PC / ABS alloy resin and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, in particular to PC / ABS alloy resin and a preparation method thereof. The alloy resin is prepared from the following components in parts by mass: 52 to 81 parts of PC (Polycarbonate) resin, 5 to 11 parts of butadiene-styrene-acrylonitrile graft copolymer, 10 to 34 parts of styrene-acrylonitrile copolymer, 0.3 to 0.8 part of pentaerythritol stearate, 0.18 to 0.3 part of beta-(3, 5-di-tert-butyl-4-hydroxyphenyl) octadecanol propionate, 2.3 to 4.2 parts of butadiene-styrene-methyl methacrylate graft copolymer, 0.2 to 0.4 part of antioxidant, 0.2 to 0.4 part of antioxidant and 0.2 to 0.4 part of lubricant. And 0.02 part of dimethyl silicone oil. According to the PC / ABS alloy resin, the fluidity of the ABS resin can be improved, the compatibility between PC and the ABS resin is improved, and high impact resistance and good weather resistance of the PC / ABS alloy resin are achieved.

Description

Technical fields:

[0001] This invention relates to the field of polymer materials technology, and in particular to a PC / ABS alloy resin and its preparation method. Background technology:

[0003] Polypropylene (PC), a high-performance thermoplastic, is commonly used in the automotive, medical equipment, and electronic equipment manufacturing industries, including optical discs. However, due to its high melt viscosity, poor flowability, and notch sensitivity, PC is often compounded with other thermoplastic resins to improve processing performance and reduce costs. ABS resin, combining the properties of acrylonitrile, butadiene, and styrene monomers, exhibits excellent low-temperature impact resistance, chemical resistance, and electrical properties, making it a superior choice for PC resin alloys.

[0004] High-performance PC / ABS material grades remain scarce in the market. As an alternative to automotive materials, PC / ABS alloy resin must possess good impact resistance and excellent weather resistance. Simultaneously, due to the large size of automotive components, high flowability of the PC / ABS alloy resin is required to ensure processability during injection molding. Therefore, developing a high-impact, weather-resistant automotive PC / ABS alloy resin is a strong demand to meet the needs of the new energy vehicle development. Summary of the Invention:

[0005] The technical problem to be solved by the present invention is to provide a PC / ABS alloy resin and its preparation method. The PC / ABS alloy resin can improve the fluidity of ABS resin, improve the compatibility between PC and ABS resin, and achieve high impact resistance and good weather resistance of PC / ABS alloy resin.

[0006] The technical solution adopted in this invention is: a PC / ABS alloy resin, which comprises the following components and their mass fractions: 52-81 parts PC resin, 5-11 parts butadiene-styrene-acrylonitrile graft copolymer, 10-34 parts styrene-acrylonitrile copolymer, 0.3-0.8 parts pentaerythritol stearate, 0.18-0.3 parts β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol ester, 2.3-4.2 parts butadiene-styrene-methyl methacrylate graft copolymer, and 0.02 parts dimethyl silicone oil.

[0007] Furthermore, the butadiene-styrene-acrylonitrile graft copolymer is grafted using an emulsion polymerization method, the grafting rate of the butadiene-styrene-acrylonitrile graft copolymer is 45% to 65%, the particle size of the graft copolymer is 220 to 350 nm, and the mass ratio of butadiene, styrene and acrylonitrile is 52 to 60: 22 to 30: 12 to 19.

[0008] Furthermore, the styrene-acrylonitrile copolymer is produced by bulk polymerization, and the system also contains solvents, including toluene, ethylbenzene, and xylene.

[0009] Furthermore, the styrene-acrylonitrile copolymer is produced by bulk polymerization, and the ratio of styrene to acrylonitrile is adjusted so that the styrene-acrylonitrile copolymer has a melt index ≥60g / 10min, a nitrogen content ≥7.0%, a bonded acrylonitrile content of 28% to 30%, and a number average molecular weight of 50,000 to 60,000 under the conditions of 220°C and 10kg.

[0010] Furthermore, in the styrene-acrylonitrile copolymer, the mass ratio of styrene to acrylonitrile is 60-80:20-40.

[0011] A method for preparing PC / ABS alloy resin includes the following steps: PC resin, butadiene-styrene-acrylonitrile graft copolymer, styrene-acrylonitrile copolymer, pentaerythritol stearate, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol ester, butadiene-styrene-methyl methacrylate graft copolymer, and dimethyl silicone oil are weighed according to the mass fractions, and after being fully mixed in a high-speed mixer for a period of time, the mixture is added to a twin-screw extruder for blending, melting, extrusion, and granulation to obtain PC / ABS alloy resin.

[0012] Furthermore, the twin-screw extruder has a screw speed of 210–250 r / min and an extrusion temperature of 230–270 °C.

[0013] Furthermore, the mixture is thoroughly mixed in the high-speed mixer for 3–5 minutes.

[0014] The beneficial effects of this invention are:

[0015] (1) The present invention uses butadiene-styrene-methyl methacrylate graft as a compatibilizer, which has good compatibility with PC resin. It is similar to the ternary components of ABS resin and can be completely compatible with ABS resin. Furthermore, it uses styrene-acrylonitrile copolymer as one of the components, which has high processing fluidity and can expand the application of PC / ABS alloy resin in the field of automotive interior parts.

[0016] (2) By adjusting the degree of polymerization of the styrene-acrylonitrile polymer, this invention enables the acrylonitrile, butadiene, and styrene components in ABS to exhibit better high fluidity during the combination process, ensuring uniform dispersion of PC and ABS when preparing PC / ABS alloy resin. Therefore, the impact performance of the PC / ABS alloy resin exceeds that of any individual component, achieving a synergistic effect greater than the sum of its parts.

[0017] (3) By adjusting the ratio of butadiene, styrene and acrylonitrile in ABS resin and using it in combination with butadiene-styrene-methyl methacrylate graft compatibilizer, the present invention improves the aging resistance of PC / ABS alloy resin. After aging, its impact strength loss rate is much smaller than that of ordinary commercially available PC / ABS. Attached image description:

[0018] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0019] Figure 1 This is a 2000x scanning electron microscope image of the impact fracture surface of PC / ABS alloy resin in Example 2.

[0020] Figure 2 This is a 4000x scanning electron microscope image of the impact fracture surface of PC / ABS alloy resin in Example 2. Detailed implementation method:

[0021] To make the objectives, technical solutions, and effects of this invention clearer, the technical solutions of this invention are described in complete and detailed form below with reference to embodiments. All reagents and instruments used, unless otherwise specified, are commercially available products.

[0022] The present invention will now be described with reference to specific embodiments, but is not limited thereto.

[0023] Example 1

[0024] Weigh out the following components by mass: 81 parts PC, 10 parts styrene-acrylonitrile copolymer, 5 parts butadiene-styrene-acrylonitrile graft copolymer, 0.8 parts pentaerythritol stearate, 0.18 parts β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol, 3 parts butadiene-styrene-methyl methacrylate graft copolymer, and 0.02 parts dimethyl silicone oil. Add these components to a high-speed mixer and mix thoroughly for 5 minutes. Then, add the mixture to a twin-screw extruder for blending, melting, extrusion, and granulation. The screw speed is 210–250 r / min. The barrel conveying section, plasticizing section, metering section, and die temperature of the co-rotating twin-screw extruder are set to 245℃, 250℃, 255℃, and 260℃, respectively. Simultaneously, the barrel is vacuumed to a vacuum degree of 0.06 MPa. After water cooling, the mixture is cut into cylindrical products of Φ3mm × Φ3mm to obtain PC / ABS alloy resin.

[0025] The mass ratio of butadiene, styrene, and acrylonitrile is 60:26:14. The melt index of the styrene-acrylonitrile copolymer at 220℃ and 10kg is 60.5g / 10min, the nitrogen content is 7.3%, the bonded acrylonitrile content is 28%, and the number average molecular weight is 60,000.

[0026] Example 2

[0027] Weigh out the following components by mass: 72 parts PC, 18 parts styrene-acrylonitrile copolymer, 6.5 parts butadiene-styrene-acrylonitrile graft copolymer, 0.68 parts pentaerythritol stearate, 0.3 parts β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol, 2.5 parts butadiene-styrene-methyl methacrylate graft copolymer, and 0.02 parts dimethyl silicone oil. Add these components to a high-speed mixer and mix thoroughly for 5 minutes. Then, add the mixture to a twin-screw extruder for blending, melting, extrusion, and granulation. The screw speed is 210–250 r / min. The barrel conveying section, plasticizing section, metering section, and die temperature of the co-rotating twin-screw extruder are set to 245℃, 255℃, 260℃, and 260℃, respectively. Simultaneously, the barrel is vacuumed to a vacuum degree of 0.05 MPa. After water cooling, the mixture is cut into cylindrical products of Φ3mm × Φ3mm to obtain PC / ABS alloy resin.

[0028] The mass ratio of butadiene, styrene, and acrylonitrile is 60:25:15. The melt index of the styrene-acrylonitrile copolymer at 220℃ and 10kg is 62.5g / 10min, the nitrogen content is 7.6%, the bonded acrylonitrile content is 29%, and the number average molecular weight is 57,000.

[0029] Example 3

[0030] Weigh the following components by weight: 67 parts PC, 22 parts styrene-acrylonitrile copolymer, 7 parts butadiene-styrene-acrylonitrile graft copolymer, 0.3 parts pentaerythritol stearate, 0.18 parts β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol, 3.5 parts butadiene-styrene-methyl methacrylate graft copolymer, and 0.02 parts dimethyl silicone oil. Add the above materials to a high-speed mixer and mix thoroughly for 5 minutes. Then, feed the mixture into a twin-screw extruder for blending, melting, extrusion, and granulation. The screw speed is 210–250 r / min. The temperatures of the barrel conveying section, plasticizing section, metering section, and die head of the co-rotating twin-screw extruder are set to 245℃, 250℃, 260℃, and 265℃, respectively. Simultaneously, the barrel is subjected to vacuum treatment to a vacuum degree of 0.06 MPa. After water cooling, the product is cut into cylindrical shapes of Φ3mm × Φ3mm to obtain PC / ABS alloy resin.

[0031] The mass ratio of butadiene, styrene, and acrylonitrile is 60:25:15. The melt index of the styrene-acrylonitrile copolymer at 220℃ and 10kg is 62.5g / 10min, the nitrogen content is 7.6%, the bonded acrylonitrile content is 29%, and the number average molecular weight is 55000.

[0032] Example 4

[0033] Weigh the following components by weight: 55 parts PC, 30 parts styrene-acrylonitrile copolymer, 10 parts butadiene-styrene-acrylonitrile graft copolymer, 0.58 parts pentaerythritol stearate, 0.2 parts β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol, 4.2 parts butadiene-styrene-methyl methacrylate graft copolymer, and 0.02 parts dimethyl silicone oil. Add the above materials to a high-speed mixer and mix thoroughly for 5 minutes. Then, feed the mixture into a twin-screw extruder for blending, melting, extrusion, and granulation. The screw speed is 210–250 r / min. The barrel conveying section, plasticizing section, metering section, and die temperature of the co-rotating twin-screw extruder are set to 250℃, 255℃, 260℃, and 265℃, respectively. Simultaneously, the barrel is subjected to vacuum treatment to a vacuum degree of 0.07 MPa. After water cooling, the product is cut into cylindrical products with a diameter of Φ3mm × Φ3mm to obtain PC / ABS alloy resin.

[0034] The mass ratio of butadiene, styrene, and acrylonitrile is 60:25:15. The melt index of the styrene-acrylonitrile copolymer at 220℃ and 10kg is 67.5g / 10min, the nitrogen content is 7.9%, the bonded acrylonitrile content is 30%, and the number average molecular weight is 52000.

[0035] Example 5

[0036] Weigh the following components by weight: 52 parts PC, 34 parts styrene-acrylonitrile copolymer, 11 parts butadiene-styrene-acrylonitrile graft copolymer, 0.48 parts pentaerythritol stearate, 0.2 parts β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate octadecyl alcohol, 2.3 parts butadiene-styrene-methyl methacrylate graft copolymer, and 0.02 parts dimethyl silicone oil. Add the above substances to a high-speed mixer and mix thoroughly for 5 minutes. Then, feed the mixture into a twin-screw extruder for blending, melting, extrusion, and granulation. The screw speed is 210–250 r / min. The barrel conveying section, plasticizing section, metering section, and die temperature of the co-rotating twin-screw extruder are set to 245℃, 250℃, 260℃, and 270℃, respectively. Simultaneously, the barrel is subjected to vacuum treatment to a vacuum degree of 0.06 MPa. After water cooling, the product is cut into cylindrical shapes of Φ3mm × Φ3mm to obtain PC / ABS alloy resin.

[0037] The mass ratio of butadiene, styrene, and acrylonitrile is 60:25:15. The melt index of the styrene-acrylonitrile copolymer at 220℃ and 10kg is 70.5g / 10min, the nitrogen content is 7.9%, the bonded acrylonitrile content is 30%, and the number average molecular weight is 50,000.

[0038] Table 1 Performance Indicators of PC / ABS Alloy Resin Examples

[0039] Performance indicators Example 1 Example 2 Example 3 Example 4 Example 5 Commercially available ABS <![CDATA[Impact strength kJ / m 2 > 62.6 65.1 70.2 95.8 65.4 25 Impact strength after 200 hours of aging 60.6 62.1 66.2 88.1 59.4 18 Tensile strength MPa 62.2 61 59.8 57.1 56.6 45 Tensile strength after 200 hours of aging 61.7 60.5 58.5 55.7 54.6 42 Elongation at break % 90 85 80 78 70 25 Elongation at break after 200 hours of aging 82 77.2 72 68 60 18 Flexural strength MPa 90.8 87.2 83.1 81.5 81 73 Bending strength after 200 hours of aging 88.2 84.1 80.3 78 76.4 70 Melting flow index g / 10min 10.023 12.34 15.875 18.7 19.58 20 Melt flow index after 200 hours of aging 11.02 15.4 17.75 20.7 22.52 21

[0040] As can be seen from Table 1, the impact strength of the PC / ABS alloy resin prepared by this invention is greater than 62 kJ / m. 2 The impact strength is significantly higher than that of commercially available ABS, meeting the high impact resistance requirements of automotive alloy resins. According to the national standard (GB / T 16422-2-2022) experimental conditions: wavelength range 300nm~400nm; exposure period: 102min drying, 18min spraying; blackboard temperature 65℃, thermal aging performance tests were conducted. It can be seen that the impact strength of the PC / ABS alloy resin prepared by this invention decreased after 200h of aging, but its loss rate was much smaller than that of ordinary commercially available ABS, indicating that the PC / ABS alloy resin prepared by this invention has good weather resistance. The melt index of the PC / ABS alloy resin prepared by this invention is also high, much higher than that of pure PC resin (1~5g / 10min), which is more conducive to improving the processing requirements of PC / ABS alloy resin, allowing for completely uniform injection molding of large parts. After the aging test, due to the loss of the double bond structure of the polybutadiene molecules in the rubber phase, its melt index improves its fluidity due to the breakage of double bonds. Therefore, the aging of the PC / ABS alloy does not affect its processing performance.

[0041] Through append Figure 1 Appendix Figure 2 As can be seen, the PC and ABS resins are well-fused together, with no obvious phase separation. Furthermore, at higher magnification... Figure 2 Rubber particles can be seen, but no phase separation was observed in the continuous phases of PC and SAN.

[0042] The above description, in conjunction with specific preferred embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. Those skilled in the art can make corresponding changes and substitutions based on the technical solutions and inventive concepts of the present invention, and any modifications or substitutions resulting in the same performance or application should be considered within the scope of protection of the present invention.

Claims

1. A PC / ABS alloy resin characterized by: The alloy resin comprises the following components and mass fractions: PC resin 52-81 parts, butadiene-styrene-acrylonitrile graft copolymer 5-11 parts, styrene-acrylonitrile copolymer 10-34 parts, pentaerythritol stearate 0.3-0.8 parts, β-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate 0.18-0.3 parts, butadiene-styrene-methyl methacrylate graft 2.3-4.2 parts, and dimethyl silicone oil 0.02 parts.

2. The PC / ABS alloy resin according to claim 1, characterized in that: The butadiene-styrene-acrylonitrile graft copolymer is prepared by emulsion polymerization grafting method, the grafting rate of the butadiene-styrene-acrylonitrile graft copolymer is 45%-65%, the particle size of the graft copolymer is 220-350 nm, and the mass ratio of butadiene, styrene and acrylonitrile is 52-60:22-30:12-19.

3. The PC / ABS alloy resin according to claim 1, characterized in that: The styrene-acrylonitrile copolymer is prepared by bulk polymerization, and the system contains a solvent, which includes toluene, ethylbenzene and xylene.

4. The PC / ABS alloy resin according to claim 1, characterized in that: The styrene-acrylonitrile copolymer is prepared by bulk polymerization, and the mass ratio of styrene and acrylonitrile is adjusted so that the melt index of the styrene-acrylonitrile copolymer is ≥60 g / 10 min under the condition of 220 ℃ and 10 kg, the N content is ≥7.0%, the bonded acrylonitrile content is 28%-30%, and the number average molecular weight is 50000-60000.

5. The PC / ABS alloy resin according to claim 1, characterized in that: In the styrene-acrylonitrile copolymer, the mass ratio of styrene and acrylonitrile is 60-80:20-40.

6. A method of producing a PC / ABS alloy resin according to claim 1, characterized by: The method comprises the following steps: PC resin, butadiene-styrene-acrylonitrile graft copolymer, styrene-acrylonitrile copolymer, pentaerythritol stearate, β-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, butadiene-styrene-methyl methacrylate graft and dimethyl silicone oil are weighed according to mass fractions, and then are fully mixed in a high-speed mixer for a period of time, and then are added to a double-screw extruder for blending, melting, extruding and granulating to obtain a PC / ABS alloy resin.

7. The method for preparing PC / ABS alloy resin according to claim 6, characterized in that: The screw rotation speed of the double-screw extruder is 210-250 r / min, and the extrusion temperature is 230-270 ℃.

8. The method for preparing PC / ABS alloy resin according to claim 6, characterized in that: The high-speed mixer is used for fully mixing for 3-5 min.

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