A PC / ABS composite material, its preparation method and application

Abstract

This invention discloses a PC / ABS composite material, its preparation method, and its applications, relating to the technical field of plastics. A PC / ABS composite material comprises the following components in parts by weight: 9-86 parts polycarbonate; 3-22 parts saline resin; 4-32 parts ABS resin; 3-8 parts SMA resin; 0.8-14 parts toughening agent; and 3-12 parts flame retardant. The saline resin includes at least one of sodium ethylene methacrylate ionic polymer, zinc ethylene methacrylate ionic polymer, and potassium ethylene methacrylate ionic polymer. The PC / ABS composite material of this invention exhibits excellent weld line strength, flame retardant properties, and mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of plastics, and more particularly to a PC / ABS composite material, its preparation method, and its applications. Background Technology

[0002] Polycarbonate (PC) is a highly transparent amorphous thermoplastic and one of the five major engineering plastics. Aromatic PCs have the best performance; the PC commonly referred to is bisphenol A type aromatic PC, which is also the most widely used PC material. Polycarbonate occupies an extremely important position in the optical field due to its unique high light transmittance, high impact resistance, dimensional stability, and ease of processing and molding. Optical grade polycarbonate (PC) has a light transmittance of up to 89%, a haze of less than 0.3%, and a refractive index of 1.58. Products made from it have excellent optical properties, a colorless and transparent appearance, and excellent infrared transmittance. It has wide applications in automotive headlights, automotive glass, electronic and electrical windows, and mechanical baffles, where high heat resistance, high rigidity, and high infrared transmittance are required.

[0003] PC / ABS alloys possess excellent molding properties, combining the superior performance of both PC and ABS (acrylonitrile-butadiene-styrene copolymer), while avoiding the drawbacks of pure PC such as high viscosity and poor processing performance. With its balanced rigidity and toughness and excellent appearance, it has a wide range of applications in home appliances, consumer electronics, automobiles and other fields.

[0004] However, the multiphase nature of halogen-free flame-retardant PC / ABS means that when multiple melt streams converge and meet during the injection molding of large and complex tea products, weld lines will form in the product. The presence of weld lines not only affects the appearance of the product, but also has a significant impact on its mechanical properties, making it prone to failure in drop and drop ball impact tests. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a PC / ABS composite material, its preparation method, and its applications. The PC / ABS composite material of this invention possesses excellent weld line strength, flame retardant properties, and mechanical properties.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a PC / ABS composite material comprising the following components in parts by weight: Polycarbonate 9-86 parts; Sarin resin 3-22 parts; ABS resin 4-32 parts; SMA resin 3-8 parts; toughening agent 0.8-14 parts; flame retardant 3-12 parts; The sarin resin includes at least one of sodium ethylene methacrylate ionic polymer, zinc ethylene methacrylate ionic polymer, and potassium ethylene methacrylate ionic polymer.

[0007] SMA resin is a random structure copolymer formed by the copolymerization of styrene and maleic anhydride.

[0008] Preferably, the weight-average molecular weight of the SMA resin is 3000-10000, for example, it can be 3000, 4000, 5000, 6000, 7000, 8000, 8500, 9000, 10000, or any two of these values. The weight-average molecular weight is tested according to GB / T 36214-2018, using the volume exclusion method to determine the molecular weight of the polymer.

[0009] More preferably, the weight-average molecular weight of the SMA resin is 3000-9000.

[0010] Preferably, the melt flow index of the ABS resin under the test condition of 220℃ / 10kg is 5-35 g / 10min, for example, it can be 5g / 10min, 10g / 10min, 15g / 10min, 20g / 10min, 25g / 10min, 30g / 10min, 35g / 10min or any two of these values.

[0011] Preferably, the melt index of the sarin resin under the test conditions of 190℃ / 2.16kg is 2-12 g / 10min, for example, it can be 5g / 10min, 6g / 10min, 7g / 10min, 8g / 10min, 9g / 10min, 10g / 10min or any two of these values.

[0012] More preferably, the melt index of the sarin resin under the test conditions of 190℃ / 2.16kg is 5-10 g / 10min.

[0013] Preferably, the polycarbonate has a melt index of 5-70 g / 10min under the test conditions of 300℃ / 1.2kg, for example, it can be 5g / 10min, 10g / 10min, 15g / 10min, 20g / 10min, 25g / 10min, 30g / 10min, 35g / 10min, 40g / 10min, 45g / 10min, 50g / 10min, 60g / 10min, 70g / 10min or any two of these values.

[0014] More preferably, the polycarbonate has a melt index of 10-50 g / 10min.

[0015] In this invention, the melt flow index was measured according to GB / T3682.1-2018.

[0016] Preferably, the polycarbonate is bisphenol A type polycarbonate.

[0017] Preferably, the flame retardant includes at least one of sulfonate flame retardants and phosphorus-containing flame retardants.

[0018] More preferably, the sulfonate flame retardant includes at least one of potassium perfluoroalkyl sulfonate, potassium benzenesulfonylbenzenesulfonate, sodium p-toluenesulfonate, and phosphorus-containing flame retardant, preferably potassium perfluoroalkyl sulfonate, and more preferably potassium perfluorobutyl sulfonate.

[0019] More preferably, the phosphorus-containing flame retardant includes at least one of hexaphenoxane triphosphazene, triphenyl phosphate, resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), and resorcinol bis[bis(2,6-dimethylphenyl phosphate)], and more preferably resorcinol bis[bis(2,6-dimethylphenyl phosphate)].

[0020] Preferably, the toughening agent includes at least one of silicone-based toughening agents, MBS-based toughening agents, and polyethylene acrylate-based toughening agents.

[0021] Preferably, the PC / ABS composite material further includes 0-5 parts of additives.

[0022] Preferably, the additives include 0-1 parts of antioxidant, 0-1 parts of lubricant, and 0-1 parts of flame retardant synergist.

[0023] Preferably, the antioxidant includes hindered phenolic antioxidants and / or phosphite antioxidants.

[0024] Preferably, the hindered phenolic antioxidant includes at least one of antioxidant 1076, antioxidant 1010, antioxidant 330, and antioxidant 2246, and more preferably antioxidant 1076 and antioxidant 1010.

[0025] Preferably, the phosphite antioxidants include antioxidant 168, antioxidant PEP-36, antioxidant 38, and antioxidant 126, and more preferably antioxidant 168 and antioxidant PEP-36.

[0026] Preferably, the lubricant includes at least one of pentaerythritol tetrastearic acid, polyethylene wax, and silicone lubricant.

[0027] Preferably, the flame retardant synergist is polytetrafluoroethylene.

[0028] The amount of polycarbonate used is 9-86 parts, for example, it can be 9 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 72 parts, 75 parts, 80 parts, 86 parts or any two of these values.

[0029] Preferably, the amount of polycarbonate used is 10-85 parts.

[0030] Preferably, the polycarbonate content in the PC / ABS composite material of the present invention is not less than 10% by weight.

[0031] More preferably, the polycarbonate content in the PC / ABS composite material is 40-80% by weight.

[0032] The amount of sarin resin used is 3-22 parts, for example, it can be 3 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 21 parts, 22 parts or any two of these values.

[0033] Preferably, the amount of sarin resin used is 5-20 parts.

[0034] The amount of ABS resin used is 4-32 parts, for example, it can be 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts or any two of these values.

[0035] Preferably, the amount of ABS resin used is 5-30 parts.

[0036] Preferably, the PC / ABS composite material comprises the following components in parts by weight: 50-80 parts polycarbonate; 8-20 parts sarin resin; 10-28 parts ABS resin; 4-6 parts SMA resin; 3-10 parts toughening agent; 6-9 parts flame retardant.

[0037] Preferably, the PC / ABS composite material of the present invention may further include at least one of colorant, weather resistant agent, antistatic agent, and ultraviolet light absorber.

[0038] The PC / ABS composite material of the present invention may include 0-1 parts of colorant, and suitable colorants include, but are not limited to, carbon black, titanium dioxide, zinc sulfide, iron oxide red, titanium yellow and combinations thereof.

[0039] The PC / ABS composite material of the present invention may include 0-1 parts of weathering agent, and suitable weathering agent includes, but is not limited to, hindered amine light stabilizer.

[0040] The PC / ABS composite material of the present invention may include 0-1 parts of antistatic agent, and suitable antistatic agents include, but are not limited to, zinc oxide, manganese dioxide, chromium trioxide and combinations thereof.

[0041] The PC / ABS composite material of the present invention may include 0-1 parts of ultraviolet light absorber. Suitable ultraviolet light absorbers include, but are not limited to, hydroxybenzophenones, benzotriazoles, hydroxybenzotriazines, cyanoacrylates, nanoscale inorganic materials (e.g., titanium oxide, cerium oxide, and zinc oxide) and combinations thereof.

[0042] Secondly, the present invention also discloses a method for preparing PC / ABS composite material, comprising the following steps: After the components are mixed evenly, they are added to a twin-screw extruder for melt mixing, extrusion granulation, and PC / ABS composite material is obtained.

[0043] Preferably, the temperature of the melt mixing is 210-250℃, and the screw speed is 30-300 rpm.

[0044] Thirdly, the present invention also discloses the application of PC / ABS composite material in automobiles, smart speakers, cosmetics, and toys. In particular, the above-mentioned polycarbonate composition can be used to prepare parts with high weld line strength, and is especially suitable for preparing complex structural parts such as automobiles, smart speakers, cosmetics, and toys.

[0045] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention uses polycarbonate and ABS resin as matrix materials. By adding sarin resin and SMA resin, the polarity difference between PC and ABS and other components can be adjusted, improving the compatibility between the components. At the same time, by introducing specific ionic polymers, char formation can be promoted in the condensed phase flame retardant process, effectively improving the flame retardant performance of the composite material. Furthermore, the interface between PC resin and ABS can be optimized, effectively improving the tensile strength and weld line strength of the composite material. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0047] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0048] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0049] Examples 1-18 Examples of the PC / ABS composite material and its preparation method according to the present invention are shown in Table 1.

[0050] The preparation method of the PC / ABS composite material includes the following steps: After the components are mixed evenly, they are added to a twin-screw extruder for melt mixing, extrusion granulation, and PC / ABS composite material is obtained.

[0051] The melting and mixing temperature is 210-250℃, and the screw speed is 300 rpm.

[0052] Comparative Examples 1-7 The only difference between the comparative examples and the embodiments is the type and ratio of components, as shown in Table 2.

[0053] In the components described in each embodiment and comparative example: Polycarbonate 1 is a bisphenol A type polycarbonate: melt index is 5 g / 10 min, grade is PC 2050, and manufacturer is Wanhua Chemical. Polycarbonate 2 is a bisphenol A type polycarbonate: melt index is 20g / 10min, grade is PC H-2000F, and manufacturer is Mitsubishi Chemical. Polycarbonate 3 is a bisphenol A type polycarbonate: melt index is 35g / 10min, grade is PC A1350, and manufacturer is Wanhua Chemical. Polycarbonate 4 is a bisphenol A type polycarbonate: melt index is 60 g / 10 min, grade is PC 2600, and manufacturer is Wanhua Chemical.

[0054] Salin resin 1 is an ionic polymer of sodium ethylene methacrylate: melt index is 10 g / 10 min, grade is 8660, and manufacturer is Dow Chemical.

[0055] Salin resin 2 is an ionic polymer of zinc ethylene methacrylate: melt index is 5.5 g / 10 min, grade is 1705, and manufacturer is Dow Chemical.

[0056] Salin resin 3 is an ionic polymer of ethylene sodium methacrylate: melt index is 2.5 g / 10 min, grade is 1605, and manufacturer is Dow Chemical. Ethylene-methylacrylic acid copolymer: melt index of 10 g / 10 min, grade 0910, manufactured by Dow Chemical.

[0057] ABS resin 1: melt index is 30g / 10min, grade is ABS 8391, manufacturer is North China Huajin Chemical Co., Ltd. ABS resin 2: melt index is 20g / 10min, grade is ABS KF-725, manufacturer is Kingfa Science & Technology; ABS resin 3: melt index is 10g / 10min, grade is ABS 275, manufacturer is Shanghai Gaoqiao.

[0058] SMA resin 1 is SMA-1#: weight average molecular weight is 5500, grade is SMA-1000, manufacturer is Krevili; SMA resin 2 is SMA-3#: weight average molecular weight is 7000, grade is SMA 1440, manufacturer is Krevili; SMA resin 3 is SMA-2#: weight average molecular weight is 7500, grade is SMA-2000, manufacturer is Krevili; SMA resin 4 is SMA-5#: weight average molecular weight is 9000, grade is SMA 2625, manufacturer is Krevili; SMA resin 5 is SMA-4#: weight average molecular weight is 9500, grade is SMA 3000, and manufacturer is Clayville.

[0059] Toughening agent 1 is MBS: brand name EM500, manufacturer is Zhongyuan Chemical.

[0060] Toughening agent 2 is a silicon-based toughening agent: brand name MR-01, manufacturer is Mitsubishi Chemical.

[0061] Flame retardant 1 is bisphenol A-bis(diphenyl phosphate): brand name WSFR-BDP, manufacturer is Zhejiang Wansheng Co., Ltd.

[0062] Flame retardant 2 is benzenesulfonyl benzenesulfonyl potassium: brand name Metro-KSS, manufacturer is Quansheng Polycarbonate Technology Co., Ltd.; Flame retardant 3 is potassium perfluorobutyl sulfonate: brand name FR-2025, manufacturer is 3M.

[0063] The flame retardant synergist is polytetrafluoroethylene (PTFE): brand name FD3150, manufactured by Shanghai Luju Polymer Technology Co., Ltd.

[0064] The antioxidants include hindered phenolic antioxidants and phosphite antioxidants in a mass ratio of 1:1; the hindered phenolic antioxidant is β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester, antioxidant 1076, commercially available; the phosphite antioxidant is tris(2,4-di-tert-butyl)phosphite phenyl ester, antioxidant 168, commercially available.

[0065] The lubricant is pentaerythritol tetrastearate, which is commercially available.

[0066] Unless otherwise specified, all components and raw materials used in the embodiments and comparative examples of this invention are commercially available, and the same type of components and raw materials are used in each parallel experiment.

[0067] Table 1 Table 2 To verify the performance of the PC / ABS composite material described in this invention, the PC / ABS composite materials prepared in each embodiment and comparative example were injection molded into specimens for testing the following properties.

[0068] Performance testing methods: 1. Tensile strength and weld line strength: Tested in accordance with ISO 527-2019; the weld line specimens are prepared by injection molding of specimens of the same size using a double-injection tensile specimen mold, with a pre-set molten glue pooling in the middle of the specimen to simulate the state of glue pooling in plastic parts during injection molding.

[0069] 2. Flame retardant performance: Tested in accordance with UL94-2018, using injection-molded 1.5mm thick burning test strips.

[0070] The performance parameters obtained from the above tests are shown in Table 3.

[0071] Table 3 As can be seen from Examples 1-18, the weld line strength of the PC / ABS composite material of the present invention is above 60MPa, the tensile strength is above 61MPa, and the flame retardant rating is V-0, indicating that the PC / ABS composite material of the present invention has excellent flame retardant properties, tensile strength, and weld line strength.

[0072] Comparing Comparative Example 1 with Example 2, it can be seen that the use of ethylene methacrylate copolymer in Comparative Example 1 will affect the weld line strength and flame retardant properties of the PC / ABS composite material. This indicates that only by using ionic polymers and SMA resin to compound the PC / ABS composite material can it achieve excellent flame retardant properties, tensile strength and weld line strength.

[0073] Comparing Comparative Examples 2-3 with Example 2, it can be seen that the PC / ABS composite material has reduced weld line strength because SMA resin was not added in Comparative Example 2 and Sarin resin was not added in Comparative Example 3. This shows that only by using Sarin resin and SMA resin in combination can the PC / ABS composite material have excellent flame retardant properties, tensile strength and weld line strength. The absence of any one of these substances will prevent the achievement of the effect of the present invention.

[0074] Comparing Comparative Examples 4-5 and 6-7 with Example 2, it can be seen that if the content of sarin resin is too low or too high, or the content of SMA resin is too low or too high, it will affect the performance of PC / ABS composite material. Therefore, by controlling the content of sarin resin and SMA resin within the range defined by the present invention, PC / ABS composite material can have excellent flame retardant properties, tensile strength and weld line strength.

[0075] 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. A PC / ABS composite material, characterized in that, Includes the following components in parts by weight: Polycarbonate 9-86 parts; Sarin resin 3-22 parts; ABS resin 4-32 parts; SMA resin 3-8 parts; toughening agent 0.8-14 parts; flame retardant 3-12 parts; The sarin resin includes at least one of sodium ethylene methacrylate ionic polymer, zinc ethylene methacrylate ionic polymer, and potassium ethylene methacrylate ionic polymer.

2. The PC / ABS composite material as described in claim 1, characterized in that, The weight-average molecular weight of the SMA resin is 3000-10000.

3. The PC / ABS composite material as described in claim 1, characterized in that, The melt flow index of the ABS resin under the test conditions of 220℃ / 10kg is 5-35 g / 10min.

4. The PC / ABS composite material as described in claim 1, characterized in that, The melt index of the sarin resin under the test conditions of 190℃ / 2.16kg is 2-12 g / 10min.

5. The PC / ABS composite material as described in claim 1, characterized in that, The polycarbonate has a melt index of 5-70 g / 10min under the test conditions of 300℃ / 1.2kg.

6. The PC / ABS composite material as described in claim 1, characterized in that, The flame retardant includes at least one of sulfonate flame retardants and phosphorus-containing flame retardants.

7. The PC / ABS composite material as described in claim 1, characterized in that, The toughening agent includes at least one of the following: organosilicon toughening agents, MBS-type toughening agents, and polyethylene acrylate toughening agents.

8. The PC / ABS composite material as described in claim 1, characterized in that, The PC / ABS composite material also includes 0-5 parts of additives.

9. A method for preparing a PC / ABS composite material as described in any one of claims 1-8, characterized in that, Includes the following steps: After the components are mixed evenly, they are added to a twin-screw extruder for melt mixing, extrusion granulation, and PC / ABS composite material is obtained.

10. The application of the PC / ABS composite material according to any one of claims 1-8 in the manufacture of automotive parts, smart speakers, cosmetics, and toys.

Images