High-impact heat-resistant ABS plate and preparation method thereof

Abstract

The application relates to the field of functional plate materials, in particular to a high-impact and heat-resistant ABS plate material and a preparation method thereof. The high-impact and heat-resistant ABS plate material comprises, in mass parts, at least: ABS base resin 55-75 parts, heat-resistant resin 15-30 parts, toughening agent 8-14 parts, reinforcing filler 3-8 parts, compatibilizer 3-6 parts and auxiliary resin combination 4-10 parts. The finally-prepared ABS plate material can simultaneously maintain high impact resistance and high heat resistance, balance the performance contradiction between the two, and simultaneously ensure that the ABS plate material has good performances in corrosion resistance, aging resistance and dimensional stability and the like, greatly improves the comprehensive application performance, and solves the performance problems of the existing ABS plate material.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of functional boards, more particularly to a high-impact and heat-resistant ABS board and a preparation method thereof. BACKGROUND

[0002] In the field of modern industrial manufacturing, acrylonitrile / butadiene / styrene copolymer (ABS) resin is widely used in the manufacturing of automotive parts, electronic device housings, and household appliances due to its excellent mechanical strength, processing convenience, and cost-effectiveness. Among them, ABS boards, as an important profile, need to be modified and optimized in process to meet the stringent requirements of specific application environments on material performance, especially in terms of high impact resistance and heat resistance. With the continuous expansion of application scenarios, such as structural supports under high temperature working conditions or functional components that need to withstand dynamic loads, the limitations of traditional ABS boards in terms of heat distortion temperature and impact toughness have gradually become apparent. Therefore, the development of high-impact and high-heat-resistant ABS boards has become an important direction for industrial technology upgrading.

[0003] In the prior art, to improve the heat resistance of ABS boards, α-methylstyrene and other heat-resistant monomers are often introduced for copolymerization, or heat-resistant resins such as polycarbonate and nylon are added for blending modification. Although this method can improve the heat distortion temperature of the material to some extent, it often leads to a decrease in impact strength, an increase in brittleness, and a decrease in processing flowability, making the board prone to cracking during stamping or deep processing. On the other hand, to improve the impact resistance of ABS, it is common to increase the content of butadiene rubber or add elastomers, but excessive rubber phase will significantly reduce the rigidity and heat resistance of the material, causing the board to soften and deform easily in a high-temperature environment, making it difficult to balance the overall performance.

[0004] In addition, existing modified ABS boards often use inorganic fillers for reinforcement in the production process in an attempt to balance mechanical and thermal properties. However, poor compatibility between fillers and the matrix can lead to interface defects, which become stress concentration points when subjected to high impact loads, thereby reducing the toughness of the material. At the same time, the addition of too high a proportion of fillers can also affect the surface quality and forming processability of the board, limiting its application in high-end appearance parts. Related patents and documents have also reported the use of multi-layer composite structures or special annealing processes to synergistically improve heat resistance and impact resistance, but such processes are complex, have poor overall performance, and have low adaptability to continuous mass production. SUMMARY

[0005] In summary, the ABS plates prepared in the prior art still have obvious deficiencies in improving the impact resistance and heat resistance at the same time, most modification schemes are difficult to break through the inverted relationship between the properties, and often at the expense of a certain property to improve another property, in addition, the existing methods also generally face problems such as complex processing process, poor material compatibility and poor comprehensive performance. Through in-depth research in this technical field, the applicant finally proposes an ABS plate and a preparation method thereof in the present application. The ABS plate finally prepared in the present application can simultaneously maintain high impact resistance and high heat resistance, balance the performance contradiction between the two, and at the same time can ensure that the ABS plate has good performance in corrosion resistance, aging resistance and dimensional stability, etc., greatly improving the comprehensive application performance, solving the performance problems of the existing ABS plate.

[0006] A high-impact heat-resistant ABS plate, by mass parts, raw materials at least include: ABS base resin 55-75 parts, heat-resistant resin 15-30 parts, toughening agent 8-14 parts, reinforcing filler 3-8 parts, compatibilizer 3-6 parts, auxiliary resin combination 4-10 parts.

[0007] Preferably, the melt flow rate of the ABS base resin is 20-50 g / 10 min, 220℃ / 10 kg.

[0008] More preferably, the melt flow rate of the ABS base resin is 25-40 g / 10 min, 220℃ / 10 kg.

[0009] Preferably, the mass ratio of the ABS base resin, the heat-resistant resin and the auxiliary resin combination is (6-7.2):(2-2.6):(0.7-1).

[0010] Preferably, the mass ratio of the ABS base resin, the heat-resistant resin and the auxiliary resin combination is (6.2-6.5):(2.2-2.4):(0.8-0.9).

[0011] Preferably, the heat-resistant resin is at least one of styrene-maleimide copolymer resin, SAN copolymer resin and ASA resin.

[0012] More preferably, the heat-resistant resin is styrene-maleimide copolymer resin or SAN copolymer resin.

[0013] Most preferably, the heat-resistant resin is styrene-maleimide copolymer resin.

[0014] Preferably, the toughening agent is at least one of hydrogenated styrene-butadiene block copolymer, polyolefin elastomer, propylene-based elastomer and maleic anhydride grafted polyethylene.

[0015] More preferably, the toughening agent is a hydrogenated styrene-butadiene block copolymer or a polyolefin elastomer.

[0016] Most preferably, the toughening agent is a polyolefin elastomer.

[0017] Preferably, the reinforcing filler is at least one of hydrophobic silica, alumina, montmorillonite, sericite powder and talc powder.

[0018] More preferably, the reinforcing filler is hydrophobic silica or alumina.

[0019] Most preferably, the reinforcing filler is hydrophobic silica.

[0020] Preferably, the average particle size of the hydrophobic silica is 25-80 nm.

[0021] More preferably, the average particle size of the hydrophobic silica is 25-50 nm.

[0022] Preferably, the compatibilizer is at least one of maleic anhydride grafted PE, maleic anhydride grafted PP and maleic anhydride grafted SEBS.

[0023] More preferably, the compatibilizer is maleic anhydride grafted PE or maleic anhydride grafted PP.

[0024] Most preferably, the compatibilizer is maleic anhydride grafted PE.

[0025] Preferably, the auxiliary resin combination is a combination of a multifunctional epoxy resin and a functional acrylate resin.

[0026] Preferably, the mass ratio of the multifunctional epoxy resin and the functional acrylate resin is (4.5-6):(1.2-2).

[0027] More preferably, the mass ratio of the multifunctional epoxy resin and the functional acrylate resin is (5-5.5):(1.5-1.8).

[0028] Preferably, the multifunctional epoxy resin is NPEL-128 from China Nan Ya Plastics.

[0029] Preferably, the functional acrylate resin is FAAR-102 from USA Dow Chemical.

[0030] The specific auxiliary resin combination used in the present application builds a flexible rubber phase core in the material and a rigid reaction product shell micro-unit, thereby effectively absorbing external energy and significantly improving toughness; and constrains the deformation of the rubber phase at high temperatures, like providing a heat-resistant skeleton, thereby avoiding the heat resistance decline caused by traditional toughening agents, and greatly improving the hot deformation temperature of the plate. On the other hand, the epoxy resin network itself enhances the binding force between molecular chains, effectively inhibiting the size change of the material when heated, improving the dimensional stability and creep resistance, and with a dense crosslinked structure to hinder the intrusion of corrosive media, enhancing the chemical resistance and greatly improving the overall comprehensive performance of the plate.

[0031] Preferably, the high-impact heat-resistant ABS plate, by mass fraction, further comprises: 0.5-1 parts of a composite antioxidant, 0.6-1.3 parts of a lubricant, and 5-8 parts of a functional polymer.

[0032] Preferably, the composite antioxidant is at least two of antioxidant 1076, antioxidant 1010, antioxidant 168, antioxidant 126, and antioxidant 1680.

[0033] More preferably, the composite antioxidant is a combination of antioxidant 1076 and antioxidant 168.

[0034] Preferably, the mass ratio of antioxidant 1076 to antioxidant 168 is (2-3):1.

[0035] Preferably, the mass ratio of the ABS base resin to the functional polymer is (6-7.2):(0.6-0.8).

[0036] More preferably, the mass ratio of the ABS base resin to the functional polymer is (6.2-6.5):(0.6-0.7).

[0037] Preferably, the lubricant is at least one of polyethylene wax, oxidized polyethylene wax, polysiloxane, and composite ester.

[0038] More preferably, the lubricant is polyethylene wax or polysiloxane.

[0039] Most preferably, the lubricant is polyethylene wax.

[0040] Preferably, the functional polymer is a combination of polyamide and polyphenyl ether.

[0041] Preferably, the mass ratio of polyamide to polyphenyl ether is (3-5):(1.5-2.5).

[0042] More preferably, the mass ratio of polyamide to polyphenyl ether is (3.5-4.5):(2-2.2).

[0043] Preferably, the polyamide is Ultramid® B40L from BASF, Germany.

[0044] Preferably, the polyphenylene ether is Noryl® PPO 640 from SABIC.

[0045] The further added functional polymers comprehensively improve the high-temperature stability, moisture resistance and corrosion resistance of the plate, while maintaining good mechanical properties. The two functional polymers form a stable composite structure through the action of the compatibilizer during melt blending, providing excellent mechanical strength and chemical resistance, and playing a role in inherent low moisture absorption and high thermal stability to form a barrier effect, effectively inhibiting the penetration and diffusion of water molecules, thereby significantly reducing the moisture absorption of the material and avoiding dimensional changes and performance degradation due to moisture absorption. At the same time, it provides a stable support framework for the entire system, so that the material can still maintain shape and performance stability in a high-temperature environment.

[0046] A method for preparing a high-impact heat-resistant ABS plate, comprising the following steps: S1: S1: Put the auxiliary resin combination and the ABS base resin into a low-speed stirring tank and mix uniformly for standby, then add the heat-resistant resin, the toughening agent, the reinforcing filler and the compatibilizer into a high-speed mixer in sequence and mix at high speed, then add the remaining raw materials and continue to mix, to obtain a premix; S2: melt blend the premix through a double-screw extruder, cool in a water cooling tank after completion and cut and dry to obtain a composite granule; S3: send the composite granule into a single-screw extrusion calender unit to produce a plate, pull the extruded, cooled and shaped plate through a puller, and finally cut into the required size.

[0047] Preferably, the method for preparing a high-impact heat-resistant ABS plate comprises the following steps: S1: Put the auxiliary resin combination and the ABS base resin into a low-speed stirring tank and mix uniformly for standby at 45-50°C and a stirring speed of 400-500 rpm for 12-15 min, then add the heat-resistant resin, the toughening agent, the reinforcing filler and the compatibilizer into a high-speed mixer in sequence and mix at high speed at 500-600 rpm for 5-8 min, then add the remaining raw materials and continue to mix for 4-6 min, to obtain a premix; S2: melt blend the premix through a double-screw extruder, with a temperature interval of 185-235°C, a die head temperature of 230-235°C and a screw rotation speed of 250-300 rpm, cool in a water cooling tank after completion, cut and dry at 80-85°C for 8-10 h, to obtain a composite granule; S3: send the composite granule into a single-screw extrusion calender unit to produce a plate, pull the extruded, cooled and shaped plate through a puller, and finally cut into the required size.

[0048] The present application has the following beneficial effects:

[0049] 1. The ABS sheet finally obtained by this application can maintain high impact resistance and high heat resistance at the same time, balancing the performance contradiction between the two, and at the same time ensuring that the ABS sheet has good performance in terms of corrosion resistance, aging resistance and dimensional stability, greatly improving the comprehensive application performance and solving the performance problems of existing ABS sheets.

[0050] 2. This application uses a combination of functional epoxy resin NPEL-128 and functional acrylate resin FAAR-102 to construct a flexible rubber phase core inside the material and a rigid reaction product as the outer shell micro-unit, thereby effectively absorbing external energy and significantly improving toughness. In addition, the epoxy resin network itself enhances the binding force between molecular chains, effectively suppressing the dimensional changes of the material when heated, improving dimensional stability and creep resistance. Furthermore, the dense cross-linked structure hinders the intrusion of corrosive media, enhances chemical resistance, and greatly improves the overall comprehensive performance of the board.

[0051] 3. The functional polymers further incorporated in this application comprehensively enhance the high-temperature stability, moisture resistance, and corrosion resistance of the sheet material, while maintaining good mechanical properties. Most notably, these two functional polymers form a stable composite structure during melt blending through the action of a compatibilizer, providing excellent mechanical strength and chemical resistance. Furthermore, their inherent low hygroscopicity and high thermal stability create a barrier effect, effectively inhibiting the penetration and diffusion of water molecules, thereby significantly reducing the material's hygroscopicity and preventing dimensional changes and performance degradation caused by moisture absorption. Attached Figure Description

[0052] Figure 1 This is a photograph of the high impact resistance and heat resistance ABS sheet obtained in Example 1 of this application. Detailed Implementation

[0053] Example 1

[0054] A high-impact and heat-resistant ABS sheet, by weight, comprises the following raw materials: 64 parts ABS base resin, 23 parts heat-resistant resin, 9.5 parts toughening agent, 5 parts reinforcing filler, 4.5 parts compatibilizer, 8.5 parts auxiliary resin combination, 0.6 parts composite antioxidant, 0.8 parts lubricant, and 6.5 parts functional polymer.

[0055] The melt flow rate of the ABS base resin is 30g / 10min, 220℃ / 10kg, model PA-757, manufactured by Chi Mei Corporation of Taiwan.

[0056] The heat-resistant resin is a styrene-maleimide copolymer resin, model MS-600, manufactured by Denki Chemical, Japan; the toughening agent is a polyolefin elastomer, model 7467, manufactured by Dow Chemical, USA; and the compatibilizer is maleic anhydride-grafted PE, model P353, manufactured by DuPont, USA.

[0057] The reinforcing filler is hydrophobic silica with an average particle size of 40 nm; the lubricant is polyethylene wax.

[0058] The auxiliary resin combination is a combination of multifunctional epoxy resin and functional acrylate resin in a mass ratio of 5.2:1.8.

[0059] The multifunctional epoxy resin is NPEL-128, sourced from Nan Ya Plastics in China; the functional acrylate resin is FAAR-102, sourced from Dow Chemical in the United States.

[0060] The compound antioxidant is a combination of antioxidant 1076 and antioxidant 168 in a mass ratio of 2:1.

[0061] The functional polymer is a combination of polyamide and polyphenylene ether in a mass ratio of 4.3:2.2.

[0062] The polyamide is Ultramid® B40L, sourced from BASF, Germany; the polyphenylene ether is Noryl® PPO 640, sourced from SABIC.

[0063] A method for preparing high-impact and heat-resistant ABS sheets includes the following steps: S1: Add auxiliary resin combination and ABS base resin to a low-speed mixing tank, stir at 50°C and 500 rpm for 15 minutes to mix evenly, and then add heat-resistant resin, toughening agent, reinforcing filler and compatibilizer to a high-speed mixer in sequence, mix at 600 rpm for 7 minutes, then add the remaining raw materials and continue mixing for 4 minutes to obtain a premix; S2: Melt-blend the premix through a twin-screw extruder, with the temperature range being 185°C in zone 1, 200°C in zone 2, 215°C in zone 3, 225°C in zone 4, and 235°C in zone 5, die temperature 230°C, screw speed 260 rpm, and after completion, cool in a water-cooling tank and granulate, then dry at 80°C for 8 hours to obtain composite granules; S3: Feed the composite granules into a single-screw extrusion calender to produce sheets, and after extrusion, cooling and shaping, the sheets are pulled by a traction machine and finally cut into the required size to obtain the final product.

[0064] The actual product of the high-impact and heat-resistant ABS sheet obtained in this embodiment is shown below. Figure 1 As shown.

[0065] Example 2

[0066] This embodiment differs from Embodiment 1 only in the following aspects: A high-impact and heat-resistant ABS sheet, by weight, comprises the following raw materials: 70 parts ABS base resin, 20 parts heat-resistant resin, 9.5 parts toughening agent, 5 parts reinforcing filler, 4.5 parts compatibilizer, 9.5 parts auxiliary resin combination, 0.6 parts composite antioxidant, 0.8 parts lubricant, and 6 parts functional polymer.

[0067] The remaining implementation methods are the same.

[0068] Example 3

[0069] This embodiment differs from Embodiment 1 only in the following aspects: A high-impact and heat-resistant ABS sheet, by weight, comprises the following raw materials: 68 parts of ABS base resin, 26 parts of heat-resistant resin, 9.5 parts of toughening agent, 5 parts of reinforcing filler, 4.5 parts of compatibilizer, 7 parts of auxiliary resin combination, 0.6 parts of composite antioxidant, 0.8 parts of lubricant, and 7 parts of functional polymer.

[0070] The remaining implementation methods are the same.

[0071] Comparative Example 1

[0072] This comparative example differs from Example 1 only in the following aspects: a high impact-resistant and heat-resistant ABS sheet, by weight, comprises the following raw materials: 85 parts of ABS base resin, 25 parts of heat-resistant resin, 9.5 parts of toughening agent, 5 parts of reinforcing filler, 4.5 parts of compatibilizer, 2.5 parts of auxiliary resin combination, 0.6 parts of composite antioxidant, 0.8 parts of lubricant, and 8.5 parts of functional polymer.

[0073] The remaining implementation methods are the same.

[0074] Comparative Example 2

[0075] This comparative example differs from Example 1 only in the following aspects: a high impact-resistant and heat-resistant ABS sheet, by weight, comprises the following raw materials: 85 parts of ABS base resin, 25 parts of heat-resistant resin, 9.5 parts of toughening agent, 6 parts of reinforcing filler, 4.8 parts of compatibilizer, 10 parts of auxiliary resin combination, 0.6 parts of composite antioxidant, 0.8 parts of lubricant, and 1.5 parts of functional polymer.

[0076] The remaining implementation methods are the same.

[0077] Comparative Example 3

[0078] The only difference between this comparative example and Example 1 is that the auxiliary resin combination is a combination of multifunctional epoxy resin and functional acrylate resin in a mass ratio of 8:1.

[0079] The remaining implementation methods are the same.

[0080] Comparative Example 4

[0081] This comparative example differs from Example 1 only in the following way: the auxiliary resin combination is a combination of multifunctional epoxy resin and functional acrylate resin in a mass ratio of 2:3.

[0082] The remaining implementation methods are the same.

[0083] Comparative Example 5

[0084] This comparative example differs from Example 1 only in the following way: the functional polymer is a combination of polyamide and polyphenylene ether in a mass ratio of 5:1.

[0085] The remaining implementation methods are the same.

[0086] Comparative Example 6

[0087] This comparative example differs from Example 1 only in the following way: the functional polymer is a combination of polyamide and polyphenylene ether in a mass ratio of 1.5:3.5.

[0088] The remaining implementation methods are the same.

[0089] Performance testing

[0090] 1. Tensile strength: The tensile strength was obtained by referring to the standard ASTM D638. The result was the average of 10 parallel tests and recorded in Table 1.

[0091] 2. Bending strength: The bending strength was obtained with reference to the standard ASTM D790. The result was the average of 10 parallel tests and recorded in Table 1.

[0092] 3. Softening temperature: The softening temperature was obtained by referring to the standard ASTM D1525. The result was the average of 10 parallel tests and recorded in Table 1.

[0093] 4. Impact resistance: Referring to the standard ASTM D256, the notched impact strength of the cantilever beam was obtained, and the average value of 10 parallel tests was recorded in Table 1.

[0094] 5. Corrosion resistance: The test references ASTM D543. The corrosive medium is xylene. The sample is continuously immersed in a constant temperature environment of 23℃ for 168h. The sample is weighed before and after the test to obtain the mass change rate. The result is the average of 10 parallel tests and recorded in Table 1.

[0095] Table 1 Performance Test Results

[0096]

[0097] Based on the final performance test results of the embodiments and comparative examples, Examples 1-3 achieved superior performance results compared to Comparative Examples 1-6. This is mainly due to the technical solutions specified in this application used in Examples 1-3, especially the combination of functional epoxy resin and functional acrylate resin, which effectively suppressed dimensional changes of the material under heat, improved dimensional stability and creep resistance, and hindered the intrusion of corrosive media with a dense cross-linked structure, enhancing chemical resistance. Furthermore, the added functional polymer effectively suppressed the penetration and diffusion of water molecules, thereby significantly reducing the hygroscopicity of the material and avoiding dimensional changes and performance degradation caused by moisture absorption. In contrast, Comparative Examples 1 and 2 did not use the raw material formulation scheme specified in this application, resulting in a significant decrease in the effectiveness of the aforementioned key raw materials in the ABS sheet system, ultimately leading to a decline in the overall performance of the sheet.

[0098] Furthermore, Comparative Examples 3 to 6, due to the failure to adopt the auxiliary resin combination scheme and functional polymer scheme specified in this application, showed a significant decrease in their actual effects compared to Examples 1 to 3, which directly reflected in the performance results, resulting in a significant negative impact on performance and thus obtaining worse performance test results.

Claims

1. A high-impact, heat-resistant ABS sheet, characterized in that: By weight, the raw materials include at least: 55-75 parts of ABS base resin, 15-30 parts of heat-resistant resin, 8-14 parts of toughening agent, 3-8 parts of reinforcing filler, 3-6 parts of compatibilizer, 4-10 parts of auxiliary resin combination, 0.5-1 part of composite antioxidant, 0.6-1.3 parts of lubricant, and 5-8 parts of functional polymer. The melt flow rate of the ABS base resin is 20~50g / 10min, 220℃ / 10kg; The auxiliary resin combination is a combination of multifunctional epoxy resin and functional acrylate resin, with a mass ratio of (4.5~6):(1.2~2). The multifunctional epoxy resin is NPEL-128; the functional acrylate resin is FAAR-102. The heat-resistant resin is a styrene-maleimide copolymer resin; The functional polymer is a combination of polyamide and polyphenylene ether in a mass ratio of (3~5):(1.5~2.5).

2. The high impact resistance and heat resistance ABS sheet according to claim 1, characterized in that: The mass ratio of the ABS base resin, heat-resistant resin and auxiliary resin combination is (6~7.2):(2~2.6):(0.7~1).

3. The high impact resistance and heat resistance ABS sheet according to claim 2, characterized in that: The toughening agent is at least one of hydrogenated styrene-butadiene block copolymer, propylene-based elastomer, and maleic anhydride-grafted polyethylene.

4. The high impact resistance and heat resistance ABS sheet according to claim 3, characterized in that: The mass ratio of the ABS base resin to the functional polymer is (6~7.2):(0.6~0.8).

5. The high impact resistance and heat resistance ABS sheet according to claim 4, characterized in that: The lubricant is at least one of polyethylene wax, oxidized polyethylene wax, polysiloxane, and complex ester.

6. A method for preparing a high-impact and heat-resistant ABS sheet according to any one of claims 1 to 5, characterized in that: S1: Add the auxiliary resin combination and ABS base resin to a low-speed mixing tank and mix evenly for later use. Then, add the heat-resistant resin, toughening agent, reinforcing filler and compatibilizer to a high-speed mixer in sequence and mix at high speed. Then add the remaining raw materials and continue mixing to obtain a premix. S2: Melt-blend the premix through a twin-screw extruder. After completion, cool it in a water-cooling tank and granulate and dry it to obtain composite granules. S3: Feed the composite granules into a single-screw extrusion calender to produce sheets. After extrusion, cooling and shaping, the sheets are pulled by a traction machine and finally cut into the required size.

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