A polycarbonate composite material, a preparation method and application thereof

Abstract

The present application relates to a kind of polycarbonate composite material and its preparation method and application.The polycarbonate composite material includes the following weight parts of component: first polycarbonate 50~90 parts, ABS resin 10~50 parts, compatibilizer 1~5 parts.The polycarbonate composite material has low screw column cracking proportion, high screw column failure torque, and is suitable for preparing different size specifications screw column.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and more specifically, to a polycarbonate composite material, its preparation method, and its application. Background Technology

[0002] Polycarbonate, as an amorphous polymer, exhibits high dimensional stability, good impact toughness, and paintability; however, its processing temperature is relatively high. Introducing ABS resin into polycarbonate yields PC / ABS alloys. The addition of ABS resin lowers the processing temperature and improves the material's processability. PC / ABS alloys are widely used in automotive parts.

[0003] Threaded assembly is one of the assembly methods for automotive parts, typically achieved through self-tapping screws. However, assembling parts made of PC / ABS alloy materials using threads presents a significant problem: during the actual molding process, the weld line defects in the stud structure cannot be completely eliminated. This area is usually the weakest point in the structure, making it prone to cracking during tapping—a phenomenon known as stud tapping cracking. Stud tapping cracking reflects the performance limitations of the stud's weakest point; if the cracking rate is too high, the part will become unusable.

[0004] Besides stud tapping cracking, the stud failure torque value is also a major performance concern. During tapping, the stud experiences increasing tension along the circumferential direction; the critical value of this tension is the stud failure torque value. A higher stud failure torque value indicates a higher upper limit for the component's value and a wider range of applications. Existing technologies primarily focus on the tapping cracking performance of studs made of PC / ABS alloy materials, paying little or no attention to the stud failure torque value, as exemplified by patent CN107163533A.

[0005] Furthermore, in actual component structural design, studs come in various sizes to meet different application scenarios. Different sizes of studs experience different stresses during the tapping process, therefore, it is necessary to pay attention to the cracking performance and failure torque values ​​of studs of different sizes.

[0006] Therefore, providing a PC / ABS alloy material with a low screw post cracking rate, high screw post failure torque, and applicability to screw posts of different sizes and specifications is of great significance for market expansion. Summary of the Invention

[0007] The primary objective of this invention is to overcome the problems of high cracking rate, low failure torque, and insufficient attention to the adaptability of screw studs of different sizes and specifications in current PC / ABS alloy materials, and to provide a polycarbonate composite material.

[0008] A further object of the present invention is to provide a method for preparing the above-mentioned polycarbonate composite material.

[0009] A further object of the present invention is to provide the application of the above-mentioned polycarbonate composite material in the preparation of automotive door panel frame parts or headlight housing parts.

[0010] The above-mentioned objective of the present invention is achieved through the following technical solution:

[0011] A polycarbonate composite material comprising the following components in parts by weight:

[0012] 50-90 parts of the first polycarbonate

[0013] 10-50 parts of ABS resin

[0014] 1-5 parts compatibilizer

[0015] The melt flow index of the first polycarbonate, measured at 300°C and 1.2 kg, was 3–10 g / 10 min.

[0016] The acrylonitrile content in the ABS resin is 22-25 wt%.

[0017] The compatibilizer is maleic anhydride-grafted ABS resin.

[0018] The inventors of this invention discovered through research that selecting a first polycarbonate with a melt index (3-10 g / 10 min) within a certain range, due to its larger molecular weight, allows it to interpenetrate between the first polycarbonate phase and the ABS resin phase, improving the bonding force between the two and thus increasing the screw failure torque of the polycarbonate composite material. Simultaneously, by controlling the acrylonitrile content in the ABS resin within this melt index range, good compatibility between the first polycarbonate and ABS resin can be achieved, thereby reducing the screw cracking rate of the polycarbonate composite material. Furthermore, adding maleic anhydride-grafted ABS resin as a compatibilizer to the polycarbonate composite material further increases the screw failure torque and screw cracking rate.

[0019] Furthermore, the polycarbonate composite material of the present invention can be used to prepare screw studs of different sizes and specifications, while maintaining a low screw stud cracking rate and a high screw stud failure torque.

[0020] That is, the polycarbonate composite material of the present invention has a low screw post cracking rate, a high screw post failure torque, and is suitable for preparing screw posts of different sizes and specifications.

[0021] In this invention, the first polycarbonate is used as the main resin, and its content in the polycarbonate composite material is more than 45 wt%. The specific amount of the first polycarbonate can be 50 parts, 60 parts, 70 parts, 80 parts or 90 parts.

[0022] In this invention, the melt index of the first polycarbonate can be measured according to standard ISO1133-1:2022.

[0023] Commonly used types of polycarbonate in the art can be used as the first polycarbonate of the present invention, including but not limited to bisphenol A type polycarbonate.

[0024] In this invention, the acrylonitrile content in the ABS resin is obtained by FT-IR analysis. After calculating the absorption peak data of the functional groups, it is converted into the content using a standard equation established with a known proportion of ABS.

[0025] The specific amount of ABS resin added can be 10 parts, 20 parts, 30 parts, 40 parts, or 50 parts. The specific amount of compatibilizer added can be 1 part, 2 parts, 3 parts, 4 parts, or 5 parts.

[0026] Preferably, the maleic anhydride grafting rate in the maleic anhydride-grafted ABS resin is 1.2 to 1.5 wt%; the grafting rate can be determined by titration.

[0027] Preferably, the polycarbonate composite material further includes 2 to 8 parts of a second polycarbonate; the melt index of the second polycarbonate measured at 300°C and 1.2 kg is 20 to 30 g / 10 min.

[0028] Commonly used types of polycarbonate in the art can be used as the second polycarbonate of the present invention, including but not limited to bisphenol A type polycarbonate.

[0029] In this invention, the melt index of the second polycarbonate can be measured according to standard ISO1133-1:2022.

[0030] Preferably, the melt flow index of the first polycarbonate, measured at 300°C and 1.2 kg, is 8–10 g / 10 min. By controlling the melt flow index of the first polycarbonate within this range, the cracking rate of the screw stud can be further reduced while maintaining a high screw stud failure torque in the polycarbonate composite material.

[0031] More preferably, the mass ratio of the first polycarbonate to the second polycarbonate is 1:(0.03 to 0.14).

[0032] More preferably, the mass ratio of the first polycarbonate to the second polycarbonate is 1:(0.06 to 0.14). By controlling the mass ratio of the first polycarbonate to the second polycarbonate within this range, the cracking rate of screw studs of different sizes of polycarbonate composite materials is lower.

[0033] Preferably, the rubber content of the ABS resin is 18-26 wt%; more preferably 18-21 wt%.

[0034] Optionally, the melt flow index of the ABS resin measured at 220°C and 10 kg is 5 to 30 g / 10 min.

[0035] In this invention, the melt flow index of ABS resin can be measured according to standard ISO 1133-1 2022.

[0036] Preferably, the polycarbonate composite material further includes 0.2 to 4 parts of other additives.

[0037] More preferably, the other additives are at least one of lubricant, antioxidant, weathering agent or colorant.

[0038] Optionally, the lubricant is at least one of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax, EVA wax, oleamide, erucamide, ethylene bis-stearamide, silicone lubricant, or pentaerythritol stearate.

[0039] Optionally, the antioxidant is at least one of the following: tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, di(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra[methylene(3,5-di-tert-butyl-4-hydroxycinnamate)]methane, distearyl thiopropionate, dilauryl thiopropionate, di(tetrazyl) thiopropionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate.

[0040] Optionally, the weathering agent is at least one of 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole or 2-hydroxy-4-n-octoxybenzophenone.

[0041] Optionally, the color powder is at least one of inorganic color powder or organic color powder.

[0042] Optionally, the inorganic pigment is at least one of zinc oxide, titanium dioxide, iron oxide, zinc sulfide, aluminate, sodium thiosilicate, sulfate, chromate, carbon black, zinc ferrite, ultramarine blue, pigment brown 24, pigment red 101, and pigment yellow 119.

[0043] Optionally, the organic pigment is at least one selected from azo, diazo, quinacridone, perylene, naphthalenetetraic acid, flavanone, isoindolone, tetrachloroisoindolone, anthraquinone, anthraquinone, dioxazine, phthalocyanine, azo lake, pigment blue 60, pigment red 122, pigment red 149, pigment red 177, pigment red 179, pigment red 202, pigment white 29, pigment blue 15, pigment green 7, pigment yellow 147, or pigment yellow 150.

[0044] The preparation method of the above-mentioned polycarbonate composite material includes the following steps: mixing the components, melt extruding, and granulating to obtain the polycarbonate composite material.

[0045] The application of the above-mentioned polycarbonate composite material in the preparation of automotive door panel frame parts or headlight housing parts is also within the scope of protection of this invention.

[0046] A polycarbonate part comprising a screw post structure and / or a screw hole structure, wherein the polycarbonate part is manufactured by processing and molding the aforementioned polycarbonate composite material.

[0047] Compared with the prior art, the beneficial effects of the present invention are:

[0048] The polycarbonate composite material of the present invention has a low screw post cracking rate, a high screw post failure torque, and is suitable for preparing screw posts of different sizes and specifications. Detailed Implementation

[0049] To more clearly and completely describe the technical solution of the present invention, the present invention will be further described in detail below through specific embodiments. It should be understood that the specific embodiments described herein are only for explaining the present invention and are not intended to limit the present invention. Various changes can be made within the scope of the claims of the present invention.

[0050] The reagents used in the various embodiments and comparative examples of this invention are described below:

[0051] First polycarbonate 1#: PC 7030PJ, Mitsubishi, melt index is 3g / 10min;

[0052] First polycarbonate 2#: PC S-2000F, Mitsubishi, melt index is 10g / 10min;

[0053] First polycarbonate 3#: PC 2100, Wanhua, melt index is 8g / 10min;

[0054] Second polycarbonate 1#: PC H-2000F, Mitsubishi, melt index is 20g / 10min;

[0055] Second polycarbonate 2#: PC H-3000F, Mitsubishi, melt index is 30g / 10min;

[0056] ABS resin #1: ABS275, Gaoqiao Petrochemical, with a rubber content of 19.57% and an acrylonitrile content of 22.31%; melt index of 8 g / 10 min.

[0057] ABS resin #2: ABSD-150, Guoqiao, with a rubber content of 20.55% and an acrylonitrile content of 24.95%; melt index of 27 g / 10 min.

[0058] ABS resin #3: ABS 8434, Gaoqiao Petrochemical, rubber content 25.25%, acrylonitrile content 21.74%; melt index 14g / 10min.

[0059] ABS resin #4: ABS PA-757, Chi Mei, with a rubber content of 20.07% and an acrylonitrile content of 28.40%; melt index of 18 g / 10 min.

[0060] Compatibilizer 1#: Maleic anhydride grafted onto ABS, KT-2, Shenyang Ketong, the grafting rate of maleic anhydride is 1.3%, determined by titration.

[0061] Compatibilizer 2#: Styrene-maleic anhydride copolymer, SMA-700, Jiaxing Huawen;

[0062] Lubricant: Pentaerythritol stearate, commercially available;

[0063] Antioxidant: Tetramethylene (3,5-di-tert-butyl-4-hydroxycinnamate)methane, commercially available;

[0064] Weather resistant agent: 2-(2H-benzotriazol-2-yl)-4,6-di(1-methyl-1-phenylethyl)-phenol, commercially available.

[0065] Unless otherwise specified, all components (e.g., lubricants, antioxidants, weathering agents) used in the parallel embodiments and comparative examples are the same commercially available products.

[0066] The performance of the polycarbonate composite materials provided in the embodiments and comparative examples of the present invention was determined according to the following test methods:

[0067] Screw stud tapping test: 4.2mm screws were used, with a total tapping angle of 3000°. The studs were M4 size, with two inner diameter sizes: 3.14mm and 3.02mm. Ten samples of each size were tested. The failure torque was taken as the average of the test values. The cracking ratio was defined as the proportion of studs exhibiting tapping cracks.

[0068] The polycarbonate composite materials of the embodiments and comparative examples of the present invention were prepared by the following preparation method:

[0069] According to the formula, each component is put into a high-speed mixer and mixed for 5 minutes at a speed of 500 r / min to obtain a mixture. The mixture is then extruded and granulated by a twin-screw extruder. The temperatures of each zone of the screw are set sequentially to 230℃, 230℃, 240℃, 240℃, 250℃, 240℃, 230℃, 230℃, and 220℃, with a speed of 600 rpm, to obtain the polycarbonate composite material.

[0070] Examples 1-11

[0071] Examples 1-11 provide a series of polycarbonate composite materials, the formulations of which are shown in Table 1.

[0072] Table 1. Formulations (parts by weight) for Examples 1-11

[0073] .

[0074] Comparative Examples 1-6

[0075] Comparative Examples 1–6 provide a series of polycarbonate composite materials, the formulations of which are shown in Table 2.

[0076] Table 2 shows the formulations (parts by weight) for Comparative Examples 1–6.

[0077]

[0078]

[0079] The properties of the polycarbonate composite materials of each embodiment and comparative example were determined according to the test methods mentioned above, and the test results are shown in Table 3.

[0080] Table 3. Performance test results of polycarbonate composite materials in each example and comparative example.

[0081]

[0082] As can be seen from Table 3:

[0083] The cracking rate of screw studs of different sizes in the polycarbonate composite materials of Examples 1 to 11 is all below 30%, the failure torque of screw studs with an inner diameter of 3.14 is above 2.56 N·m, and the failure torque of screw studs with an inner diameter of 3.02 is above 2.67 N·m. This shows that the polycarbonate composite material of the present invention has a low screw stud cracking rate, a high screw stud failure torque, and is suitable for preparing screw studs of different sizes.

[0084] In Comparative Example 1, the melt flow index of the added polycarbonate was too high, resulting in a 100% cracking rate for screw studs of different sizes in the obtained polycarbonate composite material, and the failure torque of the screw studs of different sizes was not high. In Comparative Examples 2 and 3, the acrylonitrile content of the ABS resin was either too low or too high, leading to poor compatibility with polycarbonate. This resulted in a high cracking rate for screws with an inner diameter of 3.02 mm in the obtained polycarbonate composite material, and the failure torque of the screw studs of different sizes was lower than that in Example 1. In Comparative Example 4, the compatibilizer used was unsuitable, resulting in a high cracking rate for screws with an inner diameter of 3.02 mm in the obtained polycarbonate composite material, and the failure torque of the screw studs of different sizes was lower than that in Example 1. Comparative Examples 5 and 6 are not alloy material systems, but rather single resin systems. In Comparative Example 5, the base resin only used polycarbonate. Although its screw stud tapping performance was good, this material had poor flowability and was difficult to process. In actual processing, the injection-molded samples were prone to dimensional or appearance defects.

[0085] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A polycarbonate component comprising a screw post structure and / or a screw hole structure, characterized in that, The polycarbonate component is manufactured by processing and molding a polycarbonate composite material. The polycarbonate composite material comprises the following components in parts by weight: 50-60 parts of the first polycarbonate, 35-50 parts of ABS resin 2-8 parts of the second polycarbonate, 1-5 parts compatibilizer; The content of the first polycarbonate in the polycarbonate composite material is 45 wt% or more; The melt flow index of the first polycarbonate, measured at 300°C and 1.2 kg, was 3~10 g / 10 min. The melt flow index of the second polycarbonate, measured at 300°C and 1.2 kg, was 20-30 g / 10 min. The mass ratio of the first polycarbonate to the second polycarbonate is 1:(0.06~0.14). The melt flow index of the ABS resin measured at 220℃ and 10kg was 5~30g / 10min; The acrylonitrile content in the ABS resin is 22-25 wt%. The compatibilizer is maleic anhydride-grafted ABS resin.

2. The polycarbonate part according to claim 1, characterized in that, The rubber content of the ABS resin is 18~26wt%.

3. The polycarbonate part according to claim 1, characterized in that, The polycarbonate composite material also includes 0.2 to 4 parts of other additives.

4. The polycarbonate article according to any one of claims 1 to 3, characterized in that, The preparation method of the polycarbonate composite material includes the following steps: mixing the components, melt extruding, and granulating to obtain the polycarbonate composite material.

5. The polycarbonate part according to claim 1, characterized in that, The polycarbonate component is a car door panel frame part or a headlight housing part.

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