An abs alloy composition, its preparation method and use

Abstract

The application discloses an ABS alloy and a preparation method and application thereof, and belongs to the technical field of high polymer materials. The product is prepared by compounding two kinds of SAN resins into a styrene-acrylonitrile-butadiene copolymer as a base component, and introducing polybutylene terephthalate as a dispersion component. The product has high toughness and rigidity effects, and simultaneously has high-temperature rigidity retention rate and low-temperature toughness high retention rate, and is suitable for preparation of various protective devices.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to an ABS alloy composition, its preparation method, and its application. Background Technology

[0002] ABS resin (styrene-acrylonitrile-butadiene resin) alloys are widely used in various fields due to their ease of processing, good mechanical properties, and high chemical stability. However, when applied to the manufacture of protective equipment such as helmets and bags, the impact resistance of these products often fails to meet the evolving technical requirements, especially in sub-zero environments (e.g., at temperatures as low as -30°C), where the toughness drops significantly, and the protective capability falls short. Furthermore, in addition to low-temperature impact resistance, these products also require high rigidity levels at high temperatures to ensure normal use in environments with higher temperatures (e.g., at temperatures as high as 70°C). However, existing products often fail to achieve both of these objectives simultaneously. Summary of the Invention

[0003] Based on the deficiencies of existing technologies, the present invention aims to provide an ABS alloy composition. This product uses a styrene-acrylonitrile-butadiene copolymer of two SAN resins as the matrix component, and introduces polybutylene terephthalate as the dispersing component. This not only enables the product to have high toughness and rigidity, but also has high high-temperature rigidity retention and low-temperature toughness retention, making it suitable for the manufacture of various protective equipment.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows: An ABS alloy composition comprising the following components in parts by weight: SAN resin (acrylonitrile-styrene resin) 40-60 parts, styrene-acrylonitrile-butadiene copolymer 20-30 parts, PBT resin (polybutylene terephthalate) 15-35 parts; The acrylonitrile content of the SAN resin is 20-25% by mass. The SAN resin includes SAN resin 1 and SAN resin 2, wherein the weight-average molecular weight of SAN resin 1 is 100,000 to 120,000, and the weight-average molecular weight of SAN resin 2 is 400,000 to 500,000.

[0005] To simultaneously improve the product's high-temperature rigidity and low-temperature toughness during use, while meeting the high requirements for protective equipment, the ABS alloy resin system combines two SAN resins with specific molecular weights. The acrylonitrile content of the SAN resin is specifically controlled. On one hand, the long molecular chains in the high-molecular-weight SAN resin achieve higher interchain entanglement, enhancing the overall resin's resistance to deformation. On the other hand, the short molecular chains in the low-molecular-weight SAN resin provide ample displacement space (e.g., chain slip space) during entanglement with the long molecular chains and rubber, ensuring the product's resistance to external impact even under conditions of limited molecular chain slippage at low temperatures. Upon impact, the SAN resin absorbs impact force effectively through displacement and entanglement between molecular chains, suppressing the formation and propagation of microcracks in the product. Combined with the rubber phase, this imparts excellent impact resistance and high low-temperature toughness. Simultaneously, the low molecular weight SAN resin molecular chains can increase the range of entanglement between long molecular chains, preventing rigidity weakening due to excessive entanglement. This ensures that the product maintains a high level of rigidity even under high-temperature environments with high molecular creep. At high temperatures, molecular chain entanglement effectively suppresses creep, increasing the product's upper limit of applicable temperature. On the other hand, due to the differences in the length and entanglement of the two SAN resin molecular chains, to ensure compatibility between the two resins and the SAN resin... The bonding strength between the resin and rubber phases requires maintaining a certain level of acrylonitrile content in the matrix SAN resin. If the content is too low, the bonding strength between the multiphase SAN resin and the rubber phase is low, making the product prone to excessive molecular chain movement and creep at high temperatures, resulting in low strength and unsuitability for use at extreme temperatures (e.g., 70°C). Conversely, if the content is too high, the dispersion between the multiphase SAN resins and between the SAN resin and rubber phases deteriorates, ultimately leading to a decrease in product rigidity and toughness. Furthermore, the design of the multiphase SAN resin allows for better dispersion of internal stress and more displacement space at low temperatures, which is more conducive to maintaining toughness and making it suitable for various applications. The lower limit of low temperature is even lower, but because the product contains a rubber phase, this component is more difficult to disperse than the continuous phase. If it forms agglomerates, it will form concentrated internal stress centers, which will induce microcracks or even brittle fracture in the matrix after being subjected to stress at low temperature. It will also cause a decrease in stiffness at high temperature. Therefore, in the product of the technical solution of this invention, PBT resin is further introduced as a dispersant. This component has high compatibility with both the rubber phase and the continuous phase. Therefore, it can help the rubber phase improve its dispersibility, ensure that the product still has a high toughness level at low temperature, and can also improve the interfacial bonding strength between the continuous phase and the rubber phase to a certain extent, further optimizing the high temperature rigidity and low temperature toughness of the product.

[0006] In some embodiments, the SAN resin is in the range of 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, or any two of the following: the styrene-acrylonitrile-butadiene copolymer is in the range of 20 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, or any two of the following: the PBT resin is in the range of 15 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, or any two of the following:

[0007] More preferably, the ABS alloy composition comprises the following components in parts by weight: 45-50 parts of SAN resin, 22-28 parts of styrene-acrylonitrile-butadiene copolymer, and 5-20 parts of PBT resin.

[0008] When the weight ratio of the three organic resin components in the ABS alloy composition is preferably within the range of the above-mentioned weight ratio, the product can achieve a better balance between interlayer bonding and processing performance, thereby achieving better performance.

[0009] More preferably, the SAN resin has a mass content of ≥40wt% in the ABS alloy composition.

[0010] More preferably, the styrene-acrylonitrile-butadiene rubber copolymer has a mass content of ≤50wt% and ≥15wt% in the ABS alloy composition.

[0011] More preferably, the PBT resin has a mass content of ≤50wt% and ≥15wt% in the ABS alloy composition.

[0012] Preferably, the mass percentage of butadiene rubber phase in the styrene-acrylonitrile-butadiene copolymer is 50-60 wt%.

[0013] Preferably, the mass percentage of acrylonitrile in the SAN resin is one or any two of the following: 20%, 21%, 22%, 23%, 24%, and 25%.

[0014] It should be noted that the mass percentage of acrylonitrile in the SAN resin described in this application can be controlled by adjusting the ratio of acrylonitrile monomer and styrene monomer added during the preparation process, but it is not limited to this. Those skilled in the art can also achieve changes in the acrylonitrile content of the SAN resin in the final product by purchasing commercially available products, i.e., purchasing SAN resins with different acrylonitrile contents as raw materials, and no special limitation is made in this regard.

[0015] It should be noted that the mass percentage of acrylonitrile in the SAN resin described in this application can be confirmed in the following way: Referring to "Determination of Acrylonitrile Component Content in SAN by Fourier Transform Infrared Spectroscopy" by Lin Hongxiong, SAN resin was crushed into powder, and then prepared into tablets using the potassium bromide tableting method. A Fourier transform infrared analyzer (4 cm⁻¹ resolution) was used. -1 32 scans, wavelength 4000~400cm -1 The analysis yielded a spectrum read at 2237 cm⁻¹. -1 The nearby -CN corresponds to characteristic peak A and 700 cm⁻¹ -1 The absorbance of the characteristic peak B corresponding to the nearby benzene ring is used to calculate the absorbance ratio R=A / B. A standard curve is constructed using standards with different mass contents of acrylonitrile (15%, 20%, 25%, 30%). Then, linear regression is used to fit the curve to obtain the regression equation R=ax+b (correlation coefficient greater than 0.995). Substituting R into the curve, the mass content of acrylonitrile can be read.

[0016] Preferably, the SAN resin 1 and SAN resin 2 can be commercially available products or can be obtained by self-production. The preparation method includes the following steps: mixing acrylonitrile monomer and styrene monomer in a stoichiometric ratio and adding an initiator and heating to 100~120℃ for polymerization reaction for 2~6 hours, and then adding a terminator to terminate the reaction to obtain the SAN resin.

[0017] In the preparation process, the mass percentage of acrylonitrile in the SAN resin can be controlled by the metering ratio of the amount of acrylonitrile monomer and styrene monomer added during preparation. The weight-average molecular weight of the SAN resin can be controlled by adjusting the timing of the addition of the terminator. Specifically, when the terminator is added within 2 to 3 hours after the start of the polymerization reaction, the weight-average molecular weight of the SAN resin is relatively small, reaching the range of 100,000 to 120,000. However, when it is added within 4 to 5 hours after the start of the polymerization reaction, the weight-average molecular weight of the SAN resin is relatively large, reaching the range of 400,000 to 500,000. Preferably, the amount of the initiator added is 0.1 to 0.2 wt% of the total monomer, and the initiator may be, but is not limited to, azobisisobutyronitrile; the amount of the terminator added is 0.1 to 0.2 wt% of the total monomer, and the terminator may be, but is not limited to, dodecyl mercaptan.

[0018] Preferably, in the SAN resin, the mass ratio of SAN resin 1 to SAN resin 2 is 1:(0.1~0.45).

[0019] More preferably, in the SAN resin, the mass ratio of SAN resin 1 to SAN resin 2 is 1:(0.14~0.26).

[0020] As mentioned above, the molecular chains of two SAN resins with different molecular weights will form more dispersed molecular chain entanglements with suitable displacement space, thereby improving the product's extreme high-temperature rigidity and low-temperature toughness, and increasing the upper and lower limits of the product's temperature use. When the ratio of the two is further optimized within the above range, the binding between the rubber phase and the continuous phase in the product composition will be higher, and internal stress concentration will be less likely to occur. Therefore, the toughness retention rate at low temperatures and the rigidity at high temperatures are also higher.

[0021] It should be noted that the weight-average molecular weights of SAN resins 1 and 2 described in this invention were confirmed by GPC testing. The test used a polystyrene gel chromatography column (PLgel 5μm MIXED-C), with tetrahydrofuran as the mobile phase. The concentration of the SAN resin test solution was 0.5 mg / mL. The solution was filtered through a 0.22 μm filter before testing. The test temperature was 30°C, the injection flow rate was 1 mL / min, and the injection volume was 30 μL. The obtained spectra were confirmed by fitting with GPC workstation software.

[0022] Preferably, the intrinsic viscosity of the PBT at 25°C is 0.95~1.05 dL / g according to GB / T 17931-1999.

[0023] The specific test method is as follows: Add 0.1250±0.0002g of sample to 25 mL of phenol / o-dichlorobenzene mixed solution with a weight ratio of 1:1, heat to 135~140℃, and stir continuously until the sample is completely dissolved. After the sample cools to room temperature, use an Ubbelohde viscometer to test it at a test temperature of 25±0.05℃. The capillary inner diameter of the Ubbelohde viscometer is 0.73mm.

[0024] Preferably, the PBT resin has a melt flow rate of 20~35 g / 10 min at 260°C and 2.16 kg load according to ISO 1133-2011 method.

[0025] It should be noted that the source of PBT resin is not required in the technical solution of this invention. Those skilled in the art can select appropriate raw materials according to the actual situation. It can be a commercially available product or obtained by self-made method. For example, PTA (terephthalic acid) monomer is heated and pressurized under the condition of introducing a catalyst to prepare esterified material in advance, followed by prepolymerization reaction to obtain prepolymer, and then PBT resin is obtained by polycondensation reaction of prepolymer.

[0026] Preferably, the ABS alloy composition further includes a compatibilizer.

[0027] More preferably, the compatibilizer is present in a weight fraction of 0.5 to 2 parts.

[0028] Based on the alloy resin system described in this invention, in order to further improve the durability and mechanical properties of the product, those skilled in the art can further introduce an appropriate amount of compatibilizer to improve the component compatibility of the product. However, this does not mean that the compatibilizer is a necessary component. When the SAN resin, styrene-acrylonitrile-butadiene rubber copolymer resin and PBT resin described in this invention are combined and the limitations are met, the product can already achieve high toughness and high and low temperature toughness retention effects as well as high and high temperature strength. Therefore, there are no specific limitations on whether or not to add the compatibilizer or how much to add.

[0029] More preferably, the compatibilizer includes at least one of maleic anhydride compatibilizers and methyl propionate compatibilizers. Specifically, the maleic anhydride compatibilizer may include, but is not limited to, maleic anhydride-grafted styrene-acrylonitrile-butadiene resin and maleic anhydride-styrene copolymer, and the methyl acrylate compatibilizer may include, but is not limited to, methyl acrylate and styrene-acrylonitrile-glycidyl methacrylate.

[0030] Preferably, the ABS alloy composition further contains processing aids.

[0031] More preferably, the processing aids include, but are not limited to, at least one of lubricants and antioxidants.

[0032] It should be noted that, based on the needs of those skilled in the art for processing or actual use of the product, other types of processing aids may be added without affecting the expected performance of the product. For example, the aforementioned aids may improve the antioxidant properties and release effect of the product without affecting its characteristic properties. In other words, the description of the product components in the technical solution of this invention is not a limitation on their types. In addition to the processing aids described above, those skilled in the art may also introduce other common types of processing aids that do not affect the performance of the product, such as antistatic agents.

[0033] More preferably, the processing aid is 0.1 to 5 parts by weight.

[0034] More preferably, the lubricant includes at least one of amide lubricants and silicone lubricants, and the antioxidant includes at least one of hindered phenolic antioxidants and phosphite antioxidants.

[0035] More preferably, the antioxidant can be a mixture, such as a mixture of hindered phenolic antioxidants and phosphite antioxidants in a mass ratio of 1:(1~3), wherein the hindered phenolic antioxidant can be antioxidant 1010 and the phosphite antioxidant can be antioxidant 168; the lubricant can be an amide lubricant, specifically at least one of erucamide, oleamide, and N,N'-ethylenebis-stearamide.

[0036] Another object of the present invention is to provide a method for preparing the ABS alloy composition, comprising the following steps: The components are added to a screw extruder for melt extrusion and granulation to obtain the ABS alloy composition.

[0037] Preferably, the temperature zones of the screw extruder are set as follows: Zone 1 220~250℃, Zone 2 220~240℃, Zone 3 210~220℃, Zone 4 210~230℃, Zone 5 210~230℃, Zone 6 220~230℃, and the screw speed is 100~500 rpm.

[0038] Another object of the present invention is to provide the application of the ABS alloy composition in the manufacture of protective equipment.

[0039] Another object of the present invention is to provide a protective device comprising the ABS alloy composition described herein.

[0040] The ABS alloy composition described in this invention is based on the interaction of SAN resin, ABS resin and PBT resin. Compared with existing products, when applied to protective equipment, it can not only achieve high rigidity and high toughness, but also has excellent high and low temperature toughness retention rate and high and high temperature rigidity retention rate, while taking into account an extremely wide operating temperature range, so that the product can achieve high-specification protective effect and has a wide range of applications.

[0041] Preferably, the protective equipment includes helmets and bags, especially special engineering helmets and large cargo loading bags for sea and air transport, which have high requirements for rigidity, toughness and resistance to high and low temperature environments.

[0042] The beneficial effects of this invention are that it provides an ABS alloy composition, which uses a styrene-acrylonitrile-butadiene copolymer of two SAN resins as the matrix component and introduces polybutylene terephthalate as the dispersing component. This not only gives the product high toughness and rigidity, but also high high-temperature rigidity retention and low-temperature toughness retention, making it suitable for the manufacture of various protective equipment. Detailed Implementation

[0043] To better illustrate the purpose, technical solution, and advantages of this invention, the invention will be further described below with reference to specific embodiments and comparative examples. The purpose of this description is to provide a detailed understanding of the invention, not to limit its scope. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this invention. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this invention are commonly used reagents and instruments.

[0044] Examples 1-13 The ABS alloy of the present invention has the following composition as shown in Table 1.

[0045] The preparation method of the ABS alloy includes the following steps: The components are mixed evenly, and then melt-extruded and granulated in a twin-screw extruder to obtain the ABS alloy.

[0046] During melt extrusion of the component, the temperature zones of the screw extruder are set as follows: Zone 1 220~250℃, Zone 2 220~240℃, Zone 3 210~220℃, Zone 4 210~230℃, Zone 5 210~230℃, and Zone 6 220~230℃. The screw speed is 400 rpm, and the length-to-diameter ratio is 40:1.

[0047] Comparative Examples 1-7 The only difference between each comparative example and Example 1 is the type and ratio of components, as shown in Table 2.

[0048] In the components described in each embodiment and comparative example, The SAN resins 1 a~e are self-made products. The mass percentages of acrylonitrile and styrene vary among the SAN resin products. The acrylonitrile content of SAN resin 1a and SAN resin 1e~g is 20% by mass, and the styrene content is 80% by mass. The acrylonitrile content of SAN resin 1b is 25% by mass, and the styrene content is 75% by mass. The acrylonitrile content of SAN resin 1c is 16% by mass, and the styrene content is 84% ​​by mass. The SAN resin 1 d contains 30% acrylonitrile by mass and 70% styrene by mass. The preparation methods of SAN resin 1a, SAN resin 1b, SAN resin 1c and SAN resin 1d are as follows: acrylonitrile monomer and styrene monomer are mixed in a stoichiometric ratio, and 0.1 wt% of azobisisobutyronitrile (AIB) initiator is added. The mixture is heated to 105°C for 2 hours for polymerization. Then, 0.1 wt% of dodecyl mercaptan (DIM) in DIM is added to terminate the reaction, thereby obtaining the SAN resin. The weight average molecular weight of SAN resin 1a is 111,000, that of SAN resin 1b is 110,000, that of SAN resin 1c is 113,000, and that of SAN resin 1d is 112,000. The preparation method of SAN resin 1e is as follows: acrylonitrile monomer and styrene monomer are mixed in a stoichiometric ratio and 0.1 wt% of the total monomer amount of initiator azobisisobutyronitrile is added and heated to 105°C for polymerization reaction for 3 h. Then, 0.1 wt% of the total monomer amount of terminating agent dodecyl mercaptan is added to terminate the reaction, and the SAN resin is obtained. The weight average molecular weight of the obtained SAN resin 1e is 119000. The preparation method of SAN resin 1f is as follows: acrylonitrile monomer and styrene monomer are mixed in a stoichiometric ratio and 0.1 wt% of the total monomer amount of initiator azobisisobutyronitrile is added and heated to 105°C for polymerization reaction for 1.5 h. Then, 0.1 wt% of the total monomer amount of terminating agent dodecyl mercaptan is added to terminate the reaction, and the SAN resin is obtained. The weight average molecular weight of the obtained SAN resin 1f is 80,000. The preparation method of 1g of SAN resin is as follows: acrylonitrile monomer and styrene monomer are mixed in a stoichiometric ratio and 0.1wt% of the total monomer amount of initiator azobisisobutyronitrile is added and heated to 105°C for polymerization reaction for 3.5h. Then, 0.1wt% of the total monomer amount of terminating agent dodecyl mercaptan is added to terminate the reaction, and the SAN resin is obtained. The weight average molecular weight of the obtained 1g of SAN resin is 130,000. The acrylonitrile content of SAN resin 2a and SAN resin 2e~g is 20% by mass, and the styrene content is 80% by mass. The acrylonitrile content of SAN resin 2b is 25% by mass, and the styrene content is 75% by mass. The acrylonitrile content of SAN resin 2c is 16% by mass, and the styrene content is 84% ​​by mass. The acrylonitrile content of SAN resin 2d is 30% by mass, and the styrene content is 70% by mass. The preparation methods of SAN resins 2a, SAN resin 2b, SAN resin 2c and SAN resin 2d are as follows: acrylonitrile monomer and styrene monomer are mixed in a stoichiometric ratio, and 0.1 wt% of azobisisobutyronitrile (AIB) initiator is added. The mixture is heated to 105°C for 4 hours for polymerization. Then, 0.1 wt% of dodecyl mercaptan (DIM) in DIM is added to terminate the reaction, thereby obtaining the SAN resins. The weight-average molecular weight of SAN resin 2a is 420,000, that of SAN resin 2b is 425,000, that of SAN resin 2c is 422,000, and that of SAN resin 2d is 421,000. The preparation method of SAN resin 2e is as follows: acrylonitrile monomer and styrene monomer are mixed in a stoichiometric ratio and 0.1 wt% of the total monomer amount of initiator azobisisobutyronitrile is added and heated to 105°C for polymerization reaction for 5 h. Then, 0.1 wt% of the total monomer amount of terminating agent dodecyl mercaptan is added to terminate the reaction, and the SAN resin is obtained. The weight average molecular weight of the obtained SAN resin 2e is 478,000. The preparation method of SAN resin 2f is as follows: acrylonitrile monomer and styrene monomer are mixed in a stoichiometric ratio and 0.1 wt% of the total monomer amount of initiator azobisisobutyronitrile is added and heated to 105°C for polymerization reaction for 3.5 h. Then, 0.1 wt% of the total monomer amount of terminating agent dodecyl mercaptan is added to terminate the reaction, and the SAN resin is obtained. The weight average molecular weight of the obtained SAN resin 2f is 350,000. The preparation method of SAN resin 2g is as follows: acrylonitrile monomer and styrene monomer are mixed in a stoichiometric ratio and 0.1wt% of the total monomer amount of initiator azobisisobutyronitrile is added and heated to 105℃ for polymerization reaction for 5.5h. Then, 0.1wt% of the total monomer amount of terminating agent dodecyl mercaptan is added to terminate the reaction, and the SAN resin is obtained. The weight average molecular weight of the obtained SAN resin 2g is 550,000. The styrene-acrylonitrile-butadiene copolymer 1 is EB-168 produced by Yigong Chemical, with a butadiene content of 60 wt%. The styrene-acrylonitrile-butadiene copolymer 2 is ABS POW HR181 produced by Kumho Petrochemical, with a butadiene content of 55 wt%. The PBT resin 1 is PBT GX122J produced by Yizheng Chemical Fiber, and its melt flow rate is 22g / 10min at 250℃ and 2.16kg load. The PBT resin 2 is PBT 1100A produced by Nantong Xingchen, with a melt flow rate of 32g / 10min at 250℃ and 2.16kg load. The PA6 resin is PA6 HY2800A produced by Haiyang Chemical Fiber, with a melt flow rate of 24 g / 10 min at 250℃ and 2.16 kg load. The antioxidant is a mixture of commercially available hindered phenolic antioxidant 1010 and commercially available phosphite antioxidant 168 in a mass ratio of 1:2. The lubricant is a commercially available amide-based lubricant, erucamide. The compatibilizer 1 is PMMA LG, a polymethyl methacrylate polymer manufactured by Sumitomo Chemicals. The compatibilizer 2 is SMA 700, a styrene-maleic anhydride copolymer, produced by Huawen Company. Unless otherwise specified, all raw materials used in the embodiments and comparative examples of this invention are commercially available, and the same raw materials were used in each parallel experiment. Furthermore, the average length, average diameter, and average aspect ratio of the nano-haloite in the products obtained in each embodiment and comparative example were tested using the aforementioned test methods, and the results are shown in Table 1. Table 1 Table 2 To verify the performance of the ABS alloy described in this invention, the products prepared in each embodiment and comparative example were sampled using a Ningbo Haitian Bochuang BS650-Ⅲ injection molding machine. The injection temperature was set to 230-240-240-250℃, and the following tests were then conducted: (1) Toughness test: The test was conducted at 25℃ according to ISO 180-2019 standard. The test equipment was a pendulum impact tester HIT5.5P from Zwick GmbH, Germany, with a type A notch and an impact capacity of 2.75J. The room temperature notched impact strength A0 was obtained. Then, the sample was placed in a constant temperature chamber at -30℃ for 2 hours. The low temperature notched impact strength A1 was tested using the same method. The low temperature toughness retention rate was calculated as 100%×A1 / A0. (2) Rigidity test: The test was conducted at 25℃ according to ISO 178-2010 standard. The test equipment was a Z220 mechanical testing machine from Zwick GmbH, Germany. The bending rate was 2 mm / min. The room temperature bending strength B0 was obtained. Then the sample was placed in a 70℃ constant temperature oven for 2 hours. The high temperature bending strength B1 was tested using the same method. The high temperature rigidity retention rate was calculated as 100%×B1 / B0. The test results are shown in Tables 3 and 4.

[0049] Table 3 Table 4 As can be seen from Tables 3 and 4, the ABS alloy described in this invention has ideal application effects, not only maintaining excellent rigidity and toughness at room temperature, but also achieving a notched impact strength of 40 KJ / m. 2 The bending strength can reach over 2100MPa, and the performance retention rate under high and low temperatures is high. The high temperature rigidity retention rate can reach over 73%, and the low temperature toughness retention rate can reach over 64%. The operating temperature range can reach -30~70℃, and the overall performance is excellent.

[0050] This is mainly due to the combination of two SAN resins with specific molecular weights in the product, and the specific control of the acrylonitrile content of the SAN resins. On the one hand, the long molecular chains in the high molecular weight SAN resin can achieve a high degree of inter-chain entanglement, improving the overall resin's resistance to deformation. On the other hand, the short molecular chains in the low molecular weight SAN resin can provide sufficient displacement space during the entanglement and bonding with the long molecular chains and the rubber phase. This allows the product to fully absorb the impact force when subjected to external impact, even when the molecular chain sliding is restricted at low temperatures, based on displacement and the entanglement between molecular chains. This inhibits the formation and propagation of microcracks in the product. Combined with the rubber phase, the product has excellent impact resistance and high low-temperature toughness. At the same time, the low molecular weight SAN resin molecular chains can also increase the range of entanglement of long molecular chains, avoiding the weakening of rigidity due to excessive entanglement of resin molecules. This ensures that the rigidity of the product can also reach a high level even when the molecular creep is high at high temperatures. In high-temperature environments, molecular chain entanglement can effectively inhibit creep and increase the upper limit of the product's applicable temperature. On the other hand, due to the differences in the length and entanglement of the molecular chains of the two SAN resins, the acrylonitrile content of the matrix SAN resin needs to be maintained at a certain level at the stated molecular weight, so as to ensure that the rigidity, toughness and temperature resistance of the product are all at a high level. Furthermore, PBT resin is introduced as a dispersant for the product. This component has high compatibility with both the rubber phase and the continuous phase, so it can help the rubber phase improve its dispersibility.

[0051] In contrast, Comparative Examples 1 and 2 used only one type of SAN resin as the matrix resin. Obviously, in addition to the imbalance between rigidity and toughness, the low-temperature performance and high-temperature performance of the products were not ideal. According to the examples and Comparative Examples 3 to 10, it can be seen that if the acrylonitrile content of SAN resin 1 and SAN resin 2 is too high or too low, or if the molecular weight difference distribution between the resins is not properly defined, it is impossible to take into account the rigidity and toughness mechanical properties of the products as well as the mechanical retention rate at high and low temperatures. Comparative Examples 11 and 12 show that PBT resin, as a compatibilizer, is very critical. If this component is missing, the compatibility of the two SAN resins will be insufficient, which will not only reduce the resistance to high and low temperatures, but also directly affect the rigidity and toughness under normal conditions. While using an unsuitable compatibilizer, such as PA6 resin, can achieve component compatibilization to a certain extent, the effect is not significant.

[0052] A comparison of Examples 1 and 9-11 shows that when two SAN resins are compounded, if the ratio is further optimized to 1:(0.14-0.26), in addition to controlling the rigidity and toughness, the product also exhibits higher toughness retention at low temperatures and higher rigidity at high temperatures.

[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 alloy composition, characterized in that, The components include the following parts by weight: 40-60 parts of SAN resin, 20-30 parts of styrene-acrylonitrile-butadiene copolymer, and 15-35 parts of PBT resin; The acrylonitrile content of the SAN resin is 20-25% by mass. The SAN resin includes SAN resin 1 and SAN resin 2, wherein the weight-average molecular weight of SAN resin 1 is 100,000 to 120,000, and the weight-average molecular weight of SAN resin 2 is 400,000 to 500,000.

2. The ABS alloy composition according to claim 1, characterized in that, In the SAN resin, the mass ratio of SAN resin 1 to SAN resin 2 is 1:(0.1~0.45).

3. The ABS alloy composition as described in claim 1, characterized in that, The butadiene rubber phase in the styrene-acrylonitrile-butadiene copolymer has a mass percentage of 50-60 wt%.

4. The ABS alloy composition according to claim 1, characterized in that, The PBT resin has a melt flow rate of 20~35g / 10min at 260℃ and 2.16kg load.

5. The ABS alloy composition as described in claim 1, characterized in that, The components of the ABS alloy composition also include a compatibilizer.

6. The ABS alloy composition as described in claim 5, characterized in that, The compatibilizer includes at least one of maleic anhydride compatibilizers and methylpropionate compatibilizers.

7. The ABS alloy composition according to claim 1, characterized in that, The ABS alloy composition also contains 0.1 to 5 parts of processing aids; the processing aids include at least one of lubricant and antioxidant.

8. The method for preparing the ABS alloy composition according to any one of claims 1 to 7, characterized in that, Includes the following steps: The components are added to a screw extruder for melt extrusion and granulation to obtain the ABS alloy composition.

9. The use of the ABS alloy composition according to any one of claims 1 to 7 in the preparation of protective equipment.

10. A protective device, characterized in that, Includes the ABS alloy composition according to any one of claims 1 to 7.

Images