Antistatic agent, antistatic resin composition, and use thereof

Abstract

The application relates to the field of antistatic materials and discloses an antistatic agent, an antistatic resin composition and application thereof. Based on the total mass of the antistatic agent, the antistatic agent contains 93-99 wt% of a block copolymer and 1-7 wt% of component A; the block copolymer is obtained by reacting caprolactam, a dicarboxylic compound, a diamine compound and an antioxidant in the presence of an acidic catalyst; the diamine compound is selected from the combination of at least one of a polyether diamine and a C6-C15 linear alkyl diamine; component A contains sulfonate and stannate; the sulfonate is a halogen-substituted C1-C12 alkyl sulfonate. The antistatic agent has low surface resistivity, high heat resistance and excellent flame retardant performance.

Description

Technical Field

[0001] This invention relates to the field of antistatic materials, specifically to an antistatic agent, an antistatic resin composition, and their applications. Background Technology

[0002] Insulating thermoplastic resins have permanent antistatic properties. They are usually made by adding permanent antistatic agents to form antistatic compositions, and then molded into products with permanent antistatic properties through injection molding, extrusion, blow molding, casting and other methods.

[0003] Permanent antistatic agents typically use conductive materials such as graphite, carbon black, and carbon nanotubes, or polymeric permanent antistatic agents. Polymeric permanent antistatic agents can be used on light-colored products and have relatively little impact on the processing performance of the materials.

[0004] However, problems often arise in applications, including: insufficient surface resistivity; insufficient heat resistance, which can be used for relatively low-temperature injection molding materials such as polypropylene (PP) or acrylonitrile-butadiene-styrene copolymer (ABS), but not for high-temperature resins such as polycarbonate (PC) and polyphosphate (PPE); and incompatibility with flame retardants, as some flame retardants are small molecules that tend to accumulate on the material surface after processing and molding, affecting the resistivity performance.

[0005] CN114829502A discloses an antistatic agent containing a block polymer and a sulfonate. This antistatic agent uses a variety of alkyl sulfonates as components, but the disclosed surface resistivity is usually between E10 and E11. It can be used in dustproof and other fields, but it does not reach the level required for antistatic trays. Summary of the Invention

[0006] The purpose of this invention is to provide an antistatic agent that combines low surface resistivity, high heat resistance, and excellent flame retardant properties.

[0007] To achieve the above objectives, a first aspect of the present invention provides an antistatic agent, wherein, based on the total mass of the antistatic agent, the antistatic agent contains: 93-99 wt% of a block copolymer and 1-7 wt% of component A; The block copolymer is obtained by reacting caprolactam, dicarboxylic acid compounds, diamine compounds, and antioxidants in the presence of an acidic catalyst. The diamine compound is selected from a combination of polyether diamine and C6-C15 linear alkyl diamine, and at least one of polyether diamines; Component A contains sulfonate and stannate; The sulfonate is a halogen-substituted C1-C12 alkyl sulfonate.

[0008] A second aspect of the present invention provides an antistatic resin composition comprising: a thermoplastic resin and an antistatic agent, and optionally, additives; The antistatic agent is the antistatic agent described in the first aspect.

[0009] A third aspect of the present invention provides the use of the antistatic agent described in the first aspect and the antistatic resin composition described in the second aspect in antistatic materials.

[0010] Compared with the prior art, the present invention has at least the following advantages: 1. The antistatic resin composition prepared by the antistatic agent provided by the present invention has a low surface resistivity; 2. The antistatic agent provided by this invention has high heat resistance and can be used to process high-temperature (180-350℃) resins; 3. The antistatic resin composition prepared by the antistatic agent provided by the present invention has good flame retardant properties. Detailed Implementation

[0011] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0012] In this invention, "the C1-C12 alkyl sulfonates" refers to straight-chain alkyl sulfonates or branched-chain alkyl sulfonates with a total number of carbon atoms of 1-12 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12). Exemplarily, these can be n-butyl sulfonate, hexyl ethyl sulfonate, n-octyl sulfonate, n-nonyl sulfonate, etc.

[0013] In this invention, "the C6-C15 straight-chain alkyl diamine" refers to a straight-chain alkyl group with a total number of carbon atoms of 6-15 (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15), and the straight-chain alkyl group is attached to two amino groups. Examples include nonanediamine, decanediamine, undecanediamine, etc.

[0014] As previously stated, a first aspect of the present invention provides an antistatic agent, wherein, based on the total mass of the antistatic agent, the antistatic agent contains: 93-99 wt% of a block copolymer and 1-7 wt% of component A; The block copolymer is obtained by reacting caprolactam, dicarboxylic acid compounds, diamine compounds, and antioxidants in the presence of an acidic catalyst. The diamine compound is selected from a combination of polyether diamine and C6-C15 linear alkyl diamine, and at least one of polyether diamines; Component A contains sulfonate and stannate; The sulfonate is a halogen-substituted C1-C12 alkyl sulfonate.

[0015] The present invention employs specific block copolymers that possess excellent mechanical properties, heat resistance, and electrical properties. The specific ratio (93-99 wt% block copolymer and 1-7 wt% component A) is controlled because if the ratio of sulfonates and stannates is too low, there will be no excellent resistivity, and if the ratio is too high, they will easily precipitate in the system and become powdery substances on the surface. Furthermore, the specific use of halogen-substituted C1-C12 alkyl sulfonates can possess good surface resistivity and flame retardant properties, and the combination with stannates can enhance the flame retardant properties.

[0016] In a preferred embodiment, the mass ratio of the sulfonate to the stannate in component A is 1-3:1. The inventors have found that, under this preferred embodiment, the prepared antistatic agent exhibits better surface resistivity and flame-retardant properties.

[0017] Preferably, the block copolymer has a melt index of 20-40 g / 10 min, more preferably 25-35 g / 10 min, at 230°C and a load of 2.16 kg; a Shore hardness of 40-70 D, more preferably 40-60 D; and a number-average molecular weight of 5000-50000, more preferably 35000-45000. The inventors have found that under these preferred conditions, the antistatic resin composition can maintain good mechanical properties and compatibility.

[0018] More preferably, the melting point of the block copolymer is 170-200°C.

[0019] In a preferred embodiment, the number-average molecular weight of the polyether diamine is 400-2500, more preferably 1000-1500.

[0020] Preferably, the viscosity of the polyether diamine at 50°C is 80-100 centipoise.

[0021] Preferably, the polyether diamine contains polyethylene oxide segments. The inventors have found that this preferred embodiment exhibits better resistivity.

[0022] In this invention, the poly(ethylene oxide) segment refers to a structure containing repeating ethylene oxide units in the molecule, with the structural formula -[CH2CH2O]. n -

[0023] Preferably, the dicarboxylic acid compound is selected from at least one of adipic acid, sebacic acid, octanoic acid, dodecanoic acid, cyclohexanedicarboxylic acid, and terephthalic acid.

[0024] Preferably, the C6-C15 straight-chain alkyl diamine is selected from at least one of 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, and 1,11-undecanediamine.

[0025] In a preferred embodiment, the block copolymer is prepared using a method comprising the following steps: Weigh caprolactam, diamine compounds, acid catalysts, dicarboxylic acid compounds, antioxidants, and water. Under nitrogen protection and stirring, dissolve and heat at 80-100℃ for 0.5-2 hours, then raise the temperature to 150-165℃ and react for 1-3 hours, then raise the temperature to 170-190℃ and react for 2-4 hours. Continue to raise the temperature to 220-240℃ and wait for the system viscosity to rise to 7000-9000 centipoise. Apply vacuum to 500-1000 Pa until the viscosity of the reaction system at 240℃ reaches 80000-100000 centipoise. Discharge the material, granulate it, and obtain a block copolymer (a hydrophilic, block copolymerized polyamide elastomer).

[0026] Preferably, the method for preparing the block copolymer further includes: extracting the granulated material in hot water at 70-90°C to remove unreacted caprolactam monomers, and then drying it at 80-90°C so that the water content in the obtained product is less than 0.3% by mass.

[0027] Preferably, the molar ratio of caprolactam, dicarboxylic acid compound, and diamine compound is 7-40:0.9-2.5:1.

[0028] Preferably, the amount of the acidic catalyst is 3-15g relative to 1mol of the diamine compound; the amount of the antioxidant is 3-15g.

[0029] More preferably, the amount of water used is 30-170g relative to 1 mol of the diamine compound.

[0030] In a preferred embodiment, the sulfonate is selected from at least one of halogen-substituted C1-C12 alkyl sulfonates, halogen-substituted C1-C12 alkyl sulfonates, and halogen-substituted C1-C12 alkyl sulfonates.

[0031] Preferably, in the halogen-substituted C1-C12 alkyl sulfonates, the halogen is selected from at least one of fluorine, chlorine, bromine, and iodine.

[0032] Preferably, the sulfonate is selected from at least one of potassium perfluorobutyl sulfonate, potassium perfluorohexyl ethyl sulfonate, potassium perfluorohexyl sulfonate, potassium perfluorooctyl sulfonate, potassium perfluoroheptyl sulfonate, potassium perfluorononyl sulfonate, sodium perfluorohexyl ethyl sulfonate, sodium perfluorooctyl sulfonate, sodium perfluoropropane sulfonate, sodium trifluoromethanesulfonate, and potassium trifluoromethanesulfonate.

[0033] More preferably, the sulfonate is sodium trifluoromethanesulfonate and / or potassium perfluorobutylsulfonate.

[0034] In a preferred embodiment, the stannate is selected from at least one of lithium stannate, sodium stannate, and potassium stannate.

[0035] Preferably, the stannate is sodium stannate.

[0036] The present invention does not impose any particular requirements on the preparation method of the antistatic agent, as long as the mixture is uniform, it is sufficient. Those skilled in the art can proceed according to known techniques in the field. For example, block copolymers, sulfonates, and stannates can be added to a twin-screw extruder in proportion for extrusion, granulation, and then drying to obtain the antistatic agent.

[0037] As previously described, a second aspect of the present invention provides an antistatic resin composition comprising: a thermoplastic resin and an antistatic agent, and optionally, additives; The antistatic agent is the antistatic agent described in the first aspect.

[0038] In a preferred embodiment, the content of the antistatic agent is 12-40 wt% and the content of the thermoplastic resin is 50-85 wt%, based on the total mass of the antistatic resin composition. The inventors have found that under these preferred conditions, the composition exhibits a lower surface resistivity.

[0039] Preferably, the thermoplastic resin is selected from at least one of polyoxymethylene (POM), polyethylene, polypropylene, polystyrene, polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), polyphenylene ether (PPE), butylene terephthalate (PBT), polyvinyl chloride, acrylonitrile-styrene-acrylic acid copolymer (ASA), ethylene-vinyl acetate copolymer (EVA), polyamide, and polycarbonate / acrylonitrile-butadiene-styrene alloy (PC / ABS alloy).

[0040] Preferably, the polystyrene is high-impact polystyrene (HIPS).

[0041] Preferably, the polyamide is selected from at least one of polyamide 6, polyamide 66, and polyamide 12.

[0042] According to a preferred embodiment, the content of the additive is 0.5-10 wt% based on the total mass of the antistatic resin composition.

[0043] According to another preferred embodiment, the additive is selected from at least one of antioxidants, lubricants, flame retardants, nucleating agents, UV stabilizers, colorants, reinforcing agents, compatibilizers, fillers, and anti-hydrolysis agents.

[0044] Preferably, the reinforcing agent is glass fiber and / or mica.

[0045] Preferably, the compatibilizer is selected from at least one of ethylene-butyl acrylate-GMA copolymer, maleic anhydride-grafted polyolefin elastomer (POE-grafted MAH), and maleic anhydride-grafted styrene-ethylene-butene-styrene block copolymer (SEBS-grafted MAH).

[0046] The present invention does not have any special requirements for the preparation method of the antistatic resin composition, as long as it can be mixed evenly. Those skilled in the art can carry out the preparation according to the technical means known in the art. For example, thermoplastic resin, antistatic agent and optional additives are weighed and mixed in proportion and added to a twin-screw extruder for extrusion, granulation, and then dried to obtain the antistatic resin composition.

[0047] As previously stated, a third aspect of the present invention provides the use of the antistatic agent described in the first aspect and the antistatic resin composition described in the second aspect in antistatic materials.

[0048] The present invention will be described in detail below through examples. Unless otherwise specified, specific experimental steps or conditions in the following examples can be performed according to known experimental steps or conditions described in the literature in this field. Unless otherwise specified, the raw materials or instruments used are commercially available. Unless otherwise specified, the reaction temperature in the following examples is at room temperature, which refers to 25±2℃.

[0049] Polyether diamine I: Contains polyethylene oxide segments, has a number average molecular weight of 1200, a viscosity of 90 centipoise at 50°C, brand name RE1200, purchased from Huntsman.

[0050] Polyether diamine II: Contains polyethylene oxide segments, has a number average molecular weight of 1700, a viscosity of 115 centipoise at 55°C, brand name HE1700, purchased from Huntsman.

[0051] Thermoplastic resins: Acrylonitrile-butadiene-styrene copolymer (ABS): Grade AG15A1-H, purchased from Taiwan Chemical Fiber Co., Ltd. Polyphenylene oxide (PPE): Grade ZM040, purchased from Dalian Zhongmu Chemical Co., Ltd. High-impact polystyrene (HIPS): Grade 4241, purchased from INEOS Styrol; Polycarbonate (PC): Calibre 201-15, purchased from Dow Chemical-LG. Polyoxymethylene (POM): Grade M90-44, purchased from Polyplastics, Japan.

[0052] Potassium perfluorobutyl sulfonate: content >99%, purchased from Maclean's Reagent Company.

[0053] Sodium stannate: content >99%, purchased from Maclean's Reagent Company.

[0054] 1-Ethyl-3-methylimidazolium chloride: purchased from Maclean's Reagent Company.

[0055] Antioxidants: Pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Antioxidant 1010): Purchased from BASF; β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester (antioxidant 1076): purchased from BASF; Diethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (Antioxidant 245): purchased from BASF.

[0056] Lubricant: Pentaerythritol stearate (PETS), purchased from FARK, Italy.

[0057] Compatibilizer: Ethylene-butyl acrylate-GMA copolymer: purchased from DuPont, USA; POE grafted MAH: Grade KT-9, purchased from Shenyang Ketong Company; SEBS grafted MAH: grade 7126, purchased from Taiwan Rubber & Plastics Corporation.

[0058] Acid absorbent: It is obtained by mixing melamine and zinc chloride in a mass ratio of 1:1.

[0059] The melt index of block copolymers at 230℃ and 2.16kg load is determined according to the method described in GB / T 3682.1-2018.

[0060] The Shore hardness test method for block copolymers is as follows: according to GB / T 2411-2008, using a type D needle.

[0061] The melting point of block copolymers is determined by differential scanning calorimetry according to GB / T 19466.3-2009.

[0062] The number-average molecular weight of the block copolymer was determined by gel permeation chromatography (GPC).

[0063] Preparation Example 1 S1. In a reactor equipped with a stirring, heat transfer medium heating, vacuuming and nitrogen purging device, add 1 mol of polyether diamine I, caprolactam, 1,6-adipic acid, antioxidant 1010, phosphoric acid catalyst and water. The molar ratio of caprolactam, 1,6-adipic acid, and polyether diamine I is 19.3:1:1. The amount of phosphoric acid catalyst used relative to 1 mol of polyether diamine I is 7.27 g, the amount of antioxidant 1010 used is 7.27 g, and the amount of water used is 90.9 g. S2. Under stirring conditions, heat to 90℃ for pre-melting for 1 hour. After purging the gas in the reactor with nitrogen, heat to 160℃ and react for 2 hours. Then heat to 180℃ and react for 3 hours. Continue heating to 230℃ and wait for the viscosity of the system to rise to 8000 centipoise. Then vacuum to 800 Pa. When the viscosity of the reaction system reaches 80000 centipoise at 240℃, discharge the material. After pelletizing with an underwater pelletizing device, extract the obtained particles in hot water at 80℃ for 4 hours, and then dry at 90℃ until the water content is less than 0.3% to obtain block copolymer A (a hydrophilic and block copolymerized polyamide elastomer). The block copolymer A was found to have a melt index of 25 g / 10 min, a Shore hardness of 57 D, a melting point of 194 °C, and a number-average molecular weight of 42,000 at 230 °C and a load of 2.16 kg.

[0064] Preparation Example 2 S1. In a reactor equipped with a stirring, heat transfer medium heating, vacuuming and nitrogen purging device, add 1 mol of a diamine compound (1,6-hexanediamine and polyether diamine I in a molar ratio of 1.3:1), caprolactam, a dicarboxylic acid compound (1,10-sebacic acid and 1,6-adipic acid in a molar ratio of 1.3:1), antioxidant 1010, phosphoric acid catalyst and water; The molar ratio of caprolactam, dicarboxylic acid compounds, and diamine compounds was 15.75:2.3:1. Relative to 1 mol of diamine compound, the amount of phosphoric acid catalyst used is 7.27 g, the amount of antioxidant 1010 used is 7.27 g, and the amount of water used is 83.6 g; S2. Under stirring conditions, heat to 90℃ for pre-melting for 1 hour. After purging the gas in the reactor with nitrogen, heat to 160℃ and react for 2 hours. Then heat to 180℃ and react for 4 hours. Continue heating to 230℃ and wait for the viscosity of the system to rise to 8000 centipoise. Then vacuum to 1000 Pa. When the viscosity of the reaction system reaches 80000 centipoise at 240℃, discharge the material. After pelletizing with an underwater pelletizing device, extract the obtained particles in hot water at 80℃ for 4 hours, and then dry at 90℃ until the water content is less than 0.3% to obtain block copolymer B (a hydrophilic block copolymer polyamide elastomer). The block copolymer B was measured to have a melt index of 32 g / 10 min at 230 °C and a load of 2.16 kg, a Shore hardness of 53 D, a melting point of 177 °C, and a number-average molecular weight of 37,000.

[0065] Preparation Example 3 S1. In a reactor equipped with a stirring, heating medium, vacuum and nitrogen purging device, add 1 mol of polyether diamine II, caprolactam, 1,6-adipic acid, antioxidant 1010, phosphoric acid catalyst and water. The molar ratio of caprolactam, 1,6-adipic acid and polyether diamine II is 35.68:1:1. The amount of phosphoric acid catalyst used relative to 1 mol of polyether diamine II is 12.14 g, the amount of antioxidant 1010 used is 12.14 g, and the amount of water used is 163.9 g. S2. Under stirring conditions, heat to 90℃ for pre-melting for 1 hour. After purging the gas in the reactor with nitrogen, heat to 160℃ and react for 2 hours. Then heat to 180℃ and react for 3 hours. Continue heating to 230℃ and wait for the viscosity of the system to rise to 8000 centipoise. Then vacuum to 800 Pa. When the viscosity of the reaction system reaches 100000 centipoise at 240℃, discharge the material. After pelletizing with an underwater pelletizing device, extract the obtained particles in hot water at 80℃ for 4 hours, and then dry at 90℃ until the water content is less than 0.3% to obtain block copolymer DI (a hydrophilic block copolymer polyamide elastomer). The block copolymer DI was found to have a melt index of 2 g / 10 min at 230℃ and 2.16 kg load, a Shore hardness of 63 D, a melting point of 208℃, and a number-average molecular weight of 64,000.

[0066] Example 1 (1) Block copolymer A (2820g) was dried at 90°C for 3 hours. Then, the block copolymer A: potassium perfluorobutyl sulfonate: sodium stannate was weighed and mixed in a mass ratio of 94:4:2. The mixture was added to a twin-screw extruder for extrusion (screw temperature 200°C, speed 250 rpm), granulated, and then dried at 90°C for 3 hours to obtain an antistatic agent. (2) Weigh and mix ABS and antistatic agent, add to twin-screw extruder for extrusion (screw barrel temperature set to 200℃, speed of 250 rpm), granulate, and then dry at 80℃ for 2 hours to obtain antistatic resin composition; Based on the total mass of the antistatic resin composition, the content of antistatic agent is 25 wt% and the content of thermoplastic resin is 75 wt%.

[0067] Example 2 (1) Block copolymer B (2820g) was dried at 90°C for 3 hours. Then, the block copolymer B: potassium perfluorobutyl sulfonate: sodium stannate was weighed and mixed in a mass ratio of 94:4:2. The mixture was added to a twin-screw extruder for extrusion (screw barrel temperature was 200°C and speed was 250 rpm). The mixture was granulated and then dried at 90°C for 3 hours to obtain an antistatic agent. (2) Weigh and mix POM, antistatic agent and additives (antioxidant 245, acid absorber and POE grafted MAH in a mass ratio of 1:9:15), add to a twin-screw extruder for extrusion (screw barrel temperature set to 180℃, speed of 250 rpm), granulate, and then dry at 80℃ for 2 hours to obtain an antistatic resin composition; Based on the total mass of the antistatic resin composition, the content of antistatic agent is 20 wt%, the content of thermoplastic resin is 75 wt%, and the content of additives is 5 wt%.

[0068] Example 3 (1) Block copolymer A (2820g) was dried at 90°C for 3 hours. Then, the block copolymer A: potassium perfluorobutyl sulfonate: sodium stannate was weighed and mixed in a mass ratio of 94:4:2. The mixture was added to a twin-screw extruder for extrusion (screw temperature 200°C, speed 250 rpm), granulated, and then dried at 90°C for 3 hours to obtain an antistatic agent. (2) Weigh and mix PPE, HIPS, antistatic agent and additives (the mass ratio of POE grafted MAH: SEBS grafted MAH: antioxidant 1010: PETS is 20:15:3:2), add to a twin-screw extruder for extrusion (screw temperature is 300℃, speed is 250 rpm), granulate, and then dry at 120℃ for 4 hours to obtain an antistatic resin composition; The mass ratio of PPE to HIPS is 45:31. Based on the total mass of the antistatic resin composition, the content of antistatic agent is 20 wt%, the content of thermoplastic resin is 76 wt%, and the content of additives is 4 wt%.

[0069] Example 4 (1) Block copolymer A (2820g) was dried at 90°C for 3 hours. Then, the block copolymer A: potassium perfluorobutyl sulfonate: sodium stannate was weighed and mixed in a mass ratio of 94:4:2. The mixture was added to a twin-screw extruder for extrusion (screw temperature 200°C, speed 250 rpm), granulated, and then dried at 90°C for 3 hours to obtain an antistatic agent. (2) Weigh the PC and antistatic agent, and add the additives (ethylene-butyl acrylate-GMA copolymer, antioxidant 1076 and PETS in a mass ratio of 6:1:1) and mix them. Add the mixture to a twin-screw extruder for extrusion (screw temperature of 240°C and rotation speed of 250 rpm), granulate, and then dry at 120°C for 4 hours to obtain an antistatic resin composition. Based on the total mass of the antistatic resin composition, the content of antistatic agent is 20 wt%, the content of thermoplastic resin is 76 wt%, and the content of additives is 4 wt%.

[0070] Example 5 The process was carried out using a method similar to that in Example 1, except that the block copolymer A in step (1) was replaced with an equal mass of block copolymer DI to obtain an antistatic resin composition.

[0071] Comparative Example 1 ABS and block copolymer A were weighed and mixed in a mass ratio of 75:25, and then extruded in a twin-screw extruder (screw temperature 200℃, speed 250 rpm). The mixture was then granulated and dried at 80℃ for 2 hours to obtain an antistatic resin composition.

[0072] Comparative Example 2 ABS and potassium perfluorobutyl sulfonate were weighed and mixed at a mass ratio of 99:1, and then extruded in a twin-screw extruder (screw temperature 200℃, speed 250 rpm). The mixture was then granulated and dried at 80℃ for 2 hours to obtain an antistatic resin composition.

[0073] Comparative Example 3 ABS and sodium stannate were weighed and mixed at a mass ratio of 99:1, and then extruded in a twin-screw extruder (screw temperature 200℃, speed 250 rpm). The mixture was granulated and then dried at 80℃ for 2 hours to obtain an antistatic resin composition.

[0074] Comparative Example 4 The process was carried out using a method similar to that in Example 2, except that in step (1), the block copolymer B was dried at 90°C for 3 hours, and then the block copolymer B and 1-ethyl-3-methylimidazolium chloride were weighed and mixed in a mass ratio of 96:4, added to a twin-screw extruder for extrusion (screw temperature 200°C, rotation speed 250 rpm), granulated, and then dried at 90°C for 3 hours to obtain the antistatic agent; The remaining steps are the same, resulting in an antistatic resin composition.

[0075] Comparative Example 5 The process was carried out using a method similar to that in Example 4, except that in step (1), the block copolymer A was dried at 90°C for 3 hours, and then the block copolymer A and 1-ethyl-3-methylimidazolium chloride were weighed and mixed in a mass ratio of 96:4. The mixture was then added to a twin-screw extruder for extrusion (screw temperature 200°C, rotation speed 250 rpm), granulated, and then dried at 90°C for 3 hours to obtain the antistatic agent. The remaining steps are the same, resulting in an antistatic resin composition.

[0076] Comparative Example 6 The process was carried out using a method similar to that in Example 3, except that in step (1), the block copolymer A was dried at 90°C for 3 hours, and then the block copolymer A and 1-ethyl-3-methylimidazolium chloride were weighed and mixed in a mass ratio of 96:4. The mixture was then added to a twin-screw extruder for extrusion (screw temperature 200°C, rotation speed 250 rpm), granulated, and then dried at 90°C for 4 hours to obtain the antistatic agent. The remaining steps are the same, resulting in an antistatic resin composition.

[0077] Comparative Example 7 The process was carried out using a method similar to that in Example 1, except that potassium perfluorobutyl sulfonate in step (1) was replaced with an equal mass of sodium dodecylbenzene sulfonate to obtain an antistatic resin composition.

[0078] Comparative Example 8 The procedure was carried out using a method similar to that in Example 1, except that sodium stannate was not added in step (1). Specifically, In step (1), block copolymer A is dried at 90°C for 3 hours, and then the block copolymer A and potassium perfluorobutyl sulfonate are weighed and mixed in a mass ratio of 96:4. The mixture is added to a twin-screw extruder for extrusion (screw barrel temperature is 200°C, rotation speed is 250 rpm), granulated, and then dried at 90°C for 3 hours to obtain an antistatic agent. The remaining steps are the same, resulting in an antistatic resin composition.

[0079] Comparative Example 9 The procedure was carried out using a method similar to that in Example 1, except that potassium perfluorobutyl sulfonate was not added in step (1). Specifically, In step (1), block copolymer A is dried at 90°C for 3 hours, and then the block copolymer A and sodium stannate are weighed and mixed in a mass ratio of 98:2. The mixture is added to a twin-screw extruder for extrusion (screw barrel temperature is 200°C, rotation speed is 250 rpm), granulated, and then dried at 90°C for 3 hours to obtain an antistatic agent. The remaining steps are the same, resulting in an antistatic resin composition.

[0080] Test case The antistatic resin compositions prepared in the foregoing examples and comparative examples were subjected to the following performance tests: 1. Tensile strength and elongation at break tests: conducted according to GB / T 1040.2-2006 standard at a tensile rate of 50 mm / min.

[0081] 2. Surface resistivity test: The test was conducted in accordance with GB / T 1410-2006 standard, after conditioning for one day in an environment with a relative humidity of 50%.

[0082] 3. Bending strength and bending modulus tests: conducted in accordance with GB / T 9341-2008 standard.

[0083] 4. Notched impact strength test: conducted in accordance with GB / T 1843-2008 standard, with a V-shaped notch and a depth of 2mm.

[0084] 5. Flame retardant test: According to UL94 requirements, test strips with thicknesses of 1.5mm and 2.0mm (length 127mm, width 12.7mm) were tested for horizontal and vertical burning, and their flammability rating was evaluated based on the flame lift-off time.

[0085] The results are shown in Table 1.

[0086] Table 1

[0087] As can be seen from the examples and the results in Table 1, the antistatic agent provided by the present invention has high heat resistance and can be used to process high-temperature (180-350℃) resins. For example, it can withstand a high temperature of 300℃ in the barrel. Furthermore, the antistatic resin composition prepared using the antistatic agent provided by the present invention has low surface resistivity and excellent flame retardant properties.

[0088] Specifically, as shown in Comparative Examples 1-3, if block copolymers or salts are missing in the composition, the surface resistivity is poor; as shown in Comparative Examples 8-9, stannate or fluorosulfonate alone has good resistivity but no flame retardant effect. In the examples, the simultaneous use of fluorosulfonate and sodium stannate can achieve better resistivity and flame retardant performance. As can be seen from Examples 1-4, the compositions of the present invention have excellent effects in ABS, POM, PPE and PC systems; As shown in Example 4, the antistatic PC composition system has a V0 flame retardant effect, but the resistivity and flame retardant effect of the antistatic PC composition in Comparative Example 5 are not as good as those in Example 4; the PPE compositions in Example 3 and Comparative Example 6 have certain flame retardant properties, but the resistivity of Comparative Example 6 is higher; as shown in Example 2, the antistatic POM composition has good resistivity and certain flame retardant properties, but the resistivity and flame retardant effect of the polyoxymethylene composition in Comparative Example 4 are not good.

[0089] A comparison between Example 1 and Example 5 shows that the block copolymer DI used in Example 5 has a higher molecular weight and better mechanical properties, but slightly worse surface resistivity.

[0090] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An antistatic agent, characterized in that, Based on the total mass of the antistatic agent, the antistatic agent contains: 93-99 wt% block copolymer and 1-7 wt% component A; The block copolymer is obtained by reacting caprolactam, dicarboxylic acid compounds, diamine compounds, and antioxidants in the presence of an acidic catalyst. The diamine compound is selected from a combination of polyether diamine and C6-C15 linear alkyl diamine, and at least one of polyether diamine; Component A contains sulfonate and stannate; The sulfonate is a halogen-substituted C1-C12 alkyl sulfonate.

2. The antistatic agent according to claim 1, characterized in that, In component A, the mass ratio of the sulfonate to the stannate is 1-3:1; And / or, the block copolymer has a melt index of 20-40 g / 10 min at 230°C and 2.16 kg load, a Shore hardness of 40-70 D, and a number average molecular weight of 5000-50000.

3. The antistatic agent according to claim 1 or 2, characterized in that, The number-average molecular weight of the polyether diamine is 400-2500; And / or, the dicarboxylic acid compound is selected from at least one of adipic acid, sebacic acid, octanoic acid, dodecanoic acid, cyclohexanedicarboxylic acid, and terephthalic acid.

4. The antistatic agent according to claim 1 or 2, characterized in that, The sulfonate is selected from at least one of halogen-substituted C1-C12 alkyl sulfonates, halogen-substituted C1-C12 alkyl sulfonates, and halogen-substituted C1-C12 alkyl sulfonates. And / or, the stannate is selected from at least one of lithium stannate, sodium stannate, and potassium stannate.

5. The antistatic agent according to claim 4, characterized in that, The sulfonate is selected from at least one of potassium perfluorobutyl sulfonate, potassium perfluorohexyl ethyl sulfonate, potassium perfluorohexyl sulfonate, potassium perfluorooctyl sulfonate, potassium perfluoroheptyl sulfonate, potassium perfluorononyl sulfonate, sodium perfluorohexyl ethyl sulfonate, sodium perfluorooctyl sulfonate, sodium perfluoropropane sulfonate, sodium trifluoromethanesulfonate, and potassium trifluoromethanesulfonate.

6. The antistatic agent according to claim 1 or 2, characterized in that, The molar ratio of caprolactam, dicarboxylic acid compound, and diamine compound is 7-40:0.9-2.5:1; The amount of the acidic catalyst is 3-15g relative to 1mol of the diamine compound; the amount of the antioxidant is 3-15g.

7. An antistatic resin composition, characterized in that, The composition includes: a thermoplastic resin and an antistatic agent, as well as optional additives; The antistatic agent is the antistatic agent according to any one of claims 1-6.

8. The composition according to claim 7, characterized in that, Based on the total mass of the antistatic resin composition, the content of the antistatic agent is 12-40 wt%, and the content of the thermoplastic resin is 50-85 wt%.

9. The composition according to claim 7 or 8, characterized in that, The thermoplastic resin is selected from at least one of polyoxymethylene, polyethylene, polypropylene, polystyrene, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyphenylene ether, polybutylene terephthalate, polyvinyl chloride, acrylonitrile-styrene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, polyamide, and polycarbonate / acrylonitrile-butadiene-styrene alloy.

10. The use of the antistatic agent according to any one of claims 1-6 and the antistatic resin composition according to any one of claims 7-9 in antistatic materials.

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