Antistatic ABS (acrylonitrile-butadiene-styrene) material as well as preparation method and application thereof

Abstract

The invention belongs to the field of high polymer materials, and particularly relates to an antistatic ABS (Acrylonitrile Butadiene Styrene) material as well as a preparation method and application thereof. The antistatic ABS material provided by the invention is prepared from the following components in parts by weight: 35 to 45 parts of modified ABS grafted rubber powder, 50 to 60 parts of SAN (Styrene Acrylonitrile Butadiene Styrene) resin, 2 to 4 parts of compound antistatic agent, 0.2 to 0.5 part of compound light stabilizer, 0.5 to 1.0 part of lubricant and 0.2 to 0.5 part of antioxidant. According to the antistatic ABS material provided by the invention, all the components are synergistically matched, so that high rigidity and high low-temperature toughness are kept while the antistatic ABS material has good antistatic performance.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials, and in particular relates to an antistatic ABS material and a preparation method and application thereof. Background Art

[0002] The new version of the safety helmet standard GB 2811-2019 "Head protection safety helmet" will take effect on July 1, 2020, replacing the old version GB 2811-2007. The new version of the standard distinguishes between ordinary and special types of safety helmets. In terms of basic performance testing of special anti-static safety helmets, the low-temperature test temperature is changed from -20℃ to -30℃, and higher requirements are placed on the low-temperature toughness of raw materials.

[0003] The raw materials of 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 is easily damaged by cracking in low-temperature environments. After being compounded with ABS, its toughness is enhanced, but the addition of antistatic agents will cause its mechanical properties to be greatly reduced. 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 its preparation method. It uses ABS resin as the matrix and adds polyamide 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 long-lasting, with excellent impact resistance, puncture resistance, lateral rigidity, flame retardancy, 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 stabilizer, toughening agent and filler, it is possible to give PC / ABS good antistatic properties while maintaining high rigidity and high toughness, thereby achieving an antistatic PC / ABS composition with both high rigidity and high toughness.

[0006] In view of the improvement of the low-temperature impact performance test standards of the new version of safety helmets and the current status of safety helmet raw materials on the market, it is hoped to provide a safety helmet material that can meet the strength requirements of the new version of safety helmets, has good anti-static properties, has high impact toughness in low-temperature environments, and can take into account good rigidity. Summary of the invention

[0007] The object of the present invention is to provide an antistatic ABS material, which can have good antistatic performance, high impact toughness in a low temperature environment, and good rigidity.

[0008] In order to solve the above technical problems, the present invention adopts the following technical solutions:

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

[0010] According to some embodiments of the present invention, the SAN resin is an acrylonitrile-styrene copolymer having 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.

[0011] According to some embodiments of the present invention, the compound antistatic agent is a mixture of one or more of stearic acid esters, allyl sulfonates, alkyl quaternary ammonium salts, and ethylene oxide amine adducts.

[0012] According to some embodiments of the present invention, the compound antistatic agent is a mixture of allyl sulfonate and ethylene oxide amine adducts, and the weight ratio of allyl sulfonate to ethylene oxide amine adducts is (0.2-0.5):1.

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

[0014] According to some embodiments of the present invention, 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 invention, 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 invention, the modified ABS grafted rubber powder is prepared by the following method:

[0017] Step 1: Add polybutadiene latex into a reactor, control the temperature of the reactor to 60°C-85°C, then mix the molecular weight regulator, initiator, acrylamide, styrene and acrylonitrile monomer mixed solution, and deionized water evenly, prepare the emulsion and add it into the reactor, the feeding time is 1-2h, and the modified grafted ABS emulsion is obtained after reacting for 0.5-1h;

[0018] Step 2: Add deionized water and coagulant into the coagulation kettle, control the temperature in the coagulation kettle to 70°C-90°C, start stirring, pour the modified grafted ABS emulsion into the coagulation kettle, and obtain the grafted powder slurry after coagulation for a period of time;

[0019] Step 3: Dehydrating and washing the grafted powder slurry, and then drying it to obtain the modified ABS grafted rubber powder.

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

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

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

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

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

[0025] According to some embodiments of the present invention, the amount of deionized water added in step 1 is 150%-200% of the mass of the polybutadiene latex, and the amount of deionized water added in step 2 is 280%-320% of the mass of the modified grafted ABS emulsion.

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

[0027] According to a second aspect of the present invention, there is provided a method for preparing the antistatic ABS material according to the first aspect of the present invention, comprising: weighing modified ABS grafted rubber powder, SAN resin, compound antistatic agent, compound light stabilizer, lubricant, and antioxidant according to weight proportions, 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. During the extrusion process, the speed of the screw main engine is 250r / min-350r / min, and the extrusion temperature is 180℃-220℃.

[0029] According to a third aspect of the present invention, there is provided a use of the antistatic ABS material according to the first aspect of the present invention in a safety helmet.

[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 the present 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 the present invention has good antistatic performance, high impact toughness in a low-temperature environment, and can also take into account good rigidity.

[0032] The antistatic ABS material provided by the present invention can meet the strength requirements of the new version of the safety helmet, and can be applied to the field of safety helmets with antistatic requirements. The safety helmet products prepared therefrom ensure high lateral rigidity and high low-temperature strength. DETAILED DESCRIPTION

[0033] It should be understood that the embodiments of the present invention shown in the exemplary embodiments are only illustrative. Although only a few embodiments are described in detail in the present invention, it is easy for those skilled in the art to appreciate that multiple modifications are feasible without actually departing from the teaching of the subject matter of the present invention. Accordingly, all such modifications should be included within the scope of the present invention. Without departing from the gist of the present invention, other replacements, modifications, changes and deletions may be made to the design, operating conditions and parameters of the following exemplary embodiments.

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

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

[0036] Preferably, the SAN resin is an acrylonitrile-styrene copolymer having 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 compound antistatic agent is a mixture of one or more of stearic acid esters, allyl sulfonates, alkyl quaternary ammonium salts, and ethylene oxide amine adducts.

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

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

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

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

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

[0043] Step 1: Add polybutadiene latex into a reactor, control the temperature of the reactor to 60°C-85°C, then mix the molecular weight regulator, initiator, acrylamide, styrene and acrylonitrile monomer mixed solution, and deionized water evenly, prepare the emulsion and add it into the reactor, the feeding time is 1-2h, and the modified grafted ABS emulsion is obtained after reacting for 0.5-1h;

[0044] Step 2: Add deionized water and coagulant into the coagulation kettle, control the temperature in the coagulation kettle to 70°C-90°C, start 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: Dehydrating and washing the grafted powder slurry, and then drying it to obtain the modified ABS grafted rubber powder.

[0046] The modified ABS grafted rubber powder prepared by the present invention improves the toughening efficiency and enhances the low-temperature toughness of the antistatic ABS material. The modified ABS grafted rubber powder prepared by the present invention improves the continuity of polar functional groups in the polymer by grafting acrylamide, improves 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 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 added amount is 0.15%-0.25% of the mass of the polybutadiene latex.

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

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

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

[0052] Preferably, the amount of deionized water added in step 1 is 150%-200% of the mass of the polybutadiene latex, and the amount of deionized water added in step 2 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 1, the prepared emulsion is added to the reactor continuously and at a uniform speed using a metering pump.

[0055] Preferably, in step 2, the coagulation time is 10 minutes.

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

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

[0058] The preparation method of the antistatic ABS material provided by the 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 weight proportions, mixed evenly in a high-speed mixer, and then added to a twin-screw extruder for melting and extrusion. The main screw speed is 250r / min-350r / min, the extrusion temperature is 180℃-220℃, and then pelletized to obtain the antistatic ABS material.

[0060] According to a third aspect of the present invention, there is provided a use of the antistatic ABS material according to the first aspect of the present invention in a safety helmet.

[0061] The safety helmet product made of the ABS material provided by the present invention ensures higher lateral rigidity and higher low-temperature strength, and can be applied to the field of safety helmets with anti-static requirements.

[0062] The above technical solution of the present invention is described in detail below through specific embodiments.

[0063] Preparation methods of embodiments and comparative examples:

[0064] According to the weight percentage, the modified ABS grafted rubber powder, high-impact SAN resin, compound antistatic agent, compound light stabilizer, lubricant and antioxidant are accurately measured, and then put into a high-speed mixer, mixed at 600r / min-900r / min for 2-6 minutes, and after the mixture is evenly mixed, it is added into a twin-screw extruder for melting, extrusion and pelletizing to prepare the antistatic ABS material. Among them, the main engine speed of the twin-screw extruder is 250r / min-350r / min, and the temperature of the twin-screw extruder is set to a feeding section temperature of 180℃-190℃, a second section temperature of 190℃-210℃, a third section temperature of 190℃-210℃, a fourth section temperature of 190℃-210℃, a fifth section temperature of 190℃-210℃, a sixth section temperature of 190℃-210℃, a seventh section temperature of 190℃-210℃, an eighth section temperature of 190℃-210℃, a ninth section temperature of 190℃-210℃, and a head temperature of 200℃-220℃.

[0065] Related performance test 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 test speed of 2mm / min.

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

[0069] Vicat softening temperature: tested in accordance with GB / T 1633-2000 standard, B50 method.

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

[0071] Helmet lateral rigidity and low temperature performance: tested in accordance with GB 2811-2019 standard.

[0072] Example 1 (1) 100 parts of polybutadiene latex are added to a reactor, and the temperature of the reactor is controlled to be 68°C. Then, 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator isopropylbenzene hydroperoxide, 1 part of acrylamide, 60 parts of styrene and acrylonitrile monomer mixture (the weight ratio of styrene to acrylonitrile is 5:2) and 150 parts of deionized water are mixed evenly, and after being prepared into an emulsion, they are added to the reactor at a uniform speed and continuously using a metering pump. The feeding time is 1 hour. After reacting for 30 minutes, a modified grafted ABS emulsion is obtained.

[0073] (2) Add 300 parts of deionized water and 1 part of coagulant sulfuric acid into a coagulation kettle, stir at 100 rpm, mix well, then add 100 parts of modified graft latex into the coagulation kettle, coagulate at 85°C for 10 minutes to obtain graft powder slurry, pour the slurry into a centrifugal dehydrator for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS graft 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 and ethylene oxide amine adduct is 1:5), 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 weighed and added into a high-speed mixer and mixed evenly. The mixture was added into a twin-screw extruder for melt extrusion and pelletizing to prepare an antistatic ABS material.

[0075] Example 2

[0076] (1) 100 parts of polybutadiene latex were added into a reactor, and the temperature of the reactor was controlled at 60°C. Then, 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydroperoxide, 1 part of acrylamide, 60 parts of styrene and acrylonitrile monomer mixture (the weight ratio of styrene to acrylonitrile was 5:2) and 150 parts of deionized water were mixed evenly, and the mixture was prepared into an emulsion, and then added into the reactor at a uniform speed and continuously with a metering pump. The feeding time was 1 hour, and the modified grafted ABS emulsion was obtained after the reaction time was 30 minutes.

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

[0078] (3) 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 and ethylene oxide amine adduct is 1:5), 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 weighed and added into a high-speed mixer to mix evenly, and the mixture was added into a twin-screw extruder for melt extrusion and pelletizing to prepare an antistatic ABS material.

[0079] Example 3

[0080] (1) 100 parts of polybutadiene latex were added into a reactor, and the temperature of the reactor was controlled to be 85°C. Then, 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydroperoxide, 1 part of acrylamide, 60 parts of styrene and acrylonitrile monomer mixture (the weight ratio of styrene to acrylonitrile was 5:2) and 150 parts of deionized water were mixed evenly, and the mixture was prepared into an emulsion, and then added into the reactor at a uniform speed and continuously with a metering pump. The feeding time was 1 hour, and the modified grafted ABS emulsion was obtained after the reaction time was 30 minutes.

[0081] (2) Add 300 parts of deionized water and 1 part of coagulant sulfuric acid into a coagulation kettle, stir at 100 rpm, mix well, then add 100 parts of modified graft latex into the coagulation kettle, coagulate at 85°C for 10 minutes to obtain graft powder slurry, pour the slurry into a centrifugal dehydrator for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS graft 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 and ethylene oxide amine adduct is 1:2), 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 weighed and added into a high-speed mixer to mix evenly, and the mixture was added into a twin-screw extruder for melt extrusion and pelletizing to prepare an antistatic ABS material.

[0083] Example 4

[0084] (1) 100 parts of polybutadiene latex were added into a reactor, the temperature of the reactor was controlled at 70°C, and then 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydroperoxide, 1 part of acrylamide, 60 parts of styrene and acrylonitrile monomer mixture (the weight ratio of styrene to acrylonitrile was 5:2) and 200 parts of deionized water were mixed evenly, and then prepared into an emulsion, and then added into the reactor at a uniform speed and continuously with a metering pump. The feeding time was 2 hours, and the modified grafted ABS emulsion was obtained after the reaction time was 30 minutes.

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

[0086] (3) 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 and ethylene oxide amine adduct is 1:5), 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) are weighed and added into a high-speed mixer to mix evenly, and the mixture is added into a twin-screw extruder for melt extrusion and pelletizing to prepare an antistatic ABS material.

[0087] Example 5

[0088] (1) 100 parts of polybutadiene latex were added into a reactor, and the temperature of the reactor was controlled at 72°C. Then, 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydroperoxide, 2 parts of acrylamide, 50 parts of styrene and acrylonitrile monomer mixture (the weight ratio of styrene to acrylonitrile was 5:2) and 180 parts of deionized water were mixed evenly, and the mixture was prepared into an emulsion, and then added into the reactor at a uniform speed and continuously with a metering pump. The feeding time was 1.5 hours, and the modified grafted ABS emulsion was obtained after the reaction time was 30 minutes.

[0089] (2) Add 300 parts of deionized water and 1 part of coagulant sulfuric acid into a coagulation kettle, stir at 100 rpm, mix well, then add 100 parts of modified graft latex into the coagulation kettle, coagulate at 70°C for 10 minutes to obtain graft powder slurry, pour the slurry into a centrifugal dehydrator for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS graft 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 and ethylene oxide amine adduct is 1:5), 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 weighed and added into a high-speed mixer to mix evenly, and the mixture was added into a twin-screw extruder for melt extrusion and pelletizing to prepare an antistatic ABS material.

[0091] Embodiment 6:

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

[0093] (2) Add 280 parts of deionized water and 1 part of coagulant sulfuric acid into a coagulant kettle, stir at 100 rpm, mix well, then add 100 parts of modified graft latex into the coagulant kettle, coagulate at 85°C for 10 minutes to obtain graft powder slurry, pour the slurry into a centrifugal dehydrator for dehydration, washing, and drying to obtain modified ABS graft 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 and ethylene oxide amine adduct is 1:5), 0.2 parts of compound light stabilizer (UV531 and UV329, respectively, with a weight ratio of 1:1), 0.5 parts of lubricant (magnesium stearate and fatty acid amide, respectively, with a weight ratio of 1:4) and 0.2 parts of antioxidant (antioxidant 1010 and antioxidant 168, respectively, with a weight ratio of 1:1) were weighed and added into a high-speed mixer to mix evenly, and the mixture was added into a twin-screw extruder for melt extrusion and pelletization to prepare an antistatic ABS material.

[0095] Embodiment 7:

[0096] (1) 100 parts of polybutadiene latex were added into a reactor, and the temperature of the reactor was controlled at 68°C. Then, 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydroperoxide, 60 parts of styrene and acrylonitrile monomer mixture (the weight ratio of styrene to acrylonitrile was 5:2) and 150 parts of deionized water were mixed evenly, and the mixture was prepared into an emulsion, and then added into the reactor at a uniform speed and continuously using a metering pump. The feeding time was 1 hour, and the modified grafted ABS emulsion was obtained after the reaction time was 30 minutes.

[0097] (2) Add 300 parts of deionized water and 1 part of coagulant sulfuric acid into a coagulation kettle, stir at 100 rpm, mix well, then add 100 parts of modified graft latex into the coagulation kettle, coagulate at 85°C for 10 minutes to obtain graft powder slurry, pour the slurry into a centrifugal dehydrator for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS graft 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 and ethylene oxide amine adduct is 1:5), 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 weighed and added into a high-speed mixer and mixed evenly. The mixture was added into a twin-screw extruder for melt extrusion and pelletizing to prepare an antistatic ABS material.

[0099] Comparative Example 1:

[0100] 42 parts of unmodified general ABS grafted rubber powder, 53 parts of high-impact SAN resin, 3 parts of compound antistatic agent (the weight ratio of allyl sulfonate and ethylene oxide amine adduct is 1:5), 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), 0.5 parts of antioxidant (antioxidant 1010 and antioxidant 168, respectively, with a weight ratio of 1:1) are weighed and added into a high-speed mixer for uniform mixing, and the mixture is added into a twin-screw extruder for melt extrusion and pelletizing to prepare an antistatic ABS material.

[0101] Comparative Example 2:

[0102] (1) 100 parts of polybutadiene latex were added into a reactor, the temperature of the reactor was controlled at 68°C, and then 0.25 parts of molecular weight regulator tert-dodecyl mercaptan, 0.25 parts of initiator cumene hydroperoxide, 1 part of acrylamide, 60 parts of styrene and acrylonitrile monomer mixture (the weight ratio of styrene to acrylonitrile was 5:2), and 150 parts of deionized water were mixed evenly, and the mixture was prepared into an emulsion, which was then added into the reactor at a uniform speed and continuously with a metering pump for 1 hour. After the reaction was completed, a modified grafted ABS emulsion was obtained.

[0103] (2) Add 300 parts of deionized water and 1 part of coagulant sulfuric acid into a coagulation kettle, stir at 100 rpm, mix well, then add 100 parts of modified graft latex into the coagulation kettle, coagulate at 85°C for 10 minutes to obtain graft powder slurry, pour the slurry into a centrifugal dehydrator for dehydration and washing for 5 minutes, and then dry it in a fluidized bed dryer to obtain modified ABS graft 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 weighed and added to a high-speed mixer for uniform mixing. The mixture was added to a twin-screw extruder for melt extrusion and pelletizing to prepare an antistatic ABS material.

[0105] The performance of the antistatic ABS materials prepared in Examples 1-7 and Comparative Examples 1-2 was tested using the test method mentioned above, and 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] From the data in Table 1, it can be seen that Example 1 balances the rigidity and low-temperature toughness of the antistatic ABS material and has good comprehensive performance. Compared with Example 1, Example 2 reduces the graft polymerization temperature and the proportion of toughened rubber powder, so that the low-temperature impact strength of the antistatic ABS material is slightly lower, and at the same time, the material has better rigidity. Compared with Example 1, Example 3 increases the graft polymerization temperature and the proportion of propyl sulfonate in the compound antistatic agent, and the mechanical properties are similar but the antistatic performance is slightly worse. Compared with Example 1, Example 4 increases the polymerization time of the modified ABS rubber powder and increases the proportion of toughened rubber powder, and the rigidity and heat resistance of the antistatic ABS are reduced to varying degrees. Compared with Example 1, Example 5 increases the proportion of the compound antistatic agent, so that the antistatic performance of the antistatic ABS is improved to a certain extent, and the impact performance is reduced. Compared with Example 1, Example 6 reduces the amount of molecular weight regulator, initiator and monomer added, and reduces the amount of blending aid added, and the low-temperature impact performance and rigidity are improved to a certain extent. Compared with Example 1, Example 7 shows that the modified grafted rubber powder does not contain acrylamide, and the antistatic performance is reduced, indicating that the addition of acrylamide monomer during the grafting process has a certain degree of synergistic effect on the compound antistatic agent of allyl sulfonate and ethylene oxide amine, thereby improving the antistatic efficiency. Comparative Example 1 uses unmodified common ABS rubber powder on the market, and the toughening effect is general, and the lateral rigidity and low-temperature strength of the helmet product are poor. Comparative Example 2 uses allyl sulfonate antistatic agent alone, and the antistatic performance of ABS is lower than that of Example 1.

[0109] In summary, the antistatic ABS material prepared by the present invention improves the toughening efficiency and enhances the low-temperature toughness by synthesizing modified ABS rubber powder, improves the antistatic performance by compounding an antistatic agent, and adds SAN resin, light stabilizer, lubricant, antioxidant and other components to coordinately cooperate, so that the ABS material has good antistatic performance while maintaining high rigidity and high low-temperature toughness.

[0110] The above description is only a preferred embodiment of the present invention and is not intended to limit the scope of implementation of the present invention. If the present invention is modified or replaced by equivalents without departing from the spirit and scope of the present invention, it should be included in the protection scope of the claims of the present invention.

Claims

1. An antistatic ABS material, It is characterized in that The invention comprises the following components in parts by weight: 35-45 parts of modified ABS grafted rubber powder, 50-60 parts of SAN resin, 2-4 parts of compound antistatic agent, 0.2-0.5 parts of compound light stabilizer, 0.5-1.0 parts of lubricant and 0.2-0.5 parts of antioxidant.

2. The antistatic ABS material according to claim 1, It is characterized in that The SAN resin is an acrylonitrile-styrene copolymer with an acrylonitrile content of 26%-36%, a number average molecular weight of 80000-100000, and a melt flow rate of (10-30) g / 10min.

3. The antistatic ABS material according to claim 1, It is characterized in that The compound antistatic agent is a mixture of one or more of stearic acid ester, allyl sulfonate, alkyl quaternary ammonium salt and ethylene oxide amine adduct.

4. The antistatic ABS material according to claim 3, It is characterized in that The compound antistatic agent is a mixture of allyl sulfonate and ethylene oxide amine adducts, and the weight ratio of allyl sulfonate to ethylene oxide amine adducts is (0.2-0.5):

1.

5. The antistatic ABS material according to claim 1, It is characterized in that The compound light stabilizer is a mixture of one or more of UV531, UV329, UV326, UV770 and UV3035.

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

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

8. The antistatic ABS material according to claim 1, It is characterized in that The modified ABS grafted rubber powder is prepared by the following method: Step 1: Add polybutadiene latex into a reactor, control the temperature of the reactor to 60°C-85°C, then mix the molecular weight regulator, initiator, acrylamide, styrene and acrylonitrile monomer mixed solution, and deionized water evenly, prepare the emulsion and add it into the reactor, the feeding time is 1-2h, and the modified grafted ABS emulsion is obtained after reacting for 0.5-1h; Step 2: Add deionized water and coagulant into the coagulation kettle, control the temperature in the coagulation kettle to 70°C-90°C, start 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: Dehydrating and washing the grafted powder slurry, and then drying it to obtain the modified ABS grafted rubber powder.

9. The antistatic ABS material according to claim 8, It is characterized in that The polybutadiene latex is a large-particle polybutadiene latex with a solid content of 50%-70% and a particle size of 120nm-400nm.

10. The antistatic ABS material according to claim 8, It is characterized in that The molecular weight regulator is tert-dodecyl mercaptan, and the added amount is 0.15%-0.25% of the mass of the polybutadiene latex.

11. The antistatic ABS material according to claim 8, It is characterized in that The initiator is cumene hydroperoxide, and the added amount is 0.15%-0.25% of the mass of the polybutadiene latex.

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

13. The antistatic ABS material according to claim 8, It is characterized in that The added amount of the styrene and acrylonitrile monomer mixed liquid is 40%-60% of the mass of the polybutadiene latex, wherein the mass ratio of styrene to acrylonitrile is 5:

2.

14. The antistatic ABS material according to claim 8, It is characterized in that The amount of deionized water added in step 1 is 150%-200% of the mass of the polybutadiene latex, and the amount of deionized water added in step 2 is 280%-320% of the mass of the modified grafted ABS emulsion.

15. The antistatic ABS material according to claim 8, It is characterized in that The coagulant is sulfuric acid, and the added amount is 1%-2% of the mass of the modified grafted ABS emulsion.

16. A method for preparing the antistatic ABS material according to any one of claims 1 to 15, It is characterized in that include: The modified ABS grafted rubber powder, SAN resin, compound antistatic agent, compound light stabilizer, lubricant and antioxidant are weighed according to weight proportions, mixed evenly, melted, extruded, and pelletized to obtain the antistatic ABS material.

17. The preparation method according to claim 16, It is 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 speed of the screw main engine is 250r / min-350r / min, and the extrusion temperature is 180℃-220℃.

18. Use of the antistatic ABS material according to any one of claims 1 to 15 in a safety helmet.

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