Impact-resistant and antistatic composite material and preparation method thereof

Abstract

The present invention relates to an impact-resistant antistatic composite material and a preparation method thereof, and belongs to the technical field of polymer materials. The impact-resistant antistatic composite material comprises, by weight, 60-85 parts of PE resin, 5-15 parts of ABS resin, 1-7 parts of toughening agent, 7-20 parts of modified antistatic agent, 0.1-1 parts of antioxidant, and 0.1-1 parts of lubricant; the compound in the modified antistatic agent fixes the carboxylate radical on PE to reduce the blooming phenomenon; the compound and 2,4,6-tris(dimethylaminomethyl)phenol cooperate to promote PE to form a dense carbon layer during combustion; the quaternary ammonium salt pre-product neutralizes the negative charge of PE, reduces static electricity accumulation, and further enhances the hydrophilicity of the material; the ions in the water film formed after moisture absorption serve as a conductive medium, and the cations adsorb negatively charged bacteria, thereby improving the antibacterial effect; the impact-resistant antistatic composite material prepared by the present invention not only has a good antistatic effect, but also has excellent impact resistance and antibacterial effects.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and particularly relates to an impact-resistant and antistatic composite material and a preparation method thereof. Background Art

[0002] Polyethylene (PE), as a general-purpose plastic, has the advantages of high chemical stability, good heat resistance, and strong resistance to chemical corrosion. With its excellent comprehensive performance, it is widely used in the automotive industry, chemical containers, electronic and electrical fields.

[0003] However, as a good electrical insulating material, polyethylene has high volume resistivity and surface resistivity, and is prone to accumulate static electricity during use, leading to problems such as dust absorption, electric shock, and electrostatic spark discharge, and may even cause explosions in flammable and explosive environments. In addition, although polyethylene itself has certain impact resistance, with the continuous improvement of actual application needs, its own impact resistance can no longer meet current needs. Therefore, the research and development of impact-resistant and antistatic composite materials with excellent performance has important practical significance and application value. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides an impact-resistant and antistatic composite material and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An impact-resistant and antistatic composite material and a preparation method thereof, comprising the following raw materials in parts by weight: 60-85 parts of PE resin, 5-15 parts of ABS resin, 1-7 parts of a toughening agent, 7-20 parts of a modified antistatic agent, 0.1-1 parts of an antioxidant, and 0.1-1 parts of a lubricant;

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

[0008] The antioxidant is antioxidant 1010;

[0009] The lubricant is paraffin.

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

[0011] Step A1: Undecylenic acid, magnesium hydroxide, and toluene were uniformly mixed, stirred under nitrogen atmosphere for 10-15 min, slowly heated to 60-70° C., ultrasonically reacted for 2 h, filtered, washed, and dried under vacuum at 60° C. to obtain a compound;

[0012] Furthermore, the usage ratio of undecylenic acid, magnesium hydroxide, and toluene is 0.02-0.06 mol: 0.01-0.03 mol: 20-90 mL;

[0013] First, the carboxyl group of undecylenic acid reacts with the hydroxyl group of magnesium hydroxide to prepare a compound;

[0014] Step A2: Disperse thionyl chloride in dimethyl sulfoxide, cool to 0-5°C, then add acrylic acid and tetrahydrofuran and mix well. React at room temperature for 2 hours. After the reaction is complete, distill under reduced pressure and dry in vacuo to obtain Intermediate 1.

[0015] Furthermore, the usage ratio of thionyl chloride, dimethyl sulfoxide, acrylic acid, and tetrahydrofuran is 0.01-0.03 mol: 12-15 mL: 0.01-0.03 mol: 12-15 mL;

[0016] Then the carboxyl group of acrylic acid reacts with thionyl chloride to obtain intermediate 1;

[0017] Step A3: Intermediate 1 and N,N-dimethylformamide were mixed uniformly, reacted at 60°C for 3 h, and then 2,4,6-tris(dimethylaminomethyl)phenol and triethylamine were added, and the mixture was reacted at 60°C for 3 h. After the reaction, the mixture was filtered, washed, and vacuum dried for 12 h to obtain Intermediate 2;

[0018] Furthermore, the usage ratio of intermediate 1, N,N-dimethylformamide, 2,4,6-tris(dimethylaminomethyl)phenol, and triethylamine is 0.01-0.03 mol:13-15 mL:0.01-0.03 mol:2-6 mL;

[0019] Secondly, the chlorine atom of intermediate 1 reacts with the phenolic hydroxyl group of 2,4,6-tris(dimethylaminomethyl)phenol to obtain intermediate 2;

[0020] Step A4: Mix anhydrous ethanol and intermediate 2 evenly, stir in a water bath for 5 minutes, react at 25°C for 30 minutes, then raise the temperature to 45°C, adjust the pH to 7.5-8, and slowly add epichlorohydrin. After the addition is complete, keep the temperature at 45°C for 8 hours, and evaporate under reduced pressure to obtain a pre-product.

[0021] Furthermore, the usage ratio of anhydrous ethanol, intermediate 2, and epichlorohydrin is 50 mL: 0.01-0.03 mol: 0.03-0.09 mol;

[0022] Then, the amino group of intermediate 2 and the epoxy group of epichlorohydrin undergo a ring-opening reaction to obtain a pre-product;

[0023] Step A5: The pre-product, compound and acetonitrile were mixed evenly, stirred for 10 minutes, and then azobisisobutyronitrile was added, and the mixture was stirred for 30 minutes. The mixture was reacted at 70°C for 3 hours. After the reaction was completed, the mixture was rotary evaporated and vacuum dried at 50°C for 12 hours to obtain a modified antistatic agent;

[0024] Furthermore, the ratio of the preproduct, the compound, acetonitrile, and azobisisobutyronitrile is 0.01-0.03 mol: 0.01-0.03 mol: 2-18 mL: 0.25-0.35 g;

[0025] Finally, the modified antistatic agent is prepared by copolymerizing the carbon-carbon double bond of the pre-product and the compound.

[0026] A method for preparing an impact-resistant and antistatic composite material comprises the following steps:

[0027] S1. Add PE resin, ABS resin, toughening agent, modified antistatic agent, antioxidant and lubricant into a mixing mixer and premix for 5-10 minutes to obtain a premixed material;

[0028] S2. Add the premixed material into a twin-screw extruder from a main feeding port, extrude it at a low melting temperature of 220-260° C. and a rotation speed of 300-450 rpm to obtain an impact-resistant and antistatic composite material.

[0029] Beneficial effects of the present invention:

[0030] The impact-resistant and antistatic composite material of the present invention has good antistatic effect, and also has excellent impact resistance and antibacterial effects, further extending the service life.

[0031] The modified antistatic agent prepared by the present invention, with its advantages as a macromolecular polymer, exhibits antistatic performance that surpasses traditional small-molecule antistatic agents. In the modified antistatic agent, the carboxyl group in the undecylenic acid molecule reacts with the hydroxyl group of magnesium hydroxide to form a stable magnesium salt, which fixes the carboxylate antistatic group on the PE molecular chain, effectively solving the problem of surface resistance rebound caused by migration of traditional antistatic agents. At the same time, the magnesium salt structure enhances the compatibility of the antistatic agent with PE, significantly reducing the blooming phenomenon and ensuring long-term antistatic effect. In addition, the compound synergistically acts with 2,4,6-tris(dimethylaminomethyl)phenol to promote the formation of a dense carbon layer on PE during combustion, significantly improving the flame retardancy and thermal stability of the composite material and extending the service life. life; in addition, the quaternary ammonium salt pre-product can neutralize the negative charge on the surface of the PE material through the cationic group, reduce static electricity accumulation, enhance the hydrophilicity of the material, promote moisture absorption, and the ions in the water film formed after moisture absorption act as a conductive medium, accelerate the transfer and dissipation of charge, and avoid the negative impact of static electricity on production and product quality. At the same time, the cationic group of the quaternary ammonium salt pre-product can adsorb negatively charged bacteria, penetrate the bacterial cell wall, react with the protein on the bacterial cell membrane, destroy the cell membrane structure, cause the protein in the bacteria to leak, and accelerate the death of bacteria, thereby improving the antibacterial effect. DETAILED DESCRIPTION

[0032] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0033] Example 1: A method for preparing an impact-resistant and antistatic composite material, comprising the following steps:

[0034] S1. Weigh the raw materials by weight: 60 parts of PE resin, 5 parts of ABS resin, 1 part of toughening agent, 7 parts of modified antistatic agent (prepared in this example), 0.1 part of antioxidant, and 0.1 part of lubricant; add PE resin, ABS resin, EVA-g-MAH, modified antistatic agent, antioxidant 1010, and paraffin wax into a mixer and premix for 5 minutes to obtain a premixed material;

[0035] S2, adding the premixed material into a twin-screw extruder from the main feed port, and extruding at a low melt temperature of 220° C. and a rotation speed of 300 rpm to obtain an impact-resistant and antistatic composite material;

[0036] The modified antistatic agent is prepared by the following method:

[0037] Step A1: 0.02 mol of undecylenic acid, 0.01 mol of magnesium hydroxide, and 20 mL of toluene were mixed uniformly, stirred under nitrogen atmosphere for 10 min, slowly heated to 60°C, ultrasonically reacted for 2 h, filtered, washed, and dried in vacuo at 60°C to obtain a compound;

[0038] Step A2: Disperse 0.01 mol of thionyl chloride in 12 mL of dimethyl sulfoxide, cool to 0°C, add 0.01 mol of acrylic acid and 12 mL of tetrahydrofuran, mix well, and react at room temperature for 2 h. After the reaction, distill under reduced pressure and dry in vacuo to obtain Intermediate 1;

[0039] Step A3: Mix 0.01 mol of intermediate 1 and 13 mL of N,N-dimethylformamide, react at 60°C for 3 h, then add 0.01 mol of 2,4,6-tris(dimethylaminomethyl)phenol and 2 mL of triethylamine, react at 60°C for 3 h. After the reaction, filter, wash, and vacuum dry for 12 h to obtain intermediate 2.

[0040] Step A4: Mix 50 mL of anhydrous ethanol and 0.01 mol of intermediate 2, stir in a water bath for 5 min, react at 25°C for 30 min, then raise the temperature to 45°C, adjust the pH to 7.5, and slowly add 0.03 mol of epichlorohydrin. After the addition is complete, keep the temperature at 45°C for 8 h, and evaporate under reduced pressure to obtain the pre-product.

[0041] Step A5: Mix 0.01 mol of the pre-product, 0.01 mol of the compound and 2 mL of acetonitrile, stir for 10 min, add 0.25 g of azobisisobutyronitrile, continue stirring for 30 min, react at 70 ° C for 3 h, and after the reaction is completed, rotary evaporate and vacuum dry at 50 ° C for 12 h to obtain a modified antistatic agent.

[0042] Example 2: A method for preparing an impact-resistant and antistatic composite material, comprising the following steps:

[0043] S1. Weigh the raw materials by weight: 68 parts of PE resin, 8 parts of ABS resin, 3 parts of toughening agent, 11 parts of modified antistatic agent (prepared in this example), 0.4 parts of antioxidant, and 0.4 parts of lubricant; add PE resin, ABS resin, EVA-g-MAH, modified antistatic agent, antioxidant 1010, and paraffin wax into a mixer and premix for 7 minutes to obtain a premixed material;

[0044] S2, adding the premixed material into a twin-screw extruder from the main feed port, and extruding at a low melt temperature of 233° C. and a rotation speed of 350 rpm to obtain an impact-resistant and antistatic composite material;

[0045] The modified antistatic agent is prepared by the following method:

[0046] Step A1: 0.033 mol of undecylenic acid, 0.017 mol of magnesium hydroxide, and 43 mL of toluene were mixed uniformly, stirred under nitrogen atmosphere for 12 min, slowly heated to 63°C, ultrasonically reacted for 2 h, filtered, washed, and dried in vacuo at 60°C to obtain a compound;

[0047] Step A2: Disperse 0.017 mol of thionyl chloride in 13 mL of dimethyl sulfoxide, cool to 1.5°C, add 0.017 mol of acrylic acid and 13 mL of tetrahydrofuran, mix well, and react at room temperature for 2 h. After the reaction, distill under reduced pressure and dry in vacuo to obtain Intermediate 1;

[0048] Step A3: Mix 0.017 mol of intermediate 1 and 13.7 mL of N,N-dimethylformamide, react at 60°C for 3 h, then add 0.017 mol of 2,4,6-tris(dimethylaminomethyl)phenol and 3 mL of triethylamine, react at 60°C for 3 h. After the reaction, filter, wash, and vacuum dry for 12 h to obtain intermediate 2.

[0049] Step A4: Mix 50 mL of anhydrous ethanol and 0.017 mol of intermediate 2, stir in a water bath for 5 min, react at 25°C for 30 min, then raise the temperature to 45°C, adjust the pH to 7.7, and slowly add 0.05 mol of epichlorohydrin. After the addition is complete, keep the temperature at 45°C for 8 h, and evaporate under reduced pressure to obtain the pre-product.

[0050] Step A5: Mix 0.017 mol of the pre-product, 0.017 mol of the compound and 7 mL of acetonitrile, stir for 10 min, add 0.28 g of azobisisobutyronitrile, continue stirring for 30 min, react at 70 ° C for 3 h, and after the reaction is completed, rotary evaporate and vacuum dry at 50 ° C for 12 h to obtain a modified antistatic agent.

[0051] Example 3: A method for preparing an impact-resistant and antistatic composite material, comprising the following steps:

[0052] S1. Weigh the raw materials by weight: 76 parts of PE resin, 12 parts of ABS resin, 5 parts of toughening agent, 16 parts of modified antistatic agent (prepared in this example), 0.7 parts of antioxidant, and 0.7 parts of lubricant; add PE resin, ABS resin, EVA-g-MAH, modified antistatic agent, antioxidant 1010, and paraffin wax into a mixer and premix for 9 minutes to obtain a premixed material;

[0053] S2, adding the premixed material into a twin-screw extruder from the main feed port, and extruding at a low melt temperature of 246° C. and a rotation speed of 400 rpm to obtain an impact-resistant and antistatic composite material;

[0054] The modified antistatic agent is prepared by the following method:

[0055] Step A1: 0.046 mol of undecylenic acid, 0.024 mol of magnesium hydroxide, and 66 mL of toluene were mixed uniformly, stirred under nitrogen for 14 min, slowly heated to 66°C, ultrasonically reacted for 2 h, filtered, washed, and dried in vacuo at 60°C to obtain the compound;

[0056] Step A2: Disperse 0.024 mol of thionyl chloride in 14 mL of dimethyl sulfoxide, cool to 3°C, add 0.024 mol of acrylic acid and 14 mL of tetrahydrofuran, mix well, and react at room temperature for 2 h. After the reaction, distill under reduced pressure and dry in vacuo to obtain Intermediate 1;

[0057] Step A3: Mix 0.024 mol of intermediate 1 and 14.4 mL of N,N-dimethylformamide, react at 60°C for 3 h, then add 0.024 mol of 2,4,6-tris(dimethylaminomethyl)phenol and 5 mL of triethylamine, react at 60°C for 3 h. After the reaction, filter, wash, and vacuum dry for 12 h to obtain intermediate 2.

[0058] Step A4: Mix 50 mL of anhydrous ethanol and 0.024 mol of intermediate 2, stir in a water bath for 5 min, react at 25°C for 30 min, then raise the temperature to 45°C, adjust the pH to 7.9, and slowly add 0.07 mol of epichlorohydrin. After the addition is complete, keep the temperature at 45°C for 8 h, and evaporate under reduced pressure to obtain the pre-product.

[0059] Step A5: Mix 0.024 mol of the preproduct, 0.024 mol of the compound and 12 mL of acetonitrile, stir for 10 min, add 0.31 g of azobisisobutyronitrile, continue stirring for 30 min, react at 70 ° C for 3 h, and after the reaction is completed, rotary evaporate and vacuum dry at 50 ° C for 12 h to obtain a modified antistatic agent.

[0060] Example 4: A method for preparing an impact-resistant and antistatic composite material, comprising the following steps:

[0061] S1. Weigh the raw materials by weight: 85 parts of PE resin, 15 parts of ABS resin, 7 parts of toughening agent, 20 parts of modified antistatic agent (prepared in this example), 1 part of antioxidant, and 1 part of lubricant; add PE resin, ABS resin, EVA-g-MAH, modified antistatic agent, antioxidant 1010, and paraffin into a mixer and premix for 10 minutes to obtain a premixed material;

[0062] S2, adding the premixed material into a twin-screw extruder from the main feed port, and extruding at a low melt temperature of 260° C. and a rotation speed of 450 rpm to obtain an impact-resistant and antistatic composite material;

[0063] The modified antistatic agent is prepared by the following method:

[0064] Step A1: 0.06 mol of undecylenic acid, 0.03 mol of magnesium hydroxide, and 90 mL of toluene were mixed uniformly, stirred under nitrogen atmosphere for 15 min, slowly heated to 70°C, ultrasonically reacted for 2 h, filtered, washed, and dried in vacuo at 60°C to obtain a compound;

[0065] Step A2: Disperse 0.03 mol of thionyl chloride in 15 mL of dimethyl sulfoxide, cool to 5°C, add 0.03 mol of acrylic acid and 15 mL of tetrahydrofuran, mix well, and react at room temperature for 2 h. After the reaction, distill under reduced pressure and dry in vacuo to obtain Intermediate 1;

[0066] Step A3: Mix 0.03 mol of intermediate 1 and 15 mL of N,N-dimethylformamide, react at 60°C for 3 h, then add 0.03 mol of 2,4,6-tris(dimethylaminomethyl)phenol and 6 mL of triethylamine, react at 60°C for 3 h. After the reaction, filter, wash, and vacuum dry for 12 h to obtain intermediate 2.

[0067] Step A4: Mix 50 mL of anhydrous ethanol and 0.03 mol of intermediate 2, stir in a water bath for 5 min, react at 25°C for 30 min, then raise the temperature to 45°C, adjust the pH to 8, and slowly add 0.09 mol of epichlorohydrin. After the addition is complete, keep the temperature at 45°C for 8 h, and evaporate under reduced pressure to obtain the pre-product.

[0068] Step A5: Mix 0.03 mol of the pre-product, 0.03 mol of the compound and 18 mL of acetonitrile, stir for 10 min, add 0.35 g of azobisisobutyronitrile, continue stirring for 30 min, react at 70 ° C for 3 h, and after the reaction is completed, rotary evaporate and vacuum dry at 50 ° C for 12 h to obtain a modified antistatic agent.

[0069] Comparative Example: This comparative example is an impact-resistant antistatic composite material. The difference from Example 3 is that an equal amount of carbon black is used to replace the modified antistatic agent prepared in Example 3, and the rest are the same.

[0070] Performance testing: The impact-resistant and antistatic composite materials prepared in Examples 1-4 and the comparative example were cut into standard test sizes and tested for Charpy impact strength according to standard ISO 179 at a temperature of 23° C. and a pendulum energy of 4 J. The surface resistivity was tested according to GB / T 1410-2006. The flammability was tested using GB / T 2408-2021. Antibacterial testing was performed according to standard QB / T 2591-2003. The test results are shown in Table 1 below:

[0071] Table 1

[0072]

[0073] It can be seen from the test data in Table 1 that the impact-resistant antistatic composite material prepared by the present invention has good impact resistance and flame retardant effects. It can also be seen from Table 1 that the impact-resistant antistatic composite material prepared by the present invention has good antistatic and antibacterial effects and extends the service life.

[0074] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A method for preparing an impact-resistant and antistatic composite material, characterized in that: The specific steps include: S1. Weigh the raw materials by weight: 60-85 parts of PE resin, 5-15 parts of ABS resin, 1-7 parts of toughening agent, 7-20 parts of modified antistatic agent, 0.1-1 parts of antioxidant, and 0.1-1 parts of lubricant; add the PE resin, ABS resin, toughening agent, modified antistatic agent, antioxidant, and lubricant into a mixing mixer and premix for 5-10 minutes to obtain a premixed material; S2, adding the premixed material into a twin-screw extruder from the main feed port, and extruding at a low melt temperature of 220-260° C. and a rotation speed of 300-450 rpm to obtain an impact-resistant and antistatic composite material; The modified antistatic agent is prepared by the following method: Step A1: Undecylenic acid, magnesium hydroxide, and toluene were uniformly mixed, stirred under nitrogen atmosphere for 10-15 min, slowly heated to 60-70° C., ultrasonically reacted for 2 h, filtered, washed, and dried under vacuum at 60° C. to obtain a compound; Step A2: Disperse thionyl chloride in dimethyl sulfoxide, cool to 0-5°C, then add acrylic acid and tetrahydrofuran and mix well. React at room temperature for 2 hours. After the reaction is complete, distill under reduced pressure and dry in vacuo to obtain Intermediate 1. Step A3: Intermediate 1 and N,N-dimethylformamide were mixed evenly, reacted at 60°C for 3 h, and then 2,4,6-tris(dimethylaminomethyl)phenol and triethylamine were added, and the mixture was reacted at 60°C for 3 h. After the reaction, the mixture was filtered, washed, and vacuum dried for 12 h to obtain Intermediate 2; Step A4: Mix anhydrous ethanol and intermediate 2 evenly, stir in a water bath for 5 minutes, react at 25°C for 30 minutes, then raise the temperature to 45°C, adjust the pH to 7.5-8, and slowly add epichlorohydrin. After the addition is complete, keep the temperature at 45°C for 8 hours, and evaporate under reduced pressure to obtain a pre-product. Step A5: Mix the pre-product, compound and acetonitrile evenly, stir for 10 minutes, then add azobisisobutyronitrile, continue stirring for 30 minutes, react at 70°C for 3 hours, and after the reaction is completed, rotary evaporate and vacuum dry at 50°C for 12 hours to obtain a modified antistatic agent.

2. The method for preparing an impact-resistant and antistatic composite material according to claim 1, characterized in that: In step A1, the usage ratio of undecylenic acid, magnesium hydroxide, and toluene is 0.02-0.06 mol: 0.01-0.03 mol: 20-90 mL.

3. The method for preparing an impact-resistant and antistatic composite material according to claim 1, wherein: In step A2, the usage ratio of thionyl chloride, dimethyl sulfoxide, acrylic acid and tetrahydrofuran is 0.01-0.03 mol: 12-15 mL: 0.01-0.03 mol: 12-15 mL.

4. The method for preparing an impact-resistant and antistatic composite material according to claim 1, wherein: The usage ratio of intermediate 1, N,N-dimethylformamide, 2,4,6-tris(dimethylaminomethyl)phenol, and triethylamine in step A3 is 0.01-0.03 mol:13-15 mL:0.01-0.03 mol:2-6 mL.

5. The method for preparing an impact-resistant and antistatic composite material according to claim 1, characterized in that: In step A4, the usage ratio of anhydrous ethanol, intermediate 2, and epichlorohydrin is 50 mL: 0.01-0.03 mol: 0.03-0.09 mol.

6. The method for preparing an impact-resistant and antistatic composite material according to claim 1, characterized in that: In step A5, the usage ratio of the pre-product, compound, acetonitrile and azobisisobutyronitrile is 0.01-0.03 mol: 0.01-0.03 mol: 2-18 mL: 0.25-0.35 g.

7. The method for preparing an impact-resistant and antistatic composite material according to claim 1, characterized in that: The toughening agent is EVA-g-MAH, the antioxidant is antioxidant 1010, and the lubricant is paraffin.

8. An impact-resistant and antistatic composite material, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 7.

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