Abs composite material and preparation method and application thereof

Abstract

The application discloses an ABS composite material and a preparation method and application thereof, and relates to the technical field of high polymer materials. The ABS composite material is prepared from the following components in parts by weight: 60-90 parts of styrene-butadiene-acrylonitrile copolymer, 15-35 parts of PETG resin, 3-10 parts of polybutene resin, and 0.5-2 parts of an additive. The styrene-butadiene-acrylonitrile copolymer, the PETG resin and the polybutene resin are selected as raw material components, and the ABS composite material prepared from the components is resistant to cold and solvent corrosion cracking.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to an ABS composite material, its preparation method, and its application. Background Technology

[0002] Styrene-butadiene-acrylonitrile copolymer (ABS) is a compound with a balanced rigidity and toughness, polymerized from three monomers. As an engineering plastic, it is widely used in many industries such as toys, home appliances, electronics, and transportation due to its balanced rigidity and toughness, excellent processing performance, and good cost performance. However, as a commonly used amorphous plastic, ABS has poor resistance to solvent corrosion. To improve this situation, existing technologies use the addition of crystalline components to improve its chemical resistance. However, since crystalline plastics have poor compatibility with amorphous ABS, specific compatibilizers need to be added. Even so, the system is more prone to phase separation at low temperatures, resulting in generally poor low-temperature mechanical properties.

[0003] PETG is a transparent, amorphous copolyester, officially named polyethylene terephthalate-1,4-cyclohexanediethanol ester. It is produced by the transesterification polymerization of three monomers: terephthalic acid (PTA), ethylene glycol (EG), and 1,4-cyclohexanediethanol (CHDM). This material possesses high transparency, ease of printing, high gloss, chemical resistance, and good weather resistance, making it suitable for molding products with various complex structures. Patent CN105504658B discloses a technical solution using polyimide and fluororubber to improve the solvent resistance of ABS. However, both polyimide and fluororubber are highly polar materials with high glass transition temperatures; adding them to ABS leads to a deterioration in the material's low-temperature performance, particularly a significant impact on low-temperature toughness.

[0004] Therefore, in some fields that require materials to operate in low-temperature environments and have high requirements for solvent resistance, such as the home appliance, packaging, toy, and furniture industries, there is an urgent need for a composition that is both cold-resistant and resistant to solvent erosion and cracking, as well as its preparation method. Summary of the Invention

[0005] Based on this, the purpose of the present invention is to overcome the shortcomings of the prior art and provide a cold-resistant and solvent-resistant ABS composite material, its preparation method and application.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: an ABS composite material comprising the following components in parts by weight: 60-90 parts of styrene-butadiene-acrylonitrile copolymer, 15-35 parts of PETG resin, 3-10 parts of polybutene resin, and 0.5-2 parts of additives.

[0007] Preferably, the ABS composite material comprises the following components in parts by weight: 70-80 parts of styrene-butadiene-acrylonitrile copolymer, 20-30 parts of PETG resin, 4-6 parts of polybutene resin, and 0.5-2 parts of additives.

[0008] This invention uses styrene-butadiene-acrylonitrile copolymer, PETG resin, and polybutene resin as raw material components. PETG resin and ABS generally have poor compatibility; during co-extrusion, PETG migrates to the system surface, resisting solvent erosion. The addition of polybutene resin serves two purposes: firstly, as a low-temperature toughening agent, it effectively toughens ABS while simultaneously controlling the dispersed phase size distribution of PETG within the ABS matrix, achieving synergistic toughening with PETG; secondly, polybutene resin exhibits good dispersibility in the PETG system, further enhancing the solvent resistance of the composition.

[0009] Optionally, the styrene-butadiene-acrylonitrile copolymer is in the range of 60 parts, 61 parts, 65 parts, 68 parts, 70 parts, 80 parts, and 90 parts by weight, or any two of these values; the PETG resin is in the range of 15 parts, 18 parts, 20 parts, 25 parts, 28 parts, 30 parts, 32 parts, and 35 parts by weight, or any two of these values; the polybutene resin is in the range of 3 parts, 5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, and 10 parts by weight, or any two of these values; and the additive is in the range of 0.5 parts, 1 part, 1.5 parts, 1.8 parts, and 2 parts by weight, or any two of these values.

[0010] Preferably, the styrene-butadiene-acrylonitrile copolymer accounts for no less than 60% of the total weight of the ABS composite material.

[0011] Preferably, the PETG resin content is 13-31% by weight, based on the total weight of the ABS composite material.

[0012] Preferably, the polybutene resin has a weight percentage of 2.5-10% based on the total weight of the ABS composite material.

[0013] Preferably, the weight percentage of butadiene in the styrene-butadiene-acrylonitrile copolymer is 15-30%. More preferably, the weight percentage of butadiene in the styrene-butadiene-acrylonitrile copolymer is 20-25%. The weight percentage of butadiene in the styrene-butadiene-acrylonitrile copolymer of the present invention can be determined by nuclear magnetic resonance (NMR) method, and for details, please refer to the Chinese literature "NMR Study of ABS Resin and Influence of Monomer Content on Macroscopic Properties".

[0014] Preferably, the melt flow rate of the PETG resin at 220°C and 10 kg, according to ISO 1133-1:2022, is 10-40 g / 10 min. More preferably, the melt flow rate of the PETG resin at 220°C and 10 kg, according to ISO 1133-1:2022, is 20-35 g / 10 min.

[0015] Preferably, the weight percentage of 1,4-cyclohexanediethanol in the PETG resin is 10%-30%; the weight percentage of 1,4-cyclohexanediethanol in the PETG resin can be determined by infrared absorption spectroscopy (IR) coupled with nuclear magnetic resonance (NMR), specifically referring to Chinese patent CN104569022B (an analytical method for the content of 1,4-cyclohexanediethanol units on a copolyester molecular chain).

[0016] Preferably, the melt flow rate of the polybutene resin according to ISO 1133-1:2022 at 190°C and 2.16 kg is 1-200 g / 10 min. More preferably, the melt flow rate of the polybutene resin according to ISO 1133-1:2022 at 190°C and 2.16 kg is 3-50 g / 10 min.

[0017] Optionally, the weight percentage of butadiene in the styrene-butadiene-acrylonitrile copolymer is one or any two of the following values: 15%, 18%, 20%, 23%, 25%, 28%, and 30%.

[0018] Optionally, the PETG resin, according to ISO 1133-1:2022, at 220°C and 10 kg, has a melt mass flow rate of 10 g / 10 min, 15 g / 10 min, 20 g / 10 min, 25 g / 10 min, 30 g / 10 min, 35 g / 10 min, 40 g / 10 min, or any two of these values.

[0019] Optionally, the weight percentage of 1,4-cyclohexanediethanol in the PETG resin is one or any two of the following: 10%, 15%, 20%, 25%, and 30%.

[0020] Optionally, the polybutene resin, according to ISO 1133-1:2022, has a melt mass flow rate at 190°C and 2.16 kg in the range of one or any two of the following: 1 g / 10 min, 20 g / 10 min, 50 g / 10 min, 100 g / 10 min, 120 g / 10 min, 150 g / 10 min, 180 g / 10 min, and 200 g / 10 min.

[0021] Optionally, the polybutene resin may be a homopolymer or a copolymer.

[0022] Preferably, the additives include at least one of antioxidants and lubricants.

[0023] Preferably, the antioxidant is at least one of hindered phenolic antioxidants, hindered amine antioxidants, divalent sulfur antioxidants, and phosphite antioxidants. Specifically, the antioxidant includes, but is not limited to, at least one of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine (antioxidant 1098), tris[2,4-di-tert-butylphenyl]phosphite (antioxidant 168), and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010).

[0024] Preferably, the lubricant includes at least one of amide lubricants, stearate lubricants, ester lubricants, and silicone lubricants; such as amide lubricants including erucamide.

[0025] Furthermore, the present invention provides a method for preparing the ABS composite material, comprising the following steps: mixing all components, followed by melt extrusion granulation to obtain the ABS composite material.

[0026] Preferably, the mixing speed is 1000-1500 rpm, and the mixing time is 5-10 min;

[0027] Preferably, the temperature of the melt extrusion granulation does not exceed 220°C, and the rotation speed of the melt extrusion granulation is 100-450 rpm.

[0028] Preferably, the temperature of the melt extrusion granulation is 160-200℃.

[0029] Furthermore, the present invention provides applications of the aforementioned ABS composite material in the fields of household appliances, packaging, toys, and furniture.

[0030] The invention provides a component molded from the aforementioned ABS composite material; the molding method includes, but is not limited to, injection molding, blow molding, vacuum forming, and extrusion; specifically, the component includes components in the fields of household appliances, packaging, toys, and furniture, the household appliance field including drawers, partitions, door seals of refrigerator refrigerators / freezers, freezer liners and shelves, etc.; the packaging field including rigid packaging boxes for frozen meat and seafood, etc.; the toy field including shells for ice and snow themed toys, handles for children's tableware toys, etc.

[0031] Compared to existing technologies, the beneficial effects of this invention are as follows: This invention selects styrene-butadiene-acrylonitrile copolymer, PETG resin, and polybutene resin as raw material components. PETG resin and ABS generally have low compatibility; when they are co-extruded, PETG migrates to the surface of the system, resisting the erosion of the material by solvents. The addition of polybutene resin serves two purposes: firstly, as a low-temperature toughening agent, polybutene resin can effectively toughen ABS while simultaneously controlling the dispersed phase size distribution of PETG in the ABS matrix, achieving synergistic toughening with PETG; secondly, polybutene resin exhibits good dispersibility in the PETG system, synergistically improving the solvent resistance of the composition. Detailed Implementation

[0032] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments. The purpose is to provide a detailed understanding of the invention, not to limit it. All other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention. Unless otherwise specified, the experimental reagents and instruments designed in the embodiments and comparative examples of this invention are commonly used reagents and instruments, all of which are commercially available. Unless otherwise specified, the experimental methods used in the embodiments and comparative examples are conventional methods; and unless otherwise specified, the raw materials used in parallel experiments are from the same batch.

[0033] The raw materials of this invention will now be further described, but are not limited to the following raw materials:

[0034] Table 1

[0035]

[0036] Examples and Comparative Examples

[0037] The present invention provides an ABS composite material in embodiments and comparative examples. The components and weight parts of the ABS composite material are shown in Tables 2-3. The preparation method of the ABS composite material includes the following steps:

[0038] Materials were weighed according to the designed formula and proportions, and then mixed in a mixer at 1000 rpm for 5 minutes. The mixture was then removed and fed into the feed hopper of a twin-screw extruder. The mixture was melt-extruded and granulated to obtain the ABS composite material. The parameters of the twin-screw extruder were as follows: screw temperatures from the feed port to the die head were 200℃, 200℃, 200℃, 210℃, 210℃, 210℃, 210℃, 210℃, 220℃, and 220℃, respectively; the screw speed was 300 rpm.

[0039] Performance testing

[0040] The ABS composite materials prepared in the examples and comparative examples were dried in a forced-air oven at 80°C for 4 hours, and then injection molded into standard specimens using a plastic injection molding machine at injection temperatures of 180°C, 200°C, 200°C, 200°C, and 200°C. The injection-molded specimens were then placed at 50% relative humidity and 23°C for 24 hours before the following performance tests were conducted.

[0041] (1) Low temperature cantilever beam notched impact strength: According to ISO 180-2019 method, a 4 mm thick specimen was kept at -30℃ for 24 hours and then the cantilever beam notched impact (notch type A) was tested.

[0042] (2) Solvent corrosion resistance test: According to ISO 22088-3-2006, the standard tensile specimen was loaded onto a fixture with a strain of 1.5%, coated with glacial acetic acid, and the surface cracking of the tensile specimen was observed. The time required for cracks to appear on the surface of the specimen was recorded.

[0043] The test results are shown in Table 2-3.

[0044] Table 2

[0045]

[0046] Table 3

[0047]

[0048] As shown in the table above, the ABS composite material prepared in this embodiment of the invention has a notched impact strength of >15 KJ / m at -30°C when tested with a cantilever beam. 2 It does not crack after being coated with glacial acetic acid for more than 50 hours, and has excellent cold resistance and solvent erosion cracking resistance.

[0049] As can be seen from the comparison of Examples 1-4, the weight percentage of butadiene in the ABS affects the cold resistance and solvent erosion cracking resistance. If the weight percentage of butadiene is too high, the dispersion performance of the system is poor. If the weight percentage of butadiene is too low, the cantilever beam notched impact test at -30°C is poor. When the weight percentage of butadiene in the ABS is 20-28%, the cold resistance and solvent erosion cracking resistance are better.

[0050] As can be seen from the comparison of Examples 1 and Examples 5-7, the melt flow rate of the PETG resin affects its resistance to cold and solvent erosion cracking. When the melt flow rate of the PETG resin is 20-35 g / 10 min, its resistance to cold and solvent erosion cracking is better.

[0051] As can be seen from the comparison of Example 1 and Comparative Examples 1-2, when polybutene resin is replaced by POE and LLDPE, the dispersion effect of POE and LLDPE in the system is poor, and the prepared ABS composite material has poor cold resistance and solvent erosion cracking resistance, which cannot meet the requirements. As can be seen from the comparison of Example 1 and Examples 8-10, when the polybutene resin is dispersed at a melt flow rate of 3-50 g / 10 min at 190℃ and 2.16 kg according to ISO1133-1:2022, the dispersion effect is better, and the cold resistance and solvent erosion cracking resistance are better.

[0052] Comparing Examples 1, 11-13, and Comparative Examples 3-5, it is evident that the weight percentages of the components affect the cold resistance and solvent erosion cracking resistance of the prepared ABS composite material. When the required amounts of 70-80 parts styrene-butadiene-acrylonitrile copolymer, 20-30 parts PETG resin, 4-6 parts polybutene resin, and 0.5-2 parts additives are present, the cold resistance and solvent erosion cracking resistance are superior. In Comparative Example 3, the excess polybutene resin resulted in poor compatibility with ABS. In Comparative Example 4, the excess PETG resin and insufficient polybutene resin led to poor cold resistance and solvent erosion cracking resistance, failing to meet the requirements. Comparative Example 5, lacking polybutene resin, also exhibited poor cold resistance and solvent erosion cracking resistance.

[0053] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention 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 includes the following components in parts by weight: 60-90 parts of styrene-butadiene-acrylonitrile copolymer, 15-35 parts of PETG resin, 3-10 parts of polybutene resin, and 0.5-2 parts of additives; The butadiene content in the styrene-butadiene-acrylonitrile copolymer is 15-30% by weight; The PETG resin, according to ISO 1133-1:2022, has a melt mass flow rate of 10-40 g / 10 min at 220°C and 10 kg. The polybutene resin, according to ISO 1133-1:2022, has a melt flow rate of 1-200 g / 10 min at 190°C and 2.16 kg.

2. The ABS composite material as described in claim 1, characterized in that, It includes the following components in parts by weight: 70-80 parts of styrene-butadiene-acrylonitrile copolymer, 20-30 parts of PETG resin, 4-6 parts of polybutene resin, and 0.5-2 parts of additives.

3. The ABS composite material as described in claim 1, characterized in that, The additives include at least one of antioxidants and lubricants.

4. A method for preparing the ABS composite material according to any one of claims 1-3, characterized in that, Includes the following steps: All components are mixed and then melt-extruded and granulated to obtain the ABS composite material.

5. The method for preparing ABS composite material as described in claim 4, characterized in that, Includes at least one of the following (1)-(2): (1) The mixing speed is 1000-1500 rpm, and the mixing time is 5-10 min; (2) The temperature of the melt extrusion granulation does not exceed 210°C, and the rotation speed of the melt extrusion granulation is 100-450 rpm.

6. The application of the ABS composite material as described in any one of claims 1-3 in the fields of household appliances, packaging, toys, and furniture.

7. An article formed from an ABS composite material comprising any one of claims 1-3.

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