An antistatic PC / ABS composite material and its preparation method

Abstract

This invention relates to the field of polymer materials technology and discloses an antistatic PC / ABS composite material and its preparation method. The PC / ABS composite material of this invention comprises the following raw materials in parts by weight: 45-65 parts PC resin, 15-25 parts ABS resin, 5-10 parts composite macromolecular antistatic agent, 4-8 parts toughening agent, 1-3 parts antioxidant, 0.5-1.5 parts lubricant, 3-7 parts inorganic filler, and 1-2 parts coupling agent. The composite macromolecular antistatic agent added to this composite material differs from the addition of traditional small-molecule antistatic agents and conductive fillers, possessing a permanent antistatic effect, good compatibility, and minimal impact on mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to an antistatic PC / ABS composite material and its preparation method. Background Technology

[0002] Antistatic PC / ABS composites are a class of multifunctional engineering plastics developed by introducing antistatic properties into a blend system of polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS). The blend of PC and ABS combines the excellent mechanical strength, heat resistance, and dimensional stability of PC with the good processing flow and cost advantages of ABS, making it widely used in electronics, automotive parts, and office equipment.

[0003] However, traditional PC / ABS, as a polymeric insulating material, typically has a surface resistivity of 10. 15 Electrostatic discharge (ESD) values ​​above Ω are highly susceptible to accumulation due to friction or contact, leading to dust adsorption on the product surface, affecting its appearance, and potentially causing signal interference, component breakdown, or even fire and explosion hazards in precision electronic environments. Therefore, antistatic modification of PC / ABS materials is an inevitable technical direction for expanding their application range and meeting the modern industrial requirements for material safety and reliability. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides an antistatic PC / ABS composite material and its preparation method.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] An antistatic PC / ABS composite material comprises the following raw materials in parts by weight: 45-65 parts PC resin, 15-25 parts ABS resin, 5-10 parts composite macromolecular antistatic agent, 4-8 parts toughening agent, 1-3 parts antioxidant, 0.5-1.5 parts lubricant, 3-7 parts inorganic filler, and 1-2 parts coupling agent. Furthermore, the toughening agent is one of MBS, ABS-g-MAH, or POE; Furthermore, the antioxidant is one or two of antioxidant 1010, antioxidant 1076, antioxidant 168 or antioxidant 1098; Furthermore, the lubricant is silicone powder; Furthermore, the inorganic filler is either talc powder or mica powder; Furthermore, the coupling agent is one of a silane coupling agent or a titanate coupling agent; Furthermore, the composite macromolecular antistatic agent is prepared by the following steps: Step A1: Mix imidazole and allyl acrylate separately in methanol and stir until homogeneous, and label them as imidazole solution and allyl acrylate solution; under nitrogen conditions, add allyl acrylate solution to imidazole solution and stir until homogeneous, then heat to 45℃ and stir continuously for 3-4 hours, then evaporate by rotary evaporation and dry to obtain allyl acrylate imidazole. Furthermore, in step A1, the molar ratio of imidazole to allyl acrylate is 1:1-1.2; Step A2: Allyl imidazole is stirred thoroughly in acetonitrile, then heated to 50-60℃, 1-chlorobutane is added, and the mixture is refluxed at 80-85℃ for 3.5-4.5 hours. The solvent is removed by rotary evaporation to obtain allyl imidazole quaternary ammonium salt. Furthermore, in step A2, the molar ratio of allyl ester imidazole to 1-chlorobutane is 1:1; Step A3: Add dimethyl phosphate to 1,4-dioxane and heat to 50°C. Under nitrogen protection, gradually add allyl polyoxyethylene ether and stir under reflux for 4-6 hours. Remove the solvent by rotary evaporation and dry to obtain the allyl polyether derivative. Furthermore, in step A3, the molar ratio of dimethyl phosphate to allyl polyoxyethylene ether is 1:1; Step A4: Under nitrogen atmosphere, allyl ester imidazole quaternary ammonium salt, allyl polyether derivative, maleic anhydride and modified conductive filler are mixed in xylene, then transferred to an oil bath and heated to 65°C. Azobisisobutyronitrile is then added and stirred for 10 hours. Methyl tert-butyl ether ethanol solution is added and stirred for 10 minutes. The mixture is then filtered, washed and dried to obtain the composite macromolecular antistatic agent. Further, in step A4, the molar ratio of allyl ester imidazole quaternary ammonium salt, allyl polyether derivative, maleic anhydride, and modified conductive filler is 0.1-0.3:0.05-0.2:0.1:0.1-0.2, and the amount of azobisisobutyronitrile is 0.08wt%-1.2wt% of the total reactants. Further, in step A4, the volume ratio of methyl tert-butyl ether to ethanol in the methyl tert-butyl ether ethanol solution is 5:1; Furthermore, the modified conductive filler in step A4 is a conductive filler treated with silane coupling agent KH570, wherein the conductive filler is one of carbon nanotubes, graphene oxide, or carbon nanofibers.

[0007] A method for preparing an antistatic PC / ABS composite material includes the following steps: Step S1: Weigh the raw materials according to the weight parts, mix the PC resin, ABS resin, toughening agent and inorganic filler evenly, and then put them into the internal mixer and internally mix at 180-220℃ for 5-8 minutes to obtain the premix. Step S2: Mix the composite macromolecular antistatic agent, antioxidant, lubricant and coupling agent with the premix, then put it into a twin-screw extruder for extrusion granulation, and dry it to obtain the antistatic PC / ABS composite material. The temperature of the twin-screw extruder is 210-260℃.

[0008] The beneficial effects of this invention are: The PC / ABS composite material of this invention is made by using PC resin and ABS resin as the main resin base, and adding toughening agents, inorganic fillers, composite macromolecular antistatic agents, antioxidants, lubricants and coupling agents. The composite macromolecular antistatic agent added to this composite material is different from the addition of traditional small molecule antistatic agents and conductive fillers. It has a permanent antistatic effect, good compatibility and little impact on mechanical properties.

[0009] In this invention, the composite macromolecular antistatic agent, during melt blending, exhibits excellent compatibility and uniform dispersion with PC / ABS. The conductive filler also achieves excellent dispersion due to chemical bonding and steric hindrance, thus endowing the composite material with permanent antistatic properties. The main chain of the composite macromolecular antistatic agent acts as an "anchor" and framework, achieving good compatibility and strong bonding with the PC / ABS matrix through polar interactions and hydrogen bonds, preventing the precipitation of small molecules. The hydrophilic polyether segments and phosphate groups in the allyl polyether derivative possess a certain degree of hygroscopicity, efficiently adsorbing moisture from the environment and reducing the surface resistivity of the material. The ether bonds can also form hydrogen bonds with water molecules and themselves, dissociating ions provided by the quaternary ammonium salt and acting as channels for ion hopping transport, providing bulk ionic conductivity independent of surface migration. Furthermore, the modified conductive filler can penetrate and connect these isolated ionic conductive "islands" in the composite material, establishing "bridges" between the electronic conductive network and the ionic conductive region, forming a hybrid conductive network and significantly reducing the overall resistance. In addition, the introduction of maleic anhydride improves the compatibility of antistatic agents in composite materials, thereby indirectly improving the antistatic properties of the matrix. Detailed Implementation

[0010] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0011] The modified conductive filler in the following examples was prepared by the following steps: 1g of carbon nanotubes were ultrasonically dispersed evenly in a mixture of 30mL ethanol and 6mL water, then 0.3mL KH570 was added, and the mixture was heated to 40℃ and stirred for 5h. After filtration, washing and drying, the modified conductive filler was obtained.

[0012] Example 1: The composite macromolecular antistatic agent was prepared by the following steps: Step A1: Mix 0.1 mol imidazole and 0.1 mol allyl acrylate separately in 50 mL of methanol and stir until homogeneous. These are denoted as imidazole solution and allyl acrylate solution, respectively. Under nitrogen atmosphere, add allyl acrylate solution to imidazole solution and stir until homogeneous. Then heat to 45℃ and stir continuously for 3 hours. After rotary evaporation and drying, allyl acrylate imidazole is obtained. Step A2: 0.1 mol allyl imidazole was stirred thoroughly in 50 mL of acetonitrile, then heated to 50 °C, 0.1 mol 1-chlorobutane was added, and the mixture was refluxed at 80 °C for 3.5 h. The solvent was removed by rotary evaporation to obtain allyl imidazole quaternary ammonium salt. Step A3: Add 0.1 mol of dimethyl phosphate to 100 mL of 1,4-dioxane and heat to 50 °C. Under nitrogen protection, gradually add 0.1 mol of allyl polyoxyethylene ether and stir under reflux for 4 h. Remove the solvent by rotary evaporation and dry to obtain the allyl polyether derivative. Step A4: Under nitrogen atmosphere, mix 0.1 mol allyl ester imidazole quaternary ammonium salt, 0.05 mol allyl polyether derivative, 0.1 mol maleic anhydride, and 0.1 mol modified conductive filler in 200 mL xylene. Then transfer the mixture to an oil bath and heat it to 65 °C. Add azobisisobutyronitrile and stir for 10 h. Add 60 mL of methyl tert-butyl ether ethanol solution (the volume ratio of methyl tert-butyl ether to ethanol is 5:1) and stir for 10 min. Filter, wash, and dry to obtain the composite macromolecular antistatic agent. The amount of azobisisobutyronitrile is 0.08 wt% of the total reactants.

[0013] Example 2: The composite macromolecular antistatic agent was prepared by the following steps: Step A1: Mix 0.1 mol imidazole and 0.11 mol allyl acrylate separately in 50 mL of methanol and stir until homogeneous. These are denoted as imidazole solution and allyl acrylate solution, respectively. Under nitrogen atmosphere, add allyl acrylate solution to imidazole solution and stir until homogeneous. Then heat to 45℃ and stir continuously for 3.5 h. After rotary evaporation and drying, allyl acrylate imidazole is obtained. Step A2: 0.1 mol allyl imidazole was stirred thoroughly in 50 mL of acetonitrile, then heated to 55 °C, 0.1 mol 1-chlorobutane was added, and the mixture was refluxed at 85 °C for 4 h. The solvent was removed by rotary evaporation to obtain allyl imidazole quaternary ammonium salt. Step A3: Add 0.1 mol of dimethyl phosphate to 100 mL of 1,4-dioxane and heat to 50 °C. Under nitrogen protection, gradually add 0.1 mol of allyl polyoxyethylene ether and reflux and stir for 4-6 h. Remove the solvent by rotary evaporation and dry to obtain the allyl polyether derivative. Step A4: Under nitrogen atmosphere, 0.2 mol of allyl ester imidazole quaternary ammonium salt, 0.1 mol of allyl polyether derivative, 0.1 mol of maleic anhydride, and 0.15 mol of modified conductive filler were mixed in 200 mL of xylene. The mixture was then transferred to an oil bath and heated to 65 °C. Azobisisobutyronitrile was added and stirred for 10 h. 60 mL of methyl tert-butyl ether ethanol solution (the volume ratio of methyl tert-butyl ether to ethanol was 5:1) was added and stirred for 10 min. The mixture was then filtered, washed, and dried to obtain the composite macromolecular antistatic agent. The amount of azobisisobutyronitrile used was 0.1 wt% of the total reactants.

[0014] Example 3: The composite macromolecular antistatic agent was prepared by the following steps: Step A1: Mix 0.1 mol imidazole and 0.12 mol allyl acrylate separately in 50 mL of methanol and stir until homogeneous. These are denoted as imidazole solution and allyl acrylate solution, respectively. Under nitrogen atmosphere, add allyl acrylate solution to imidazole solution and stir until homogeneous. Then heat to 45℃ and stir continuously for 4 hours. After rotary evaporation and drying, allyl acrylate imidazole is obtained. Step A2: 0.1 mol allyl imidazole was stirred thoroughly in 50 mL of acetonitrile, then heated to 60 °C, 0.1 mol 1-chlorobutane was added, and the mixture was refluxed at 85 °C for 4.5 h. The solvent was removed by rotary evaporation to obtain allyl imidazole quaternary ammonium salt. Step A3: Add 0.1 mol of dimethyl phosphate to 100 mL of 1,4-dioxane and heat to 50 °C. Under nitrogen protection, gradually add 0.1 mol of allyl polyoxyethylene ether and stir under reflux for 6 h. Remove the solvent by rotary evaporation and dry to obtain the allyl polyether derivative. Step A4: Under nitrogen atmosphere, 0.3 mol of allyl ester imidazole quaternary ammonium salt, 0.2 mol of allyl polyether derivative, 0.3 mol of maleic anhydride, and 0.2 mol of modified conductive filler were mixed in 200 mL of xylene. The mixture was then transferred to an oil bath and heated to 65 °C. Azobisisobutyronitrile was added and stirred for 10 h. 60 mL of methyl tert-butyl ether ethanol solution (the volume ratio of methyl tert-butyl ether to ethanol was 5:1) was added and stirred for 10 min. The mixture was then filtered, washed, and dried to obtain the composite macromolecular antistatic agent. The amount of azobisisobutyronitrile used was 1.2 wt% of the total reactants.

[0015] Example 4: A method for preparing an antistatic PC / ABS composite material includes the following steps: 45 parts PC resin, 15 parts ABS resin, 5 parts of the composite macromolecular antistatic agent prepared in Example 1, 4 parts MBS, 1 part antioxidant 1010, 0.5 parts silicone powder, 3 parts talc powder, and 1-2 parts silane coupling agent KH550. Step S1: Weigh the raw materials according to the weight parts, mix PC resin, ABS resin, MBS and inorganic filler evenly, and then put them into an internal mixer and internally mix at 180°C for 5 minutes to obtain the premix. Step S2: Mix the composite macromolecular antistatic agent, antioxidant 1010, silicone powder and silane coupling agent KH550 prepared in Example 1 with the premix, then put it into a twin-screw extruder for extrusion granulation, and dry it to obtain the antistatic PC / ABS composite material. The temperature of the twin-screw extruder is 210-260℃.

[0016] Example 5: A method for preparing an antistatic PC / ABS composite material includes the following steps: 55 parts PC resin, 20 parts ABS resin, 8 parts of the composite macromolecular antistatic agent prepared in Example 2, 6 parts ABS-g-MAH, 2 parts antioxidant 1076, 1 part silicone powder, 5 parts mica powder, and 1.5 parts tetrabutyl titanate. Step S1: Weigh the raw materials according to the weight parts, mix PC resin, ABS resin, ABS-g-MAH and mica powder evenly, and then put them into an internal mixer and internally mix at 200℃ for 7 minutes to obtain the premix. Step S2: Mix the composite macromolecular antistatic agent, antioxidant 1076, silicone powder and tetrabutyl titanate prepared in Example 2 with the premix, then put it into a twin-screw extruder for extrusion granulation, and dry it to obtain the antistatic PC / ABS composite material. The temperature of the twin-screw extruder is 210-260℃.

[0017] Example 6: A method for preparing an antistatic PC / ABS composite material includes the following steps: 65 parts PC resin, 25 parts ABS resin, 10 parts of the composite macromolecular antistatic agent prepared in Example 3, 8 parts POE, 3 parts antioxidant 168, 1.5 parts silicone powder, 7 parts talc powder, and 2 parts silane coupling agent KH560. Step S1: Weigh the raw materials according to the weight parts, mix PC resin, ABS resin POE and talc powder evenly, and then put them into an internal mixer and internally mix at 220°C for 8 minutes to obtain the premix. Step S2: Mix the composite macromolecular antistatic agent, antioxidant 168, silicone powder and silane coupling agent KH560 prepared in Example 3 with the premix, then put it into a twin-screw extruder for extrusion granulation, and dry it to obtain the antistatic PC / ABS composite material. The temperature of the twin-screw extruder is 210-260℃.

[0018] Comparative Example 1: This comparative example is a PC / ABS composite material. The difference between this example and Example 6 is that carbon nanotubes are used instead of the composite macromolecular antistatic agent prepared in Example 3. All other aspects are the same.

[0019] Comparative Example 2: This comparative example is a PC / ABS composite material. The difference from Example 6 is that a commercially available polycarbonate antistatic agent (purchased from Dongguan Shengbang Polymer Materials Co., Ltd.) is used instead of the composite macromolecular antistatic agent prepared in Example 3. All other aspects are the same.

[0020] Comparative Example 3: This comparative example is a PC / ABS composite material. The difference from Example 6 is that conductive graphite is used instead of the composite macromolecular antistatic agent prepared in Example 3.

[0021] Comparative Example 4: This comparative example is a PC / ABS composite material. The difference from Example 6 is that the high-resistance polyether amide type antistatic agent PELESTAT-6500 (purchased from Sanyo Chemicals, Japan) is used instead of the composite macromolecular antistatic agent prepared in Example 3.

[0022] The PC / ABS composite materials prepared in Examples 4-6 and Comparative Examples 1-3 were subjected to performance tests: Surface resistivity: Tested according to standard ASTM D257-2014; injection molded 40 60 A 2mm square plate sample was tested using a ZST-121 insulating material volume surface resistivity tester. Tensile strength: Tested according to ASTM D638-2014 on a Zwick electronic universal testing machine; The test results are shown in Table 1: Table 1: Performance Test Results

[0023] As can be seen from Table 1, the PC / ABS composite material prepared by this invention has excellent antistatic properties while maintaining mechanical properties.

[0024] The above content is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the scope defined by the inventive concept, they should all fall within the protection scope of the present invention.

Claims

1. An antistatic PC / ABS composite material, characterized in that, The raw materials include the following parts by weight: 45-65 parts PC resin, 15-25 parts ABS resin, 5-10 parts composite macromolecular antistatic agent, 4-8 parts toughening agent, 1-3 parts antioxidant, 0.5-1.5 parts lubricant, 3-7 parts inorganic filler, and 1-2 parts coupling agent. The composite macromolecular antistatic agent is prepared by copolymerization of allyl ester imidazole quaternary ammonium salt, allyl polyether derivative, maleic anhydride, and modified conductive filler; the allyl ester imidazole quaternary ammonium salt is prepared by quaternization of allyl ester imidazole; the allyl ester imidazole is prepared by Michael addition reaction of imidazole and allyl acrylate; the allyl polyether derivative is prepared by reaction of dimethyl phosphate and allyl polyoxyethylene ether.

2. The antistatic PC / ABS composite material according to claim 1, characterized in that, The composite macromolecular antistatic agent is prepared by the following steps: Step A1: Mix imidazole and allyl acrylate separately in methanol and stir until homogeneous, and label them as imidazole solution and allyl acrylate solution; under nitrogen conditions, add allyl acrylate solution to imidazole solution and stir until homogeneous, then heat to 45℃ and stir continuously for 3-4 hours, then evaporate by rotary evaporation and dry to obtain allyl acrylate imidazole. Step A2: Allyl imidazole is stirred thoroughly in acetonitrile, then heated to 50-60℃, 1-chlorobutane is added, and the mixture is refluxed at 80-85℃ for 3.5-4.5 hours. The solvent is removed by rotary evaporation to obtain allyl imidazole quaternary ammonium salt. Step A3: Add dimethyl phosphate to 1,4-dioxane and heat to 50°C. Under nitrogen protection, gradually add allyl polyoxyethylene ether and stir under reflux for 4-6 hours. Remove the solvent by rotary evaporation and dry to obtain the allyl polyether derivative. Step A4: Under nitrogen atmosphere, allyl ester imidazole quaternary ammonium salt, allyl polyether derivative, maleic anhydride and modified conductive filler are mixed in xylene, then transferred to an oil bath and heated to 65°C. Azobisisobutyronitrile is then added and stirred for 10 hours. Methyl tert-butyl ether ethanol solution is added and stirred for 10 minutes. The mixture is then filtered, washed and dried to obtain the composite macromolecular antistatic agent.

3. The antistatic PC / ABS composite material according to claim 2, characterized in that, In step A1, the molar ratio of imidazole to allyl acrylate is 1:1-1.

2.

4. The antistatic PC / ABS composite material according to claim 2, characterized in that, In step A2, the molar ratio of allyl ester imidazole to 1-chlorobutane is 1:

1.

5. The antistatic PC / ABS composite material according to claim 2, characterized in that, In step A3, the molar ratio of dimethyl phosphate to allyl polyoxyethylene ether is 1:

1.

6. The antistatic PC / ABS composite material according to claim 2, characterized in that, In step A4, the molar ratio of allyl ester imidazole quaternary ammonium salt, allyl polyether derivative, maleic anhydride and modified conductive filler is 0.1-0.3:0.05-0.2:0.1:0.1-0.2, and the amount of azobisisobutyronitrile is 0.08wt%-1.2wt% of the total reactants.

7. The antistatic PC / ABS composite material according to claim 2, characterized in that, In step A4, the volume ratio of methyl tert-butyl ether to ethanol in the methyl tert-butyl ether ethanol solution is 5:

1.

8. The antistatic PC / ABS composite material according to claim 2, characterized in that, The modified conductive filler mentioned in step A4 is a conductive filler treated with silane coupling agent KH570, wherein the conductive filler is one of carbon nanotubes, graphene oxide, or carbon nanofibers.

9. The antistatic PC / ABS composite material according to claim 1, characterized in that, The toughening agent is one of MBS, ABS-g-MAH or POE; the antioxidant is one or two of antioxidant 1010, antioxidant 1076, antioxidant 168 or antioxidant 1098; the lubricant is silicone powder; the inorganic filler is one of talc powder or mica powder; and the coupling agent is one of silane coupling agent or titanate coupling agent.

10. A method for preparing the antistatic PC / ABS composite material according to any one of claims 1-9, characterized in that, Includes the following steps: Step S1: Weigh the raw materials according to the weight parts, mix the PC resin, ABS resin, toughening agent and inorganic filler evenly, and then put them into the internal mixer and internally mix at 180-220℃ for 5-8 minutes to obtain the premix. Step S2: Mix the composite macromolecular antistatic agent, antioxidant, lubricant and coupling agent with the premix, then put it into a twin-screw extruder for extrusion granulation, and dry it to obtain the antistatic PC / ABS composite material. The temperature of the twin-screw extruder is 210-260℃.

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