a preparation method of the weather-resistant flame-retardant ABS material, including the following steps:

[0018] Weigh each component in the weather-resistant flame-retardant ABS material in proportion and mix them evenly to obtain a premixed material;

[0019] Process the premixed material obtained in step (1) through mixing and extrusion to obtain the weather-resistant flame-retardant ABS material.

[0020] The present invention also provides the application of the weather-resistant flame-retardant ABS material in the preparation of bathroom wares, household appliances, and automotive products.

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention provides a weather-resistant flame-retardant ABS material, its preparation method and application. By simultaneously using ABS resin, SAN resin and CPE resin in the ABS material, the three resins act together within a specific content range to improve the problem of decreased toughness of the flame-retardant ABS material, and at the same time, the weather resistance of the material will not be reduced; adding a high-molecular brominated epoxy resin to the ABS material, which is compounded with an antimony-based flame retardant to enable the ABS material to achieve a flame-retardant function. At the same time, the high-molecular brominated epoxy resin has higher photothermal stability compared with traditional brominated flame retardants (bromotriazine, tetrabromobisphenol A and low-molecular brominated epoxy), and is not easily migrated and precipitated to the surface of the material, which greatly improves the overall weather resistance of the material. Detailed Embodiments

[0022] To better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0023] The raw materials used in the embodiments and comparative examples of the present invention are described as follows, but are not limited to these materials:

[0024] ABS Resin 1: ABS 8391, bulk ABS, the weight of butadiene is 20%, Shanghai Gaoqiao Petrochemical Co., Ltd.;

[0025] ABS Resin 2: ABS 8434, bulk ABS, the weight of butadiene is 25%, Shanghai Gaoqiao Petrochemical Co., Ltd.;

[0026] ABS Resin 3: ABS 0215H, emulsion ABS, the weight of butadiene is 23%, Jilin Petrochemical Branch of PetroChina;

[0027] SAN Resin: SAN NF2200 AK, Formosa Chemicals & Fibre Corporation, Taiwan Province, China;

[0028] CPE Resin: CPE-132C, Keli Chemical Co., Ltd.;

[0029] High-Molecular Brominated Epoxy 1: F-2016, number-average molecular weight is 1600, EP-type brominated epoxy, Dead Sea Bromine Company, Israel;

[0030] High-Molecular Brominated Epoxy 2: F-2100L, number-average molecular weight is 10000, EP-type brominated epoxy, Dead Sea Bromine Company, Israel;

[0031] High-Molecular Brominated Epoxy 3: F-2100, number-average molecular weight is 20000, EP-type brominated epoxy, Dead Sea Bromine Company, Israel;

[0032] High molecular weight brominated epoxy 4: F-2100H, number average molecular weight of 25,000, EP type brominated epoxy, Dead Sea Bromine Company, Israel;

[0033] High molecular weight brominated epoxy 5: F-2400E, number average molecular weight of 32,000, EP type brominated epoxy, Dead Sea Bromine Company, Israel;

[0034] Brominated polycarbonate: FG-8500, Teijin Limited, Japan;

[0035] High molecular weight brominated epoxy: F-3100, number average molecular weight of 15,000, EC type brominated epoxy, Dead Sea Bromine Company, Israel;

[0036] Antimony-based flame retardant: antimony trioxide, commercially available;

[0037] Maleic anhydride grafted ABS: KT-2, grafting rate of 1.1%, Shenyang Ketong Plastic Technology Co., Ltd.;

[0038] Styrene-maleic anhydride copolymer: SMA-700, Shanghai Huawei New Electronic Materials Co., Ltd.;

[0039] MBS type compatibilizer: M-521, Kaneka Corporation, Japan;

[0040] Light stabilizer: TINUVIN 770DF, low molecular weight hindered amine light stabilizer, commercially purchased, the same substance in each example and comparative example;

[0041] Antioxidant: phosphite antioxidant tris(2,4-di-tert-butylphenyl) phosphite, commercially purchased, the same substance in each example and comparative example;

[0042] Lubricant: zinc stearate, commercially purchased, the same substance in each example and comparative example.

[0043] Examples 1 to 15, Comparative Examples 1 to 16

[0044] The composition components of the weather-resistant flame-retardant ABS materials of Examples 1 to 15 and Comparative Examples 1 to 16 of the present invention are shown in Tables 1 and 2.

[0045] Table 1 Components of the weather-resistant flame-retardant ABS materials of Examples 1 to 15 (parts by weight)

[0046]

[0047] Table 2 Components of the weather-resistant flame-retardant ABS materials of Comparative Examples 1 to 16 (parts by weight)

[0048]

[0049]

[0050] The preparation methods of the weather-resistant flame-retardant ABS materials of Examples 1 to 15 and Comparative Examples 1 to 16 of the present invention include the following steps:

[0051] (1) Weigh each raw material component and add it to a high-speed mixer to mix evenly to obtain a premix;

[0052] (2) Feed the prepared premix into an extruder for mixing, extrusion, and post-processing to obtain the product.

[0053] The weather-resistant flame-retardant ABS materials of Examples 1 to 15 and Comparative Examples 1 to 16 were made into sample specimens, and their relevant properties were tested. The specific performance detection methods are as follows:

[0054] (1) Flame retardancy test standard: The test standard refers to "Test for Flammability of Plastics Used in Equipment and Appliance Parts UL 94-2018", and the thickness of the specimen is 2.0 mm;

[0055] (2) Izod notched impact strength: The test standard refers to "Determination of Izod Impact Strength of Plastics ISO 180-2000", and the notch type is Type A notch;

[0056] (3) Flexural modulus: The test standard refers to "Determination of Flexural Properties of Plastics ISO 178-2010";

[0057] (4) Weather resistance test: The test standard refers to "ISO 4892-2:2013 Cycle1, B1, 4, B4 (Plastics, Outdoor)", and the test is carried out for 168 h.

[0058] The test results are shown in Table 3.

[0059] Table 3 Performance test results of the weather-resistant flame-retardant ABS materials of the examples and comparative examples

[0060]

[0061]

[0062] As can be seen from Table 3, by comparing Example 2 and 12 with Comparative Example 1, it can be known that using the bulk method to prepare ABS resin can improve the weather resistance of ABS materials; by comparing Example 2 with Comparative Example 4, it can be known that the high molecular weight brominated epoxy resin can improve the weather resistance of ABS materials compared with the traditional brominated flame retardant; by comparing Example 2 with Comparative Example 5, it can be known that when using EP type brominated epoxy resin to prepare ABS materials, compared with EC type brominated epoxy resin, it can significantly improve the weather resistance of ABS materials; by comparing Example 2, 13 to 14 with Comparative Examples 2 and 3, it can be known that adding high molecular weight brominated epoxy resin with a number average molecular weight of 10,000 to 25,000, the impact strength of the prepared ABS material is 18 kJ / m 2Above, the flexural modulus is above 2000 MPa, the color difference is less than 1, and the flame retardancy reaches the V-0 level, greatly improving the weather resistance of the material. It can be seen from the comparison between Example 2 and Comparative Examples 15 and 16 that in the ABS material of the present invention, ABS resin, SAN resin and CPE resin are used simultaneously, and the three resins act together within a specific content range to improve the problem of the decrease in toughness of the flame-retardant ABS material, and at the same time will not reduce the weather resistance of the material.

[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A weather-resistant and flame-retardant ABS material, characterized in that, it comprises the following components in parts by weight: 34 - 42 parts of ABS resin, 15 - 25 parts of SAN resin, 15 - 25 parts of CPE resin, 2 - 4 parts of compatibilizer, 12 - 18 parts of brominated flame retardant, and 3 - 5 parts of antimony-based flame retardant; the ABS resin is synthesized by bulk polymerization method; the brominated flame retardant is EP type high molecular weight brominated epoxy resin; the number average molecular weight of the high molecular weight brominated epoxy resin is 10,000 - 25,000; the compatibilizer is maleic anhydride grafted ABS.

2. The weather-resistant and flame-retardant ABS material according to claim 1, characterized in that, the antimony-based flame retardant comprises at least one of antimony trioxide and antimony pentoxide.

3. The weather-resistant and flame-retardant ABS material according to claim 1, characterized in that, the mass ratio of the brominated flame retardant to the antimony-based flame retardant is 4 - 6:

1.

4. The weather-resistant and flame-retardant ABS material according to claim 1, characterized in that, the weather-resistant and flame-retardant ABS material further comprises the following components in parts by weight: 0.5 - 1 part of light stabilizer, 0.3 - 1 part of antioxidant, and 0.5 - 1 part of lubricant.

5. The weather-resistant and flame-retardant ABS material according to claim 4, characterized in that, it comprises at least one of (a) - (b): (a) the antioxidant is a hindered phenol antioxidant or a phosphite antioxidant; (b) the lubricant is at least one of silicone lubricants, amide lubricants, and ester lubricants; (c) the light stabilizer is a benzotriazole light stabilizer or a hindered amine light stabilizer.

6. The preparation method of the weather-resistant and flame-retardant ABS material according to any one of claims 1 - 5, characterized in that, it comprises the following steps: (1) Weigh each component in the weather-resistant and flame-retardant ABS material according to the proportion and mix them evenly to obtain a premixed material; (2) Process the premixed material obtained in step (1) through mixing and extrusion to obtain the weather-resistant and flame-retardant ABS material.

7. The application of the weather-resistant and flame-retardant ABS material according to any one of claims 1 - 5 in the preparation of bathroom, household appliance, and automotive products.

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