Antistatic PA composite material and preparation method thereof

Abstract

This invention relates to a permanently antistatic PA composite material and its preparation method, belonging to the field of polymer materials technology. The permanently antistatic PA composite material comprises, by weight, 70-90 parts PA resin, 30-60 parts polyethylene, 5-15 parts polythiophene, 1-5 parts modified antistatic agent, 1-5 parts modified flame retardant, 1-3 parts toughening agent, 1-3 parts dispersant, and 1-3 parts lubricant. The modified antistatic agent, containing alkyl amide bonds, forms a conductive layer on the material surface, reducing resistivity. The pre-product enhances the material's hydrophilicity and accelerates charge transfer and dissipation. The modified flame retardant, containing diphenyl chlorophosphate, forms an expanded char layer during combustion, absorbing heat, diluting combustible gases, and isolating the flame. It synergistically strengthens the char layer with phosphorus and nitrogen flame retardants, significantly improving the material's flame retardant performance. The permanently antistatic PA composite material prepared by this invention not only has good antistatic effects but also excellent flame retardant effects.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to an antistatic PA composite material and its preparation method. Background Technology

[0002] PA (nylon), as an important engineering plastic, dominates the market due to its superior performance and is widely used in many fields such as automobiles, aircraft, electronics, petrochemicals, medical, textiles, packaging, and transportation.

[0003] However, nylon engineering plastics are prone to accumulating static electricity during use, which is difficult to eliminate. This not only causes the plastic to attract dust from the air, affecting its appearance, but can also damage sensitive components inside electronic devices during the manufacturing process. Furthermore, the accumulation of static electricity can lead to electric shocks, equipment malfunctions, and even fires. In addition, nylon materials are inherently flammable; in the event of a fire, they burn rapidly and release a large amount of heat, are difficult to extinguish themselves, and produce thick smoke, posing a significant threat to personal safety and public property, and creating a considerable risk to social stability and security. Therefore, the development of antistatic PA composite materials with superior properties has significant practical significance and application value. Summary of the Invention

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

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

[0006] An antistatic PA composite material and its preparation method, comprising the following raw materials in parts by weight: 70-90 parts PA resin, 30-60 parts polyethylene, 5-15 parts polythiophene, 1-5 parts modified antistatic agent, 1-5 parts modified flame retardant, 1-3 parts toughening agent, 1-3 parts dispersant, and 1-3 parts lubricant.

[0007] The toughening agent is EVA-g-MAH;

[0008] The dispersant is talc powder;

[0009] The lubricant mentioned is paraffin wax.

[0010] The modified antistatic agent is prepared by the following method:

[0011] Step A1: Mix lauric acid, diethanolamine and sodium methoxide evenly, stir for 5 minutes under nitrogen atmosphere, slowly heat to 170-180℃, react for 2-3 hours, filter, wash and dry to obtain the compound;

[0012] Furthermore, the mass ratio of lauric acid, diethanolamine, and sodium methoxide is 0.01-0.03 mol: 0.01-0.03 mol: 0.05-0.15 g;

[0013] The compound was prepared by reacting the amino group of diethanolamine with the carboxyl group of lauric acid.

[0014] Step A2: Mix the compound, 4-chloromethylstyrene and triethylamine, heat to 70°C under nitrogen atmosphere, react for 12 h, cool the system to 40°C, wash, filter, and dry under vacuum at 40°C to obtain the preproduct;

[0015] Furthermore, the ratio of the compound, 4-chloromethylstyrene, and triethylamine is 0.01-0.03 mol: 0.01-0.03 mol: 2 mL;

[0016] Secondly, a positively charged preproduct was prepared by quaternizing the chlorine atom of 4-chloromethylstyrene with the amino group of the compound.

[0017] Step A3: Mix the preproduct, N-vinylpyrrolidone, glycidyl methacrylate and acetonitrile evenly, stir for 10 min, then add azobisisobutyronitrile, continue stirring for 30 min, react at 70℃ for 3 h, after the reaction is completed, rotary evaporate, vacuum dry at 50℃ for 12 h to obtain the modified antistatic agent.

[0018] Furthermore, the ratio of the preproduct, N-vinylpyrrolidone, glycidyl methacrylate, acetonitrile, and azobisisobutyronitrile is 0.01-0.03 mol: 0.01-0.03 mol: 0.01-0.03 mol: 2 mL: 0.25-0.35 g;

[0019] Finally, a modified antistatic agent was prepared by copolymerizing the preproduct, N-vinylpyrrolidone, and glycidyl methacrylate via carbon-carbon double bonds.

[0020] The modified flame retardant is prepared by the following method:

[0021] Step B1: Mix 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and anhydrous ethanol evenly, place in an oil bath, heat to 85°C while stirring, then add formaldehyde solution dropwise. After reacting for 8 hours, cool to room temperature, filter, wash, and dry under vacuum at 80°C to obtain the intermediate.

[0022] Furthermore, the ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, anhydrous ethanol, and formaldehyde solution is 0.01-0.03 mol: 40-60 mL: 0.01-0.03 mol, and the volume ratio of formaldehyde to water in the formaldehyde solution is 2:5.

[0023] The intermediate was prepared by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with formaldehyde.

[0024] Step B2: Under nitrogen protection, the intermediate and acetonitrile are mixed evenly and stirred in an ice-water bath for 6 hours. Triethylamine is added and stirring is continued in an ice-water bath for 1 hour. Then diphenyl chlorophosphate is added and reacted at room temperature for 12 hours. The mixture is filtered, washed, distilled under reduced pressure, and dried to obtain the modified flame retardant.

[0025] Furthermore, the ratio of intermediate, acetonitrile, triethylamine, and diphenyl chlorophosphate is 0.01-0.03 mol: 20-30 mL: 14-20 mL: 0.01-0.03 mol;

[0026] Finally, the modified flame retardant was prepared by reacting the hydroxyl group of the intermediate with the chlorine atom of diphenyl chlorophosphate.

[0027] A method for preparing an antistatic PA composite material specifically includes the following steps:

[0028] S1. PA resin, polyethylene, polythiophene, modified antistatic agent, modified flame retardant, toughening agent, dispersant and lubricant are mixed evenly to obtain a mixture.

[0029] S2. The mixture is added to a twin-screw extruder and extruded and granulated to obtain an antistatic PA composite material; the temperatures of each section of the twin-screw extruder are as follows: Zone 1 170-190℃, Zone 2 230-240℃, Zone 3 230-240℃, Zone 4 220-230℃, Zone 5 180-190℃, Zone 6 180-190℃, Zone 7 180-190℃, Zone 8 210-220℃, Die head 220-230℃, and screw speed 190-350 r / min.

[0030] The beneficial effects of this invention are:

[0031] The antistatic PA composite material of the present invention has good antistatic effect and excellent flame retardant effect, further extending its service life.

[0032] The modified antistatic agent prepared by this invention exhibits superior antistatic performance compared to traditional small-molecule antistatic agents due to the advantages of its macromolecular polymer. In this modified antistatic agent, compounds containing alkyl amide bonds can form a conductive layer on the material surface, reducing resistivity, accelerating the dissipation of static charge, achieving an antistatic effect, and imparting lubricity to the material, reducing friction and thus lowering static electricity generation. Simultaneously, the quaternary ammonium salt preproduct enhances the material's hydrophilicity, promoting moisture absorption. The ions in the water film formed after moisture absorption act as a conductive medium, accelerating charge transfer and dissipation, preventing static electricity from negatively impacting production and product quality. Furthermore, the polymerized N-vinylpyrrolidone contains hydrophilic groups, and the epoxy groups in the polymerized glycidyl methacrylate can react with the hydroxyl groups in PA, enhancing intermolecular forces, improving material toughness, and forming a conductive network, further reducing surface resistivity. This synergistic effect with the quaternary ammonium salt enhances the conductivity of ions on the material surface, reducing static electricity accumulation.

[0033] The modified flame retardant prepared in this invention contains diphenyl chlorophosphate, which forms an expanded char layer during combustion. This char layer absorbs heat, dilutes combustible gases, and isolates the flame, inhibiting its spread. Synergistically, it strengthens the char layer with phosphorus-nitrogen flame retardants, significantly improving the flame retardant properties, tensile strength, and smoke suppression performance of the material. Simultaneously, the phosphorus element in diphenyl chlorophosphate forms a phosphate protective layer, decomposing to produce acidic substances such as phosphoric acid, which captures free radicals in the combustion reaction and inhibits the combustion chain reaction. Furthermore, the phosphorus-nitrogen flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, as a highly thermally stable phosphaphenanthrene compound, promotes the formation of a dense and continuous char layer during combustion, isolating oxygen, blocking heat and combustible gas exchange, enhancing the flame retardant effect, and extending the material's service life. Moreover, the modified flame retardant prepared in this invention is halogen-free, reducing environmental pollution and ecosystem damage, and is harmless to human health, thus achieving sustainable development. Detailed Implementation

[0034] 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.

[0035] Example 1: A method for preparing an antistatic PA composite material, specifically including the following steps:

[0036] S1. Weigh the raw materials according to the following parts by weight: 70 parts PA resin, 30 parts polyethylene, 5 parts polythiophene, 1 part modified antistatic agent, 1 part modified flame retardant, 1 part toughening agent, 1 part dispersant, and 1 part lubricant; mix PA resin, polyethylene, polythiophene, modified antistatic agent, modified flame retardant, EVA-g-MAH, talc powder, and paraffin wax evenly to obtain a mixture.

[0037] S2. The mixture is added to a twin-screw extruder and extruded and granulated to obtain an antistatic PA composite material; the temperatures of each section of the twin-screw extruder are as follows: Zone 1 170℃, Zone 2 230℃, Zone 3 230℃, Zone 4 220℃, Zone 5 180℃, Zone 6 180℃, Zone 7 180℃, Zone 8 210℃, Die head 220℃, and screw speed 190r / min;

[0038] The modified antistatic agent is prepared by the following method:

[0039] Step A1: Mix 0.01 mol lauric acid, 0.01 mol diethanolamine and 0.05 g sodium methoxide evenly, stir for 5 min under nitrogen atmosphere, slowly heat to 170 °C, react for 2 h, filter, wash and dry to obtain the compound;

[0040] Step A2: Mix 0.01 mol of the compound, 0.01 mol of 4-chloromethylstyrene and 2 mL of triethylamine, heat to 70 °C under nitrogen atmosphere, react for 12 h, cool the system to 40 °C, wash, filter, and dry under vacuum at 40 °C to obtain the preproduct;

[0041] Step A3: Mix 0.01 mol of preproduct, 0.01 mol of N-vinylpyrrolidone, 0.01 mol of glycidyl methacrylate and 2 mL of acetonitrile evenly, stir for 10 min, then add 0.25 g of azobisisobutyronitrile, continue stirring for 30 min, react at 70 °C for 3 h, after the reaction is completed, rotary evaporate, and vacuum dry at 50 °C for 12 h to obtain the modified antistatic agent;

[0042] The modified flame retardant is prepared by the following method:

[0043] Step B1: Mix 0.01 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 40 mL of anhydrous ethanol evenly, place in an oil bath, heat to 85 °C while stirring, then add 0.01 mol of formaldehyde solution dropwise. After reacting for 8 hours, cool to room temperature, filter, wash, and dry under vacuum at 80 °C to obtain the intermediate. The formaldehyde to water volume ratio of the formaldehyde solution is 2:5.

[0044] Step B2: Under nitrogen protection, 0.01 mol of intermediate and 20 mL of acetonitrile were mixed evenly and stirred in an ice-water bath for 6 h. 14 mL of triethylamine was added and the mixture was stirred in an ice-water bath for another 1 h. Then 0.01 mol of diphenyl chlorophosphate was added and the mixture was reacted at room temperature for 12 h. The mixture was filtered, washed, distilled under reduced pressure, and dried to obtain the modified flame retardant.

[0045] Example 2: A method for preparing an antistatic PA composite material, specifically including the following steps:

[0046] S1. Weigh the raw materials according to the following parts by weight: 80 parts PA resin, 45 parts polyethylene, 10 parts polythiophene, 3 parts modified antistatic agent, 3 parts modified flame retardant, 2 parts toughening agent, 2 parts dispersant, and 2 parts lubricant; mix the PA resin, polyethylene, polythiophene, modified antistatic agent, modified flame retardant, EVA-g-MAH, talc powder, and paraffin wax evenly to obtain a mixture.

[0047] S2. The mixture is added to a twin-screw extruder and extruded and granulated to obtain an antistatic PA composite material; the temperatures of each section of the twin-screw extruder are as follows: Zone 1 180℃, Zone 2 235℃, Zone 3 235℃, Zone 4 225℃, Zone 5 185℃, Zone 6 185℃, Zone 7 185℃, Zone 8 215℃, Die head 225℃, and screw speed 220r / min;

[0048] The modified antistatic agent is prepared by the following method:

[0049] Step A1: Mix 0.02 mol lauric acid, 0.02 mol diethanolamine and 0.10 g sodium methoxide evenly, stir for 5 min under nitrogen atmosphere, slowly heat to 175 °C, react for 2.5 h, filter, wash and dry to obtain the compound;

[0050] Step A2: Mix 0.02 mol of the compound, 0.02 mol of 4-chloromethylstyrene and 2 mL of triethylamine, heat to 70 °C under nitrogen atmosphere, react for 12 h, cool the system to 40 °C, wash, filter, and dry under vacuum at 40 °C to obtain the preproduct;

[0051] Step A3: Mix 0.02 mol of preproduct, 0.02 mol of N-vinylpyrrolidone, 0.02 mol of glycidyl methacrylate and 2 mL of acetonitrile evenly, stir for 10 min, then add 0.3 g of azobisisobutyronitrile, continue stirring for 30 min, react at 70 °C for 3 h, after the reaction is completed, rotary evaporate, and vacuum dry at 50 °C for 12 h to obtain the modified antistatic agent;

[0052] The modified flame retardant is prepared by the following method:

[0053] Step B1: Mix 0.02 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 50 mL of anhydrous ethanol evenly, place in an oil bath, heat to 85 °C while stirring, then add 0.02 mol of formaldehyde solution dropwise. After reacting for 8 hours, cool to room temperature, filter, wash, and dry under vacuum at 80 °C to obtain the intermediate. The formaldehyde to water volume ratio of the formaldehyde solution is 2:5.

[0054] Step B2: Under nitrogen protection, 0.02 mol of intermediate and 25 mL of acetonitrile were mixed evenly and stirred in an ice-water bath for 6 h. 17 mL of triethylamine was added and the mixture was stirred in an ice-water bath for another 1 h. Then 0.02 mol of diphenyl chlorophosphate was added and the mixture was reacted at room temperature for 12 h. The mixture was filtered, washed, distilled under reduced pressure, and dried to obtain the modified flame retardant.

[0055] Example 3: A method for preparing an antistatic PA composite material, specifically including the following steps:

[0056] S1. Weigh the raw materials according to the following parts by weight: 90 parts PA resin, 60 parts polyethylene, 15 parts polythiophene, 5 parts modified antistatic agent, 5 parts modified flame retardant, 3 parts toughening agent, 3 parts dispersant, and 3 parts lubricant; mix PA resin, polyethylene, polythiophene, modified antistatic agent, modified flame retardant, EVA-g-MAH, talc powder, and paraffin wax evenly to obtain a mixture.

[0057] S2. The mixture is added to a twin-screw extruder and extruded and granulated to obtain an antistatic PA composite material; the temperatures of each section of the twin-screw extruder are as follows: Zone 1 190℃, Zone 2 240℃, Zone 3 240℃, Zone 4 230℃, Zone 5 190℃, Zone 6 190℃, Zone 7 190℃, Zone 8 220℃, Die head 230℃, and screw speed 350r / min;

[0058] The modified antistatic agent is prepared by the following method:

[0059] Step A1: Mix 0.03 mol lauric acid, 0.03 mol diethanolamine and 0.15 g sodium methoxide evenly, stir for 5 min under nitrogen atmosphere, slowly heat to 180 °C, react for 3 h, filter, wash and dry to obtain the compound;

[0060] Step A2: Mix 0.03 mol of the compound, 0.03 mol of 4-chloromethylstyrene and 2 mL of triethylamine, heat to 70 °C under nitrogen atmosphere, react for 12 h, cool the system to 40 °C, wash, filter, and dry under vacuum at 40 °C to obtain the preproduct;

[0061] Step A3: Mix 0.03 mol of preproduct, 0.03 mol of N-vinylpyrrolidone, 0.03 mol of glycidyl methacrylate and 2 mL of acetonitrile evenly, stir for 10 min, then add 0.35 g of azobisisobutyronitrile, continue stirring for 30 min, react at 70 °C for 3 h, after the reaction is completed, rotary evaporate, and vacuum dry at 50 °C for 12 h to obtain the modified antistatic agent;

[0062] The modified flame retardant is prepared by the following method:

[0063] Step B1: Mix 0.03 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 60 mL of anhydrous ethanol evenly, place in an oil bath, heat to 85 °C while stirring, then add 0.03 mol of formaldehyde solution dropwise. After reacting for 8 h, cool to room temperature, filter, wash, and dry under vacuum at 80 °C to obtain the intermediate. The formaldehyde to water volume ratio of the formaldehyde solution is 2:5.

[0064] Step B2: Under nitrogen protection, 0.03 mol of intermediate and 30 mL of acetonitrile were mixed evenly and stirred in an ice-water bath for 6 h. 20 mL of triethylamine was added and the mixture was stirred in an ice-water bath for another 1 h. Then 0.03 mol of diphenyl chlorophosphate was added and the mixture was reacted at room temperature for 12 h. The mixture was filtered, washed, distilled under reduced pressure, and dried to obtain the modified flame retardant.

[0065] Comparative Example 1: This comparative example is an antistatic PA composite material. The difference between this example and Example 3 is that an equal amount of carbon black is used instead of the modified antistatic agent prepared in Example 3. All other aspects are the same.

[0066] Comparative Example 2: This comparative example is an antistatic PA composite material. The difference between this example and Example 3 is that an equal amount of magnesium hydroxide is used instead of the modified flame retardant prepared in Example 3. All other aspects are the same.

[0067] Performance testing: The antistatic PA composite materials prepared in Examples 1-3 and Comparative Examples 1-2 were cut into standard test sizes, and the surface resistivity was tested according to GB / T 1410-2006; the vertical burning performance was tested according to GB / T 2048-1996 Plastics Burning Performance Test Method; and the tensile strength was tested according to GB / T 1040-2018. The test results are shown in Table 1 below:

[0068] Table 1

[0069]

[0070] As can be seen from the test data in Table 1, the antistatic PA composite material prepared by the present invention has good flame retardant effect. Table 1 also shows that the antistatic PA composite material prepared by the present invention has good antistatic effect and extends service life.

[0071] The above description 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 concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing an antistatic PA composite material, characterized in that, Specifically, the following steps are included: S1. Weigh the raw materials according to the following parts by weight: 70-90 parts PA resin, 30-60 parts polyethylene, 5-15 parts polythiophene, 1-5 parts modified antistatic agent, 1-5 parts modified flame retardant, 1-3 parts toughening agent, 1-3 parts dispersant, and 1-3 parts lubricant; mix the PA resin, polyethylene, polythiophene, modified antistatic agent, modified flame retardant, toughening agent, dispersant, and lubricant evenly to obtain a mixture. S2. The mixture is added to a twin-screw extruder and extruded and granulated to obtain an antistatic PA composite material; the temperatures of each section of the twin-screw extruder are as follows: Zone 1 170-190℃, Zone 2 230-240℃, Zone 3 230-240℃, Zone 4 220-230℃, Zone 5 180-190℃, Zone 6 180-190℃, Zone 7 180-190℃, Zone 8 210-220℃, Die head 220-230℃, and screw speed 190-350 r / min; The modified antistatic agent is prepared by the following method: Step A1: Mix lauric acid, diethanolamine and sodium methoxide evenly, stir for 5 minutes under nitrogen atmosphere, slowly heat to 170-180℃, react for 2-3 hours, filter, wash and dry to obtain the compound; Step A2: Mix the compound, 4-chloromethylstyrene and triethylamine, heat to 70°C under nitrogen atmosphere, react for 12 h, cool the system to 40°C, wash, filter, and dry under vacuum at 40°C to obtain the preproduct; Step A3: Mix the preproduct, N-vinylpyrrolidone, glycidyl methacrylate and acetonitrile evenly, stir for 10 min, then add azobisisobutyronitrile, continue stirring for 30 min, react at 70℃ for 3 h, after the reaction is completed, rotary evaporate, vacuum dry at 50℃ for 12 h to obtain the modified antistatic agent. The modified flame retardant is prepared by the following method: Step B1: Mix 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and anhydrous ethanol evenly, place in an oil bath, heat to 85°C while stirring, then add formaldehyde solution dropwise. After reacting for 8 hours, cool to room temperature, filter, wash, and dry under vacuum at 80°C to obtain the intermediate. Step B2: Under nitrogen protection, the intermediate and acetonitrile are mixed evenly and stirred in an ice-water bath for 6 hours. Triethylamine is added, and stirring is continued in an ice-water bath for 1 hour. Then diphenyl chlorophosphate is added, and the mixture is reacted at room temperature for 12 hours. The mixture is filtered, washed, distilled under reduced pressure, and dried to obtain the modified flame retardant.

2. The method for preparing an antistatic PA composite material according to claim 1, characterized in that, In step A1, the ratio of lauric acid, diethanolamine, and sodium methoxide is 0.01-0.03 mol: 0.01-0.03 mol: 0.05-0.15 g.

3. The method for preparing an antistatic PA composite material according to claim 1, characterized in that, In step A2, the ratio of the compound, 4-chloromethylstyrene, and triethylamine is 0.01-0.03 mol: 0.01-0.03 mol: 2 mL.

4. The method for preparing an antistatic PA composite material according to claim 1, characterized in that, In step A3, the ratio of the preproduct, N-vinylpyrrolidone, glycidyl methacrylate, acetonitrile, and azobisisobutyronitrile is 0.01-0.03 mol: 0.01-0.03 mol: 0.01-0.03 mol: 2 mL: 0.25-0.35 g.

5. The method for preparing an antistatic PA composite material according to claim 1, characterized in that, In step B1, the ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, anhydrous ethanol, and formaldehyde solution is 0.01-0.03 mol: 40-60 mL: 0.01-0.03 mol, and the volume ratio of formaldehyde to water in the formaldehyde solution is 2:

5.

6. The method for preparing an antistatic PA composite material according to claim 1, characterized in that, In step B2, the ratio of the intermediate, acetonitrile, triethylamine, and diphenyl chlorophosphate is 0.01-0.03 mol: 20-30 mL: 14-20 mL: 0.01-0.03 mol.

7. The method for preparing an antistatic PA composite material according to claim 1, characterized in that, The toughening agent is EVA-g-MAH, the dispersant is talc, and the lubricant is paraffin wax.

8. An antistatic PA composite material, characterized in that, Prepared according to any one of claims 1-7.

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