ABS composite material as well as preparation method and application thereof

Abstract

The invention discloses an ABS (Acrylonitrile Butadiene Styrene) composite material as well as a preparation method and application thereof, and relates to the technical field of modified ABS composite materials. The invention provides an ABS (Acrylonitrile Butadiene Styrene) composite material. The ABS composite material comprises the following components in parts by weight: 50-80 parts of ABS resin, 5-20 parts of a heat-resistant agent, 3-10 parts of a titanium dioxide coloring agent, 0.5-4 parts of ionic liquid and 0.1-1.5 parts of an antioxidant, the ionic liquid is composed of positive ions and negative ions, the positive ions comprise at least one of 1-methylpyridinium ions, 1-butylpyridinium ions, 1-butyl-4-methylpyridinium ions, 1-allyl-1-methylpyrrolidinium ions and 1-butyl-1-methylpyrrolidinium ions, and the negative ions comprise at least one of 1-methylpyridinium ions, 1-butylpyridinium ions, 1-butyl-4-methylpyridinium ions, 1-allyl-1-methylpyrrolidinium ions and 1-butyl-1-methylpyrrolidinium ions. The anions comprise at least one of chloride ions, bromide ions, iodide ions and bis (trifluoromethylsulfonyl) imine ions. Through the special compounding effect of all the components, the weather-resistant ABS composite material with high flowability is prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of modified ABS composite materials, and in particular to an ABS composite material, a preparation method thereof and an application thereof. Background Art

[0002] Acrylonitrile-butadiene-styrene copolymer (referred to as ABS) is the fifth largest general-purpose plastic in the world and is also one of the most widely used rubber toughened plastics. It is a high-demand and fast-developing polymer material between engineering plastics and general-purpose plastics. ABS resin combines the rigidity, heat resistance and chemical resistance of acrylonitrile, the toughness of butadiene and the gloss and processability of styrene, and is widely used in electronics, electrical appliances, automobiles, textile equipment, construction and daily necessities. Although ABS resin has excellent comprehensive properties, there are still problems of insufficient weather resistance in some application fields, so it is necessary to improve the weather resistance of ABS resin to meet the development needs of domestic industries such as automobiles, household appliances and office machinery. However, due to the easy oxidation and fracture of polybutadiene in the structure of ABS resin itself, it is prone to aging and degradation under wind, sun or high-temperature storage, resulting in color change and decline in mechanical properties.

[0003] With the development of electronic products, people's requirements for plastic parts are getting higher and higher. For example, the requirements for the color of automotive interior door panels and household appliance shells are not only high, but also the environmental resistance requirements are getting higher and higher. Therefore, the fluidity and weather resistance of the materials suitable for the above parts are very crucial. CN115505235A discloses a high-flow, high-impact, weather-resistant ABS resin material and a preparation method thereof, which are composed of the following components in parts by weight: 70-80 parts of ABS resin, 10-30 parts of weather resistance enhancer, 1-5 parts of antioxidant, and 1-5 parts of lubricant; the weather resistance enhancer is at least one or a mixture of two of AES resin, ultraviolet light absorber and light shielding agent. This method improves the weather resistance of the material to a certain extent, but AES resin causes a decrease in fluidity and a higher cost. CN104212118A discloses a heat-resistant and weather-resistant ABS resin alloy and a preparation method thereof, in which 10-20 parts of PC resin and 11-14 parts of ABS grafted maleic anhydride are added to improve the heat resistance of the material, and 1-2 parts of 2-(2'-hydroxy-3',5'-di-tert-phenyl)-5-chlorobenzotriazole and 0.8-1.2 parts of glyceryl tristearate are added to meet the weather resistance requirements. This method is simple to prepare, but the improvement in heat resistance and weather resistance is limited and it is difficult to meet the requirements of more application materials.

[0004] Therefore, an ABS composite material with high fluidity and weather resistance has broad application prospects. Summary of the Invention

[0005] Based on this, the object of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide an ABS composite material with high fluidity and weather resistance, as well as its preparation method and application.

[0006] To achieve the above object, the technical solution adopted by the present invention is: an ABS composite material, comprising the following components in parts by weight: 50 - 80 parts of ABS resin, 5 - 20 parts of heat-resistant agent, 3 - 10 parts of titanium dioxide colorant, 0.5 - 4 parts of ionic liquid, 0.1 - 1.5 parts of antioxidant; the ionic liquid is composed of a cation and an anion, the cation includes at least one of 1-methylpyridinium ion, 1-butylpyridinium ion, 1-butyl-4-methylpyridinium ion, 1-allyl-1-methylpyrrolidinium ion, 1-butyl-1-methylpyrrolidinium ion, and the anion includes at least one of chloride ion, bromide ion, iodide ion, bis(trifluoromethanesulfonyl)imide ion; the heat-resistant agent is a styrene copolymer heat-resistant agent.

[0007] Preferably, the weight percentage content of the ABS resin in the ABS composite material is not less than 55%.

[0008] Optionally, the parts by weight of the ABS resin are one of 50 parts, 51 parts, 53 parts, 55 parts, 58 parts, 60 parts, 61 parts, 63 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 80 parts or the range value of any two of them; the parts by weight of the heat-resistant agent are one of 5 parts, 6 parts, 7 parts, 8 parts, 10 parts, 11 parts, 13 parts, 15 parts, 18 parts, 20 parts or the range value of any two of them; the parts by weight of the titanium dioxide colorant are one of 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 10 parts or the range value of any two of them; the parts by weight of the ionic liquid are one of 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or the range value of any two of them; the parts by weight of the antioxidant are one of 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.1 parts, 1.3 parts, 1.5 parts or the range value of any two of them.

[0009] The present invention selects a specific type of ionic liquid for the ABS composite material, which improves the dispersion effect of the heat-resistant agent and the titanium dioxide colorant in the composite material, and further improves the fluidity of the composite material, thereby preparing an ABS material with good fluidity and better weather resistance.

[0010] Preferably, the weight ratio of the heat-resistant agent, the titanium dioxide colorant, and the ionic liquid is heat-resistant agent:titanium dioxide colorant:ionic liquid = (10 - 15):(5 - 6):3.

[0011] During the actual experiment, the inventor found that when the weight ratio of the heat-resistant agent, titanium dioxide colorant, and ionic liquid is within the above specific range, the prepared ABS composite material has better weather resistance and better fluidity.

[0012] Preferably, the ionic liquid includes at least one of 1-butylpyridinium chloride and 1-butyl-4-methylpyridinium bromide.

[0013] Preferably, the heat-resistant agent is at least one of styrene-N-phenylmaleimide-maleic anhydride copolymer, styrene-N-phenylmaleimide copolymer, and α-methylstyrene-acrylonitrile copolymer.

[0014] Preferably, the glass transition temperature of the heat-resistant agent is 180-200 °C, and the test method for the glass transition temperature of the heat-resistant agent is: GB / T 19466.2-2004 Plastics - Differential scanning calorimetry (DSC) - Part 2: Determination of glass transition temperature.

[0015] Preferably, the mass percentage content of TiO2 in the titanium dioxide colorant is ≥92%. The test method for the mass percentage content of TiO2 in the titanium dioxide is the XFR method.

[0016] Optionally, the mass percentage content of TiO2 in the titanium dioxide colorant is one of 92%, 93%, 95%, 96%, 97% or the range value of any two of them.

[0017] Preferably, the melt mass flow rate of the ABS resin is 6-60 g / 10 min at a test temperature of 220 °C and a load of 10 kg according to ISO 1133-2022; the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.

[0018] Preferably, the hindered phenol antioxidants include at least one of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and bis[β-(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)]hydrazine; the phosphite antioxidants include at least one of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite and tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyldiphosphite.

[0019] Optionally, the ABS resin has a melt mass flow rate of 6 g / 10 min, 10 g / 10 min, 15 g / 10 min, 18 g / 10 min, 25 g / 10 min, 30 g / 10 min, 35 g / 10 min, 40 g / 10 min, 43 g / 10 min, 45 g / 10 min, 50 g / 10 min, 55 g / 10 min, 60 g / 10 min or a range value of any two of them according to ISO 1133-2022 under the conditions of a test temperature of 220 °C and a load of 10 kg.

[0020] In addition, the present invention provides a method for preparing the ABS composite material, comprising the following steps: mixing each component evenly, followed by melt extrusion and pelletization to obtain the ABS composite material.

[0021] Preferably, the conditions for melt extrusion are: 180 ± 10 °C, 220 ± 10 °C, 220 ± 10 °C, 220 ± 10 °C, 220 ± 10 °C, 210 ± 10 °C, and the rotation speed is 200 - 300 rpm.

[0022] Furthermore, the present invention provides the application of the ABS composite material in the preparation of automotive interior door panels and outer shells of household appliances.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows: The ABS composite material of the present invention selects a specific type of ionic liquid, which improves the dispersion effect of the heat-resistant agent and the titanium dioxide colorant in the composite material, and further improves the fluidity of the composite material, thereby preparing an ABS material with good fluidity and better weather resistance. Specific Embodiments

[0024] To better illustrate the purpose, technical solution and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. The purpose is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the protection scope of the present invention. The experimental reagents and instruments designed in the embodiments and comparative examples of the present invention are all common ordinary reagents and instruments unless otherwise specified, and can be obtained from commercial channels. In the embodiments and comparative examples, the experimental methods used are all conventional methods unless otherwise specified; and unless otherwise specified, the raw materials used in parallel experiments are from the same batch of raw materials.

[0025] The raw materials used in the examples and comparative examples are described as follows, but are not limited to these materials:

[0026] ABS resin - 1: Melt mass flow rate 7 g / 10 min (220 °C, 10 kg), grade ABS MA201, manufacturer LG Chem;

[0027] ABS Resin - 2: Melt mass flow rate of 22 g / 10 min (at 220 °C, 10 kg), grade GP22, manufacturer Benling Chemical;

[0028] ABS Resin - 3: Melt mass flow rate of 55 g / 10 min (at 220 °C, 10 kg), grade HG - 174, manufacturer LG Chem;

[0029] Heat - resistant agent - 1: Styrene - N - phenylmaleimide copolymer, grade MS - NB, manufacturer Denki Kagaku Kogyo Co., Ltd., glass transition temperature is 196 °C (by DSC method);

[0030] Heat - resistant agent - 2: Styrene - N - phenylmaleimide - maleic anhydride copolymer, grade MS - NI, manufacturer Denki Kagaku Kogyo Co., Ltd., glass transition temperature is 185 °C (by DSC method);

[0031] Heat - resistant agent - 3: Polycarbonate, grade FN 1900, manufacturer Idemitsu Kosan Co., Ltd., glass transition temperature is 149 °C (by DSC method);

[0032] Titanium dioxide colorant - 1: TiO₂ content of 95%, grade KRONOS2225, manufacturer KRONOS;

[0033] Titanium dioxide colorant - 2: TiO₂ content of 92%, grade PC - 3, manufacturer ISK Corporation, Japan;

[0034] Titanium dioxide colorant - 3: TiO₂ content of 97%, grade R - 103, manufacturer Chemours;

[0035] Ionic liquid - 1: Purity of 97%, 1 - butylpyridinium chloride (CAS: 1124 - 64 - 7), purchased from TCI (Tokyo Chemical Industry) Chemical Co., Ltd.; Anion: chloride ion, Cation: 1 - butylpyridinium ion;

[0036] Ionic liquid - 2: Purity of 96%, 1 - butyl - 4 - methylpyridinium bromide (CAS: 65350 - 59 - 6), purchased from TCI Chemical Co., Ltd.; Anion: bromide ion, Cation: 1 - butyl - 4 - methylpyridinium ion;

[0037] Ionic liquid - 3: Purity of 97%, 1 - methylpyridinium bis(trifluoromethanesulfonyl)imide (CAS: 742086 - 10 - 8), purchased from TCI Chemical Co., Ltd.; Anion: bis(trifluoromethanesulfonyl)imide ion, Cation: 1 - methylpyridinium ion;

[0038] Ionic liquid - 4: Purity 97%, 1 - butyl - 1 - methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (CAS: 223437 - 11 - 4), purchased from TCI Chemical Company; Anion: bis(trifluoromethanesulfonyl)imide ion, Cation: 1 - butyl - 1 - methylpyrrolidinium ion;

[0039] Ionic liquid - 5: Purity 96%, tetrabutylphosphonium tetrafluoroborate (CAS: 1813 - 60 - 1), purchased from TCI Chemical Company; Anion: tetrafluoroborate ion, Cation: tetrabutylphosphonium ion;

[0040] Ionic liquid - 6: Purity 97%, trihexyl(tetradecyl)phosphonium dicyanamide (CAS: 701921 - 71 - 3), purchased from TCI Chemical Company; Anion: dicyanamide ion, Cation: trihexyl(tetradecyl)phosphonium ion;

[0041] Ionic liquid - 7: Purity 96%, triethylsulfonium bis(trifluoromethanesulfonyl) - imide (CAS: 321746 - 49 - 0), purchased from TCI Chemical Company; Anion: bis(trifluoromethanesulfonyl) - imide ion, Cation: triethylsulfonium ion;

[0042] The antioxidant is a composite of commercially available hindered phenolic antioxidant 1010 and commercially available phosphite antioxidant PEP - 36 in a mass ratio of 1:5.

[0043] Examples and Comparative Examples

[0044] The composition components of the ABS composites in the examples and comparative examples of the present invention are shown in Table 1 and Table 2. The preparation method of the ABS composites includes the following steps: Mix each component evenly, and obtain the ABS composites through melt extrusion and pelletizing. The conditions for the melt extrusion are: 180 °C, 220 °C, 220 °C, 220 °C, 220 °C, 210 °C, and the rotation speed is 250 rpm.

[0045] Table 1

[0046]

[0047]

[0048] Table 2

[0049]

[0050]

[0051] Performance Testing

[0052] To verify the performance of the ABS composite material of the present invention, the products prepared in each example and comparative example were subjected to the following performance tests. The specific steps are as follows:

[0053] The ABS materials provided in the above examples and comparative examples were respectively dried in an oven at 80 °C for 3 - 4 hours and then injection-molded into color plate specimens (standard size 80 mm * 60 mm * 2.0 mm). The injection temperature was 250 °C. After the injection-molded color plates were placed at 25 °C and 50% relative humidity for 24 hours, other performances were tested.

[0054] The helix length measures the injection molding fluidity: The dried particles mentioned above were molded into a helix product with a thickness of 2.0 mm and a width of 5 mm, and the fluidity was judged according to its flow length. Among them, the injection temperature was 250 °C, the mold temperature was 65 °C, the injection speed was 70 mm / s, and the holding pressure was 50 Mpa for 10 seconds for comparative evaluation.

[0055] Referring to the D47 1431 test method of the automotive OEM Stellantis, it was tested with a xenon arc Fade-Omter CI3000 aging instrument. The injection-molded color plate was fixed in a xenon lamp weather resistance chamber, and the temperature was adjusted to 66 °C, and the irradiance was 420 nm @ 1.4 W / m 2 。

[0056] The color difference was carried out under the D65 light source according to the GB16422.2 - 2014 standard. The light aging effect was evaluated by comparing the b value in the Lab value before and after light irradiation. The light aging time was 300 hours. The smaller the change △b value of the b value after the weather resistance test, the better the weather resistance (light aging) performance of the material.

[0057] The performance test results of the examples and comparative examples are shown in Table 3 respectively.

[0058] Table 3

[0059]

[0060]

[0061] As can be seen from the above table, for the ABS composite material prepared in the examples of the present invention, through the compounding of a specific heat-resistant agent, titanium dioxide colorant, and ionic liquid, the injection molding helix length of the material can reach more than 10 mm, and injection molding can be well completed. The change △b of the b value after the weather resistance test is within 2, indicating good weather resistance.

[0062] From the comparison of Example 1 and Examples 10 - 12, when the weight ratio of the heat-resistant agent, titanium dioxide colorant, and ionic liquid is heat-resistant agent: titanium dioxide colorant: ionic liquid = (10 - 15):(5 - 6):3, the weather resistance is better.

[0063] It can be seen from the comparison between Example 1, Example 4, and Comparative Examples 4-5 that the type of heat-resistant agent affects the change in the b value (Δb value) after the final weather resistance test. When the heat-resistant agent is a styrene copolymer, the weather resistance is good.

[0064] It can be seen from the comparison between Example 1, Examples 7-9, Comparative Examples 1-3, and Comparative Example 7 that the selection of ionic liquid has a great influence on the weather resistance of the ABS composite material. When the ionic liquid includes at least one of 1-butylpyridinium chloride and 1-butyl-4-methylpyridinium bromide, the change in the b value (Δb value) of the ABS composite material after the weather resistance test is smaller, and the weather resistance is better.

[0065] 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. An ABS composite material, characterized in that, It comprises the following components in parts by weight: 50 - 80 parts of ABS resin, 5 - 20 parts of heat-resistant agent, 3 - 10 parts of titanium dioxide colorant, 0.5 - 4 parts of ionic liquid, and 0.1 - 1.5 parts of antioxidant; the ionic liquid is composed of a cation and an anion, the cation includes at least one of 1-methylpyridinium ion, 1-butylpyridinium ion, 1-butyl-4-methylpyridinium ion, 1-allyl-1-methylpyrrolidinium ion, 1-butyl-1-methylpyrrolidinium ion, and the anion includes at least one of chloride ion, bromide ion, iodide ion, bis(trifluoromethanesulfonyl)imide ion; the heat-resistant agent is a styrene copolymer-based heat-resistant agent.

2. The ABS composite material according to claim 1, wherein, The weight ratio of the heat-resistant agent, titanium dioxide colorant, and ionic liquid is heat-resistant agent : titanium dioxide colorant : ionic liquid = (10 - 15) : (5 - 6) :

3.

3. The ABS composite material according to claim 1, characterized in that, The ionic liquid includes at least one of 1-butylpyridinium chloride salt and 1-butyl-4-methylpyridinium bromide salt.

4. The ABS composite material according to claim 1, wherein, The heat-resistant agent is at least one of styrene-N-phenylmaleimide-maleic anhydride copolymer, styrene-N-phenylmaleimide copolymer, and α-methylstyrene-acrylonitrile copolymer.

5. The ABS composite material according to claim 1, wherein The mass percentage content of TiO2 in the titanium dioxide colorant is ≥92%.

6. The ABS composite material according to claim 1, wherein, The ABS resin has a melt mass flow rate of 6 - 60 g / 10 min according to ISO 1133-2022 under the conditions of a test temperature of 220°C and a load of 10 kg; the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.

7. A method for preparing an ABS composite material according to any one of claims 1-6, characterized in that, It includes the following steps: mixing the components evenly, followed by melt extrusion and pelletization to obtain the ABS composite material.

8. Use of the ABS composite material according to any one of claims 1 - 6 in the preparation of automotive interior door panels and outer shells of household appliances.

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