Antistatic abs material and its preparation method and application

Abstract

The application belongs to the field of high polymer materials, and particularly relates to an antistatic ABS material and a preparation method and application thereof. The antistatic ABS material provided by the application contains the following components in parts by weight: modified ABS grafting glue powder 35-45 parts, SAN resin 50-60 parts, compounded antistatic agent 2-4 parts, compounded light stabilizer 0.2-0.5 parts, lubricant 0.5-1.0 parts, and antioxidant 0.2-0.5 parts. The antistatic ABS material provided by the application has good antistatic performance, high rigidity and high low-temperature toughness through the synergistic cooperation of the components.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of high polymer materials, and particularly relates to an antistatic ABS material and a preparation method and application thereof. BACKGROUND

[0002] The new edition of safety helmet standard GB 2811-2019 "Head Protection Safety Helmet" came into effect on July 1, 2020, and replaced the old edition of GB 2811-2007. The new edition of the standard distinguishes between ordinary and special types of safety helmets, and the basic performance test of the special type of antistatic safety helmet changes the low temperature test temperature from-20℃ to-30℃, which has higher requirements for the low temperature toughness of raw materials.

[0003] The raw materials for safety helmets on the market are mainly ABS, PC / ABS alloy, fiber reinforced composite materials, etc. PC has high toughness and rigidity at room temperature, but its disadvantage is that it is sensitive to notches and temperature, and it is easily damaged in the form of cracking in low temperature environment. The toughness is enhanced after being compounded with ABS, but the addition of antistatic agents will cause a substantial reduction in mechanical properties. Fiber reinforced composite materials have good rigidity and heat resistance, but the material uniformity is poor, the low temperature performance is relatively unstable, and there are disadvantages such as low production efficiency and high cost.

[0004] Chinese patent CN110387103A introduces a high-strength antistatic material for safety helmets and a preparation method thereof. ABS resin is used as the matrix, and polyamide is added to increase the toughness and impact resistance of the material. By adding ionic liquids and conductive polymers, the surface resistivity of the product can be reduced to 107Ω, and the performance is durable, with excellent impact resistance, puncture resistance, lateral rigidity, flame resistance, etc.

[0005] Chinese patent CN115627064A introduces an antistatic PC / ABS composition, a preparation method and application thereof. In the PC / ABS material system, by selecting a specific antistatic agent and adding a certain amount of stabilizers, toughening agents and fillers, the PC / ABS can have good antistatic properties while maintaining high rigidity and high toughness, thereby realizing an antistatic PC / ABS composition with high rigidity and high toughness.

[0006] In view of the improvement of the low temperature impact performance test standard of the new edition of safety helmet and the current situation of safety helmet raw materials on the market, it is expected to provide a safety helmet material that can meet the strength requirements of the new edition of safety helmet, has good antistatic performance, has high impact toughness in low temperature environment, and can also have good rigidity. SUMMARY

[0007] The present application aims to provide an antistatic ABS material, which can have good antistatic performance, high impact toughness in low temperature environment and good rigidity.

[0008] To solve the above technical problems, the present application adopts the following technical solutions.

[0009] According to the first aspect of the present application, an antistatic ABS material is provided, which comprises the following components in parts by weight: modified ABS grafting glue powder 35-45 parts, SAN resin 50-60 parts, compounded antistatic agent 2-4 parts, compounded light stabilizer 0.2-0.5 parts, lubricant 0.5-1.0 parts, and antioxidant 0.2-0.5 parts.

[0010] According to some embodiments of the present application, the SAN resin is acrylonitrile-styrene copolymer with acrylonitrile content of 26%-36%, number average molecular weight of 80000-100000, and melt flow rate of (10-30) g / 10 min.

[0011] According to some embodiments of the present application, the compounded antistatic agent is a mixture of one or more of stearate, allyl sulfonate, alkyl quaternary ammonium salt, and oxirane amine addition product.

[0012] According to some embodiments of the present application, the compounded antistatic agent is a mixture of allyl sulfonate and oxirane amine addition product, and the weight ratio of allyl sulfonate to oxirane amine addition product is (0.2-0.5):1.

[0013] According to some embodiments of the present application, the compounded light stabilizer is a mixture of one or more of UV531, UV329, UV326, UV770, and UV3035.

[0014] According to some embodiments of the present application, the lubricant is a mixture of one or more of magnesium stearate, zinc stearate, fatty acid amide, stearate, and silicone powder.

[0015] According to some embodiments of the present application, the antioxidant is a mixture of one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant 618.

[0016] According to some embodiments of the present application, the modified ABS grafting glue powder is prepared by the following method:

[0017] Step one: add polybutadiene latex into the reaction kettle, control the temperature of the reaction kettle at 60-85 DEG C, then mix the molecular weight regulator, initiator, acrylamide, styrene and acrylonitrile monomer mixture, deionized water uniformly, configure into emulsion and add into the reaction kettle, the feeding time is 1-2h, after reaction for 0.5-1h, the modified graft ABS emulsion is obtained;

[0018] Step two: add deionized water and coagulant into the coagulation kettle, control the temperature in the coagulation kettle at 70-90 DEG C, open the stirring, pour the modified graft ABS emulsion into the coagulation kettle, after coagulation for a period of time, the graft powder slurry is obtained;

[0019] Step three: the graft powder slurry is dehydrated and washed, then dried to obtain the modified ABS grafting rubber powder.

[0020] According to some embodiments of the present application, the polybutadiene latex is large particle size polybutadiene latex with solid content of 50-70% and particle size of 120-400nm.

[0021] According to some embodiments of the present application, the molecular weight regulator is tertiary dodecyl mercaptan, and the addition amount is 0.15-0.25% of the mass of the polybutadiene latex.

[0022] According to some embodiments of the present application, the initiator is cumene peroxide, and the addition amount is 0.15-0.25% of the mass of the polybutadiene latex.

[0023] According to some embodiments of the present application, the addition amount of acrylamide is 1-2% of the mass of the polybutadiene latex.

[0024] According to some embodiments of the present application, the addition amount of the styrene and acrylonitrile monomer mixture is 40-60% of the mass of the polybutadiene latex, and the mass ratio of styrene to acrylonitrile is 5:2.

[0025] According to some embodiments of the present application, the addition amount of deionized water in step one is 150-200% of the mass of the polybutadiene latex, and the addition amount of deionized water in step two is 280-320% of the mass of the modified graft ABS emulsion.

[0026] According to some embodiments of the present application, the coagulant is sulfuric acid, and the addition amount is 1-2% of the mass of the modified graft ABS emulsion.

[0027] According to a second aspect of the present invention, a method for preparing an antistatic ABS material according to the first aspect of the present invention is provided, comprising: weighing modified ABS grafted adhesive powder, SAN resin, compounded antistatic agent, compounded light stabilizer, lubricant, and antioxidant in parts by weight, mixing them evenly, melting and extruding them, and then pelletizing them to obtain the antistatic ABS material.

[0028] According to some embodiments of the present invention, the mixing process is carried out in a high-speed mixer, and the extrusion process is carried out in a twin-screw extruder, wherein the screw speed is 250 r / min-350 r / min and the extrusion temperature is 180℃-220℃.

[0029] According to a third aspect of the invention, the application of the antistatic ABS material according to the first aspect of the invention in safety helmets is provided.

[0030] By adopting the above technical solution, the present invention has the following advantages compared with the prior art:

[0031] The antistatic ABS material provided by this invention enhances low-temperature toughness by adding modified ABS grafted rubber powder and improves antistatic performance by adding a compounded antistatic agent. Due to the synergistic effect of the modified ABS grafted rubber powder, SAN resin, compounded antistatic agent, compounded light stabilizer, lubricant, and antioxidant, the ABS material provided by this invention exhibits excellent antistatic properties, high impact toughness in low-temperature environments, and good rigidity.

[0032] The antistatic ABS material provided by this invention can meet the strength requirements of the new version of safety helmets and can be applied to the field of safety helmets with antistatic requirements. Safety helmet products made from it ensure high lateral rigidity and high low temperature strength. Detailed Implementation

[0033] It should be understood that the embodiments of the invention shown in the exemplary embodiments are merely illustrative. Although only a few embodiments have been described in detail in this invention, those skilled in the art will readily recognize that various modifications are possible without substantially departing from the teachings of the invention. Accordingly, all such modifications should be included within the scope of the invention. Other substitutions, modifications, variations, and deletions can be made to the design, operating conditions, and parameters of the following exemplary embodiments without departing from the spirit of the invention.

[0034] According to a first aspect of the present invention, an antistatic ABS material is provided, comprising, by weight, the following components: 35-45 parts of modified ABS grafted adhesive powder, 50-60 parts of SAN resin, 2-4 parts of compounded antistatic agent, 0.2-0.5 parts of compounded light stabilizer, 0.5-1.0 parts of lubricant, and 0.2-0.5 parts of antioxidant.

[0035] Due to the synergistic effect of modified ABS grafted adhesive powder, SAN resin, compound antistatic agent, compound light stabilizer, lubricant, and antioxidant, the ABS material provided by this invention has good antistatic properties, high impact toughness in low-temperature environments, and good rigidity.

[0036] Preferably, the SAN resin is an acrylonitrile-styrene copolymer with an acrylonitrile content of 26%-36%, a number average molecular weight of 80,000-100,000, and a melt flow rate of (10-30) g / 10 min.

[0037] Preferably, the compounded antistatic agent is one or more of stearate, allyl sulfonate, alkyl quaternary ammonium salt, and ethylene oxide amine adduct.

[0038] Preferably, the compound antistatic agent is a mixture of allyl sulfonate and ethylene oxide amine adduct, with the weight ratio of allyl sulfonate to ethylene oxide amine adduct being (0.2-0.5):1.

[0039] Preferably, the compound light stabilizer is one or a mixture of UV531, UV329, UV326, UV770 and UV3035.

[0040] Preferably, the lubricant is one or more of magnesium stearate, zinc stearate, fatty acid amide, stearate, and silicone powder.

[0041] Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant 618.

[0042] In some embodiments, the modified ABS grafted adhesive powder is prepared by the following method:

[0043] Step 1: Add polybutadiene latex to the reactor and control the reactor temperature at 60℃-85℃. Then, mix the molecular weight regulator, initiator, acrylamide, styrene and acrylonitrile monomer mixture, and deionized water evenly to prepare an emulsion. Add the emulsion to the reactor and add it over 1-2 hours. After reacting for 0.5-1 hour, the modified grafted ABS emulsion is obtained.

[0044] Step 2: Add deionized water and coagulant to the coagulation kettle, control the temperature inside the coagulation kettle to 70℃-90℃, turn on the stirring, pour the modified grafted ABS emulsion into the coagulation kettle, and obtain the grafted powder slurry after coagulation for a period of time.

[0045] Step 3: Dehydrate and wash the grafted slurry, and then dry it to obtain modified ABS grafted adhesive powder.

[0046] The modified ABS grafted adhesive powder prepared by this invention improves toughening efficiency and enhances the low-temperature toughness of antistatic ABS materials. By grafting acrylamide, the modified ABS grafted adhesive powder prepared by this invention improves the continuity of polar functional groups in the polymer, enhances the dispersibility and compatibility of the antistatic agent, and thus improves the antistatic performance of the antistatic ABS material to a certain extent.

[0047] Preferably, the polybutadiene latex is a large-particle-size polybutadiene latex with a solid content of 50%-70% and a particle size of 120nm-400nm.

[0048] Preferably, the molecular weight regulator is tert-dodecyl mercaptan, and the amount added is 0.15%-0.25% of the mass of polybutadiene latex.

[0049] Preferably, the initiator is cumene hydrogen peroxide, and the amount added is 0.15%-0.25% of the mass of polybutadiene latex.

[0050] Preferably, the amount of acrylamide added is 1%-2% of the mass of the polybutadiene latex.

[0051] Preferably, the amount of styrene and acrylonitrile monomer mixture added is 40%-60% of the mass of polybutadiene latex, wherein the mass ratio of styrene to acrylonitrile is 5:2.

[0052] Preferably, in step one, the amount of deionized water added is 150%-200% of the mass of the polybutadiene latex, and in step two, the amount of deionized water added is 280%-320% of the mass of the modified grafted ABS emulsion.

[0053] Preferably, the coagulant is sulfuric acid, and the amount added is 1%-2% of the mass of the modified grafted ABS emulsion.

[0054] Preferably, in step one, the prepared emulsion is added to the reaction vessel at a constant speed and continuously using a metering pump.

[0055] Preferably, in step two, the coagulation time is 10 minutes.

[0056] Preferably, in step three, the grafted powder slurry is dehydrated and washed in a centrifugal dewatering machine for 5 minutes.

[0057] According to a second aspect of the present invention, a method for preparing an antistatic ABS material according to the first aspect of the present invention is provided, comprising: weighing modified ABS grafted adhesive powder, SAN resin, compounded antistatic agent, compounded light stabilizer, lubricant, and antioxidant in parts by weight, mixing them evenly, melting and extruding them, and then pelletizing them to obtain the antistatic ABS material.

[0058] The method for preparing antistatic ABS material provided by this invention is simple to operate, easy to implement, and convenient for industrial production.

[0059] In some embodiments, modified ABS grafted rubber powder, SAN resin, compound antistatic agent, compound light stabilizer, lubricant, and antioxidant are weighed according to the weight parts, mixed evenly in a high-speed mixer, and then added to a twin-screw extruder for melting and extrusion. The screw speed is 250r / min-350r / min, the extrusion temperature is 180℃-220℃, and then pelletized to obtain antistatic ABS material.

[0060] According to a third aspect of the invention, the application of the antistatic ABS material according to the first aspect of the invention in safety helmets is provided.

[0061] The safety helmet products made of ABS material provided by this invention ensure high lateral rigidity and high low-temperature strength, and can be applied in the field of safety helmets with anti-static requirements.

[0062] The technical solutions of the present invention will be described in detail below through specific embodiments.

[0063] Preparation methods of the examples and comparative examples:

[0064] According to the weight parts, accurately measure the modified ABS grafted rubber powder, high-impact SAN resin, compound antistatic agent, compound light stabilizer, lubricant and antioxidant, and then put them into a high-speed mixer. Mix at 600r / min-900r / min for 2-6 minutes. After the mixture is evenly mixed, add it to a twin-screw extruder for melting, extrusion and pelletizing to prepare antistatic ABS material. The twin-screw extruder has a main motor speed of 250 r / min-350 r / min and its temperature settings are as follows: feeding section 180℃-190℃, second section 190℃-210℃, third section 190℃-210℃, fourth section 190℃-210℃, fifth section 190℃-210℃, sixth section 190℃-210℃, seventh section 190℃-210℃, eighth section 190℃-210℃, ninth section 190℃-210℃, and die head temperature 200℃-220℃.

[0065] Relevant performance testing methods:

[0066] Tensile strength: Samples were prepared and tested in accordance with GB / T 1040.1-2006 standard, with a tensile speed of 50 mm / min.

[0067] Bending strength: Samples were prepared and tested in accordance with GB / T 9341-2008 standard, with a testing speed of 2 mm / min.

[0068] Impact strength: Samples were prepared and tested in accordance with GB / T 1043.1-2008 standard, using a simply supported beam notch method, with a notch depth of (2±0.2) mm.

[0069] Vicat softening temperature: Tested according to GB / T 1633-2000 standard, B50 method.

[0070] Surface resistivity: Tested in accordance with GB / T 1410-2006 standard, with ambient humidity of 45%-55% and test voltage of 1000V.

[0071] Lateral stiffness and low-temperature performance of safety helmets: tested in accordance with GB 2811-2019 standard.

[0072] Example 1 (1) 100 parts of polybutadiene latex were added to the reactor and the reactor temperature was controlled at 68°C. Then, 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydrogen peroxide, 1 part of acrylamide, 60 parts of styrene and acrylonitrile monomer mixture (styrene to acrylonitrile weight ratio of 5:2) and 150 parts of deionized water were mixed evenly to prepare an emulsion. The emulsion was then added to the reactor at a constant speed and continuously using a metering pump. The feeding time was 1 hour. After reacting for 30 minutes, the modified grafted ABS emulsion was obtained.

[0073] (2) Add 300 parts of deionized water and 1 part of coagulant sulfuric acid to the coagulation kettle, stir at 100 rpm, mix evenly, add 100 parts of modified graft emulsion to the coagulation kettle, coagulate at 85°C for 10 minutes to obtain grafted powder slurry, pour the slurry into a centrifugal dewatering machine for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS grafted rubber powder.

[0074] (3) 42 parts of modified ABS grafted rubber powder, 53 parts of high-impact SAN resin, 3 parts of compound antistatic agent (the weight ratio of allyl sulfonate to ethylene oxide amine adduct is 1:5), 0.5 parts of compound light stabilizer (UV531 and UV329, respectively, the weight ratio is 1:1), 1 part of lubricant (magnesium stearate and fatty acid amide, respectively, the weight ratio is 1:4), and 0.5 parts of antioxidant (antioxidant 1010 and antioxidant 168, respectively, the weight ratio is 1:1) were added to a high-speed mixer and mixed evenly. The mixture was then added to a twin-screw extruder for melt extrusion and pelletizing to prepare antistatic ABS material.

[0075] Example 2

[0076] (1) Add 100 parts of polybutadiene latex to the reactor and control the reactor temperature to 60℃. Then, mix 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydrogen peroxide, 1 part of acrylamide, 60 parts of styrene and acrylonitrile monomer mixture (styrene to acrylonitrile weight ratio of 5:2) with 150 parts of deionized water to form an emulsion. Then, add the emulsion to the reactor at a constant speed and continuously using a metering pump. The feeding time is 1 hour. After reacting for 30 minutes, the modified grafted ABS emulsion is obtained.

[0077] (2) Add 280 parts of deionized water and 1 part of coagulant sulfuric acid to the coagulation kettle, stir at 100 rpm, mix evenly, add 100 parts of modified graft emulsion to the coagulation kettle, coagulate at 85°C for 10 minutes to obtain grafted powder slurry, pour the slurry into a centrifugal dewatering machine for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS grafted rubber powder.

[0078] (3) Measure 35 parts of modified ABS grafted rubber powder, 60 parts of high-impact SAN resin, 3 parts of compound antistatic agent (the weight ratio of allyl sulfonate to ethylene oxide amine adduct is 1:5), 0.5 parts of compound light stabilizer (UV531 and UV329, respectively, the weight ratio is 1:1), 1 part of lubricant (magnesium stearate and fatty acid amide, respectively, the weight ratio is 1:4), and 0.5 parts of antioxidant (antioxidant 1010 and antioxidant 168, respectively, the weight ratio is 1:1) and add them to a high-speed mixer and mix evenly. Add the mixture to a twin-screw extruder for melt extrusion and pelletizing to prepare antistatic ABS material.

[0079] Example 3

[0080] (1) Add 100 parts of polybutadiene latex to the reactor and control the reactor temperature to 85℃. Then, mix 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydrogen peroxide, 1 part of acrylamide, 60 parts of styrene and acrylonitrile monomer mixture (styrene to acrylonitrile weight ratio of 5:2) with 150 parts of deionized water to form an emulsion. Then, add the emulsion to the reactor at a constant speed and continuously using a metering pump. The feeding time is 1 hour. After reacting for 30 minutes, the modified grafted ABS emulsion is obtained.

[0081] (2) Add 300 parts of deionized water and 1 part of coagulant sulfuric acid to the coagulation kettle, stir at 100 rpm, mix evenly, add 100 parts of modified graft emulsion to the coagulation kettle, coagulate at 85°C for 10 minutes to obtain grafted powder slurry, pour the slurry into a centrifugal dewatering machine for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS grafted rubber powder.

[0082] (3) 42 parts of modified ABS grafted rubber powder, 54 parts of high-impact SAN resin, 2 parts of compound antistatic agent (the weight ratio of allyl sulfonate to ethylene oxide amine adduct is 1:2), 0.5 parts of compound light stabilizer (UV531 and UV329, respectively, the weight ratio is 1:1), 1 part of lubricant (magnesium stearate and fatty acid amide, respectively, the weight ratio is 1:4), and 0.5 parts of antioxidant (antioxidant 1010 and antioxidant 168, respectively, the weight ratio is 1:1) were added to a high-speed mixer and mixed evenly. The mixture was then added to a twin-screw extruder for melt extrusion and pelletizing to prepare antistatic ABS material.

[0083] Example 4

[0084] (1) Add 100 parts of polybutadiene latex to the reactor and control the reactor temperature to 70℃. Then, mix 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydrogen peroxide, 1 part of acrylamide, 60 parts of styrene and acrylonitrile monomer mixture (styrene to acrylonitrile weight ratio of 5:2) with 200 parts of deionized water to form an emulsion. Then, add the emulsion to the reactor at a constant speed and continuously using a metering pump. The feeding time is 2 hours. After reacting for 30 minutes, the modified grafted ABS emulsion is obtained.

[0085] (2) Add 320 parts of deionized water and 2 parts of coagulant sulfuric acid to the coagulation kettle, stir at 100 rpm, mix evenly, add 100 parts of modified graft emulsion to the coagulation kettle, coagulate at 90℃ for 10 minutes to obtain grafted powder slurry, pour the slurry into a centrifugal dewatering machine for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS grafted rubber powder.

[0086] (3) Measure 45 parts of modified ABS grafted rubber powder, 50 parts of high-impact SAN resin, 3 parts of compound antistatic agent (the weight ratio of allyl sulfonate to ethylene oxide amine adduct is 1:5), 0.5 parts of compound light stabilizer (UV531 and UV329, respectively, the weight ratio is 1:1), 1 part of lubricant (magnesium stearate and fatty acid amide, respectively, the weight ratio is 1:4), and 0.5 parts of antioxidant (antioxidant 1010 and antioxidant 168, respectively, the weight ratio is 1:1) and add them to a high-speed mixer and mix evenly. Add the mixture to a twin-screw extruder for melt extrusion and pelletizing to prepare antistatic ABS material.

[0087] Example 5

[0088] (1) Add 100 parts of polybutadiene latex to the reactor and control the reactor temperature to 72℃. Then, mix 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydrogen peroxide, 2 parts of acrylamide, 50 parts of styrene and acrylonitrile monomer mixture (styrene to acrylonitrile weight ratio of 5:2) with 180 parts of deionized water to form an emulsion. Then, add the emulsion to the reactor at a constant speed and continuously using a metering pump. The feeding time is 1.5h. After reacting for 30 minutes, the modified grafted ABS emulsion is obtained.

[0089] (2) Add 300 parts of deionized water and 1 part of coagulant sulfuric acid to the coagulation kettle, stir at 100 rpm, mix evenly, add 100 parts of modified graft emulsion to the coagulation kettle, coagulate at 70°C for 10 minutes to obtain grafted powder slurry, pour the slurry into a centrifugal dewatering machine for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS grafted rubber powder.

[0090] (3) 42 parts of modified ABS grafted rubber powder, 52 parts of high-impact SAN resin, 4 parts of compound antistatic agent (the weight ratio of allyl sulfonate to ethylene oxide amine adduct is 1:5), 0.5 parts of compound light stabilizer (UV531 and UV329, respectively, the weight ratio is 1:1), 1 part of lubricant (magnesium stearate and fatty acid amide, respectively, the weight ratio is 1:4) and 0.5 parts of antioxidant (antioxidant 1010 and antioxidant 168, respectively, the weight ratio is 1:1) were added to a high-speed mixer and mixed evenly. The mixture was then added to a twin-screw extruder for melt extrusion and pelletizing to prepare antistatic ABS material.

[0091] Example 6:

[0092] (1) 100 parts of polybutadiene latex, 0.15 parts of molecular weight regulator tert-dodecyl mercaptan, 0.15 parts of initiator cumene hydrogen peroxide, 1 part of acrylamide and 150 parts of deionized water were added to a reaction vessel and stirred evenly to prepare an emulsion. Then, 40 parts of a mixture of styrene and acrylonitrile monomers (styrene to acrylonitrile weight ratio of 5:2) were continuously added. The reaction vessel temperature was 68°C, the feeding time was 1 hour, and the reaction time was 1 hour to obtain modified grafted ABS emulsion.

[0093] (2) Add 280 parts of deionized water and 1 part of coagulant sulfuric acid to the coagulation kettle, stir at 100 rpm, mix evenly, add 100 parts of modified graft emulsion to the coagulation kettle, coagulate at 85°C for 10 minutes to obtain grafted powder slurry, pour the slurry into a centrifugal dewatering machine for dehydration, washing, and drying to obtain modified ABS grafted rubber powder.

[0094] (3) 42 parts of modified ABS grafted rubber powder, 54.1 parts of high-impact SAN resin, 3 parts of compound antistatic agent (the weight ratio of allyl sulfonate to ethylene oxide amine adduct is 1:5), 0.2 parts of compound light stabilizer (UV531 and UV329, respectively, the weight ratio is 1:1), 0.5 parts of lubricant (magnesium stearate and fatty acid amide, respectively, the weight ratio is 1:4) and 0.2 parts of antioxidant (antioxidant 1010 and antioxidant 168, respectively, the weight ratio is 1:1) were added to a high-speed mixer and mixed evenly. The mixture was then added to a twin-screw extruder for melt extrusion and pelletizing to prepare antistatic ABS material.

[0095] Example 7:

[0096] (1) Add 100 parts of polybutadiene latex to the reactor and control the reactor temperature to 68℃. Then, mix 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydrogen peroxide, 60 parts of styrene and acrylonitrile monomer mixture (styrene to acrylonitrile weight ratio of 5:2) with 150 parts of deionized water to form an emulsion. Then, add the emulsion to the reactor at a constant speed and continuously using a metering pump. The feeding time is 1 hour. After reacting for 30 minutes, the modified grafted ABS emulsion is obtained.

[0097] (2) Add 300 parts of deionized water and 1 part of coagulant sulfuric acid to the coagulation kettle, stir at 100 rpm, mix evenly, add 100 parts of modified graft emulsion to the coagulation kettle, coagulate at 85°C for 10 minutes to obtain grafted powder slurry, pour the slurry into a centrifugal dewatering machine for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS grafted rubber powder.

[0098] (3) 42 parts of modified ABS grafted rubber powder, 53 parts of high-impact SAN resin, 3 parts of compound antistatic agent (the weight ratio of allyl sulfonate to ethylene oxide amine adduct is 1:5), 0.5 parts of compound light stabilizer (UV531 and UV329, respectively, the weight ratio is 1:1), 1 part of lubricant (magnesium stearate and fatty acid amide, respectively, the weight ratio is 1:4), and 0.5 parts of antioxidant (antioxidant 1010 and antioxidant 168, respectively, the weight ratio is 1:1) were added to a high-speed mixer and mixed evenly. The mixture was then added to a twin-screw extruder for melt extrusion and pelletizing to prepare antistatic ABS material.

[0099] Comparative Example 1:

[0100] 42 parts of unmodified general-purpose ABS grafted rubber powder, 53 parts of high-impact SAN resin, 3 parts of compound antistatic agent (allyl sulfonate and ethylene oxide amine adduct in a weight ratio of 1:5), 0.5 parts of compound light stabilizer (UV531 and UV329 in a weight ratio of 1:1), 1 part of lubricant (magnesium stearate and fatty acid amide in a weight ratio of 1:4), and 0.5 parts of antioxidant (antioxidant 1010 and antioxidant 168 in a weight ratio of 1:1) were added to a high-speed mixer and mixed evenly. The mixture was then added to a twin-screw extruder for melt extrusion and pelletizing to prepare antistatic ABS material.

[0101] Comparative Example 2:

[0102] (1) Add 100 parts of polybutadiene latex to the reactor and control the reactor temperature to 68℃. Then, mix 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydrogen peroxide, 1 part of acrylamide, 60 parts of styrene and acrylonitrile monomer mixture (styrene to acrylonitrile weight ratio of 5:2), and 150 parts of deionized water evenly to prepare an emulsion. Then, add the emulsion to the reactor at a constant speed and continuously using a metering pump for 1 hour. After the reaction is completed, the modified grafted ABS emulsion is obtained.

[0103] (2) Add 300 parts of deionized water and 1 part of coagulant sulfuric acid to the coagulation kettle, stir at 100 rpm, mix evenly, add 100 parts of modified graft emulsion to the coagulation kettle, coagulate at 85°C for 10 minutes to obtain grafted powder slurry, pour the slurry into a centrifugal dewatering machine for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS grafted rubber powder.

[0104] (3) 42 parts of modified ABS grafted rubber powder, 53 parts of high-impact SAN resin, 3 parts of allyl sulfonate antistatic agent, 0.5 parts of compound light stabilizer (UV531 and UV329, respectively, with a weight ratio of 1:1), 1 part of lubricant (magnesium stearate and fatty acid amide, respectively, with a weight ratio of 1:4), and 0.5 parts of antioxidant (antioxidant 1010 and antioxidant 168, respectively, with a weight ratio of 1:1) were added to a high-speed mixer and mixed evenly. The mixture was then added to a twin-screw extruder for melt extrusion and pelletizing to prepare antistatic ABS material.

[0105] The antistatic ABS materials prepared in Examples 1-7 and Comparative Examples 1-2 were tested using the test methods mentioned above. The test results are shown in Table 1 below.

[0106] Table 1 Performance test results of Examples 1-7 and Comparative Examples 1-2

[0107]

[0108] As can be seen from the data in Table 1: Example 1 balances the rigidity and low-temperature toughness of antistatic ABS material, exhibiting good overall performance. Compared with Example 1, Example 2 lowers the graft polymerization temperature and the proportion of toughening powder, resulting in slightly lower low-temperature impact strength of the antistatic ABS material, while maintaining better rigidity. Compared with Example 1, Example 3 increases the graft polymerization temperature and the proportion of propyl sulfonate in the compounded antistatic agent, achieving similar mechanical properties but slightly poorer antistatic performance. Compared with Example 1, Example 4 increases the polymerization time of the modified ABS powder and increases the proportion of toughening powder, resulting in varying degrees of reduction in both rigidity and heat resistance of the antistatic ABS. Compared with Example 1, Example 5 increases the proportion of compounded antistatic agent, improving the antistatic performance of the antistatic ABS to some extent, while reducing impact performance. Compared with Example 1, Example 6 reduces the amount of molecular weight regulator, initiator, and monomer added, and decreases the amount of blending additives, resulting in some improvement in low-temperature impact performance and rigidity. Compared to Example 1, Example 7 showed a decrease in antistatic performance due to the absence of acrylamide in the modified grafted ABS powder. This indicates that the addition of acrylamide monomer during the grafting process has a synergistic effect on the allyl sulfonate and ethylene oxide amine compound antistatic agent, thus improving antistatic efficiency. Comparative Example 1 used unmodified commercially available ABS powder, resulting in only moderate toughening effect and poor lateral rigidity and low-temperature strength in the safety helmet product. Comparative Example 2 used allyl sulfonate antistatic agent alone, and the antistatic performance of the ABS was lower compared to Example 1.

[0109] In summary, the antistatic ABS material prepared by this invention improves toughening efficiency and enhances low-temperature toughness by synthesizing modified ABS powder, improves antistatic performance by compounding antistatic agents, and synergistically combines components such as SAN resin, light stabilizer, lubricant and antioxidant to give the ABS material good antistatic properties while maintaining high rigidity and high low-temperature toughness.

[0110] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention. Any modifications or equivalent substitutions made to the present invention without departing from the spirit and scope thereof should be covered within the protection scope of the claims of the present invention.

Claims

1. An antistatic ABS material, characterized in that, By weight, it contains the following components: 35-45 parts modified ABS grafted adhesive powder, 50-60 parts SAN resin, 2-4 parts compounded antistatic agent, 0.2-0.5 parts compounded light stabilizer, 0.5-1.0 parts lubricant, and 0.2-0.5 parts antioxidant. The SAN resin is an acrylonitrile-styrene copolymer with an acrylonitrile content of 26%-36%, a number average molecular weight of 80,000-100,000, and a melt flow rate of (10-30) g / 10min. The compound antistatic agent is a mixture of allyl sulfonate and ethylene oxide amine adduct, with a weight ratio of allyl sulfonate to ethylene oxide amine adduct of (0.2-0.5):

1. The modified ABS grafted adhesive powder is prepared by the following method: Step 1: Add polybutadiene latex to the reactor and control the reactor temperature at 60℃-85℃. Then, mix the molecular weight regulator, initiator, acrylamide, styrene and acrylonitrile monomer mixture, and deionized water evenly to prepare an emulsion. Add the emulsion to the reactor and add it over 1-2 hours. After reacting for 0.5-1 hour, the modified grafted ABS emulsion is obtained. Step 2: Add deionized water and coagulant to the coagulation kettle, control the temperature inside the coagulation kettle to 70℃-90℃, turn on the stirring, pour the modified grafted ABS emulsion into the coagulation kettle, and obtain the grafted powder slurry after coagulation for a period of time. Step 3: Dehydrate and wash the grafted slurry, and then dry it to obtain modified ABS grafted adhesive powder.

2. The antistatic ABS material according to claim 1, characterized in that, The compound light stabilizer is a mixture of several of UV531, UV329, UV326, UV770 and UV3035.

3. The antistatic ABS material according to claim 1, characterized in that, The lubricant is one or more of magnesium stearate, zinc stearate, fatty acid amide, stearate, and silicone powder.

4. The antistatic ABS material according to claim 1, characterized in that, The antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant 618.

5. The antistatic ABS material according to claim 1, characterized in that, The polybutadiene latex is a large-particle-size polybutadiene latex with a solid content of 50%-70% and a particle size of 120nm-400nm.

6. The antistatic ABS material according to claim 1, characterized in that, The molecular weight regulator is tert-dodecyl mercaptan, and the amount added is 0.15%-0.25% of the mass of the polybutadiene latex.

7. The antistatic ABS material according to claim 1, characterized in that, The initiator is cumene hydrogen peroxide, and the amount added is 0.15%-0.25% of the mass of the polybutadiene latex.

8. The antistatic ABS material according to claim 1, characterized in that, The amount of acrylamide added is 1%-2% of the mass of the polybutadiene latex.

9. The antistatic ABS material according to claim 1, characterized in that, The amount of the styrene and acrylonitrile monomer mixture added is 40%-60% of the mass of the polybutadiene latex, wherein the mass ratio of styrene to acrylonitrile is 5:

2.

10. The antistatic ABS material according to claim 1, characterized in that, In step one, the amount of deionized water added is 150%-200% of the mass of the polybutadiene latex, and in step two, the amount of deionized water added is 280%-320% of the mass of the modified grafted ABS emulsion.

11. The antistatic ABS material according to claim 1, characterized in that, The coagulant is sulfuric acid, and the amount added is 1%-2% of the mass of the modified grafted ABS emulsion.

12. A method for preparing an antistatic ABS material as described in any one of claims 1-11, characterized in that, include: Modified ABS grafted adhesive powder, SAN resin, compound antistatic agent, compound light stabilizer, lubricant, and antioxidant are weighed according to the weight parts, mixed evenly, melted, extruded, and then pelletized to obtain antistatic ABS material.

13. The preparation method according to claim 12, characterized in that, The mixing process is carried out in a high-speed mixer, and the extrusion process is carried out in a twin-screw extruder. During the extrusion process, the screw speed is 250r / min-350r / min, and the extrusion temperature is 180℃-220℃.

14. The use of the antistatic ABS material according to any one of claims 1-11 in safety helmets.

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