Long-acting antistatic ABS composite material as well as preparation method and application thereof

Abstract

The invention discloses a long-acting antistatic ABS (Acrylonitrile Butadiene Styrene) composite material and a preparation method and application thereof. The long-acting antistatic ABS composite material is prepared from 85 to 95 percent of ABS, 2 to 10 percent of long-acting antistatic agent, 0.5 to 5 percent of compatilizer, 0.1 to 1 percent of antioxidant and 0.5 to 5 percent of lubricant, wherein the long-acting antistatic agent is polyether ester amide containing a branched polyether structure. The ABS composite material provided by the invention has stable and long-acting antistatic performance and good mechanical properties, and can be used for preparing antistatic or dustproof plastic parts.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, specifically to a modified ABS composite material, and more particularly to a long-lasting antistatic ABS composite material, its preparation method, and its application. Background Technology

[0002] ABS (acrylonitrile-butadiene-styrene copolymer) possesses excellent mechanical strength, impact resistance, and processing properties, and is widely used in electronics, automobiles, office equipment, and other fields. However, ABS material itself does not have antistatic properties and easily accumulates static charge in dry environments, leading to problems such as dust attraction and discharge damage to sensitive components.

[0003] In the field of polymer antistatic modification, common strategies can be categorized into three types: conductive filler type, low-molecular-weight surfactant type, and high-molecular-weight antistatic agent type. Conductive fillers, represented by carbon black or metal powder, can achieve significant antistatic effects by improving the overall conductivity of the material. However, their inherent coloring properties can cause the composite material to darken or turn grayish, making them unsuitable for light-colored or film-type products where strict color requirements exist. Another commonly used antistatic method is to add small-molecular-weight surfactants, including anionic, cationic, nonionic, and amphoteric surfactants. These low-molecular-weight additives release surface charge by adsorbing moisture from the air and forming a hygroscopic film on the material surface. Therefore, their antistatic performance is highly dependent on the relative humidity of the environment. In addition, small-molecular-weight surfactants tend to migrate from the matrix to the surface and concentrate, which is not conducive to long-term stable use. High-molecular-weight antistatic agents release charge by establishing ionic or electronic conduction pathways within the matrix. Their molecular weight and chain structure determine their fixation and migration within the matrix. Compared to small molecules, polymeric systems typically exhibit advantages such as low migration, no volatilization loss, and less dependence on environmental humidity, making it easier to achieve long-lasting antistatic effects. However, the design of polymeric antistatic agents must consider compatibility with the matrix, the required dosage, and the impact on material mechanics and processability; otherwise, problems such as phase separation, molding defects, or decreased mechanical properties may occur.

[0004] Polyether ester amides are a class of antistatic agents widely reported and industrially applied, used in the preparation of long-lasting antistatic resin composites due to their good thermal stability and compatibility with engineering plastic matrices. Polyether ester amides contain hydrophobic hard segments (polyamide) and hydrophilic soft segments (polyether ester amide). Currently, the polyether segments in polyether ester amide antistatic agents are all linear structures, and under long-term service, some degree of molecular chain migration and accumulation on the surface still occurs within the resin material, making it difficult to guarantee stable long-lasting antistatic properties. Using multi-block polyether ester amides to form a network within the resin can effectively reduce the migration of hydrophilic segments; however, this strategy may also affect the mechanical properties of the material.

[0005] To solve the above problems, it is necessary to develop an ABS composite material that combines long-lasting antistatic properties with good mechanical properties. Summary of the Invention

[0006] The purpose of this application is to provide a long-lasting antistatic ABS composite material, its preparation method, and its application.

[0007] To achieve the above objectives, this application provides the following technical solution: A long-lasting antistatic ABS composite material, composed of the following components: ABS, long-lasting antistatic agent, compatibilizer, antioxidant, and lubricant; the formula is as follows: ABS: 85-95 wt% Long-lasting antistatic agent: 2-10 wt% Compatibilizer: 0.5-5 wt% Antioxidant: 0.1-1 wt% Lubricant: 0.5-5 wt% The long-lasting antistatic agent is a polyether ester amide containing a branched polyether structure.

[0008] This application also provides the following technical solutions: A method for preparing a long-lasting antistatic ABS composite material includes the following steps: Weigh each component according to the aforementioned formula; after drying the ABS, compatibilizer, antioxidant and lubricant, add them together with the long-lasting antistatic agent into a high-speed mixer and mix at 500-1000 rpm for 1-10 minutes to obtain a premix; continuously feed the premix into a twin-screw extruder and extrude and granulate at 160-260°C; optionally, dry the granulated material at 80-90°C for 2-3 hours.

[0009] This application also provides the following technical solutions: An application of the aforementioned long-lasting antistatic ABS composite material in the preparation of plastic parts; the parts have antistatic or dustproof functions.

[0010] The technical solution provided in this application has the following beneficial effects: (1) The ABS composite material provided in this application uses polyether ester amide containing branched polyether structure as a long-lasting antistatic agent. The branched polyether structure helps to improve the distribution of the conductive network inside the material, thereby significantly improving the antistatic performance. On the other hand, the branched polyether structure can also enhance the anchoring effect of polyether segments in the matrix by providing additional free hydroxyl groups to covalently couple with compatibilizers, thereby preventing the migration of hydrophilic segments and more effectively reducing the rate of degradation of antistatic performance.

[0011] (2) The ABS composite material provided in this application has a component formulation that achieves long-lasting antistatic function while ensuring that the mechanical properties of the material are not significantly affected. Through optimization, this formulation can achieve similar or better performance than conventional solutions while reducing the amount of antistatic agent used. Invention Details 1. Terminology Explanation All patents and other publications cited herein are incorporated herein in their entirety. In the event of any conflict between any description of terminology herein and any document incorporated herein by reference, this document shall prevail.

[0012] Numerical ranges can be represented by a hyphen "-" or a tilde "~", and their endpoints are included by default. The numerical types within the range include, but are not limited to, integers, non-integers, percentages, and fractions.

[0013] The terms “including,” “containing,” and similar expressions have a non-restrictive meaning.

[0014] A “combination” of enumeration items means any two or more enumeration items used together, unless the combination is technically impossible or the context explicitly excludes it.

[0015] ABS is a copolymer of acrylonitrile, butadiene, and styrene. Typically, ABS contains 15-35% acrylonitrile, 5-30% butadiene, and 40-60% styrene.

[0016] The content of each component in the composite material is expressed as a weight percentage.

[0017] The molecular weight of the polymer is assumed to be number average. When the unit of molecular weight is not given, it is assumed to be Daltons (Da). The molecular weight of polydisperse polymers is allowed to be within ±10% of a given value; for example, 2000 Da is equivalent to 1800-2200 Da. Unless otherwise stated, all polymers in this application are polydisperse polymers.

[0018] Polyether ester amides refer to copolymers having a polyamide structure and a polyether structure bonded by ester bonds.

[0019] Exemplary polyamides include substances obtained by polycondensation of diacids (such as oxalic acid, succinic acid, adipic acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, etc.) and diamines (such as ethylenediamine, butanediamine, pentanediamine, hexamethylenediamine, decanediamine, trimethylhexanediamine, isophoronediamine, m-phenylenediamine, p-phenylenediamine, etc.), substances obtained by ring-opening polymerization of lactams (such as caprolactam, laurolactam, etc.), substances obtained by polycondensation of amino acids (such as 6-aminohexanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.), and substances obtained by copolymerization of any of the aforementioned lactams, diacids, and diamines. This application uses "PAx.y" to name polyamides, where x represents the number of carbon atoms in the diamine structural unit and y represents the number of carbon atoms in the diacid structural unit. For example, PA10.10 indicates a polyamide containing two structural units: sebacic acid and decanoic acid.

[0020] Exemplary polyethers include polyethylene glycol, polypropylene glycol, polybutane glycol, and polyphenylene ether. Branched polyethers are non-linear polyethers formed by one or more branching nuclei linking two or more polyether segments. Based on the number of polyether segments they contain, branched polyethers can be classified as two-armed, three-armed, four-armed, and more-armed polyethers. Common branching nuclei include, but are not limited to, glycerol, pentaerythritol, and trimethylolpropane.

[0021] Compatibilizers are functional additives used to improve the interfacial compatibility and adhesion between components of composite materials. Their core function is to reduce interfacial tension and enhance interfacial adhesion by introducing functional groups (such as maleic anhydride) that can physically entangle or undergo specific chemical reactions with the blended components. This optimizes the phase structure of the blend system and improves the mechanical properties and stability of the final material. Compatibilizers can be polymers with high compatibility between the main chain and the blend matrix, and grafted with maleic anhydride (MAH) functional groups. During melt blending, the maleic anhydride groups can react with the free hydroxyl groups of the polyether ester amide to form ester bonds, improving the compatibility between components. Exemplary compatibilizers include ABS-g-MAH (maleic anhydride-grafted acrylonitrile-butadiene-styrene copolymer) and SAN-g-MAH (maleic anhydride-grafted styrene-acrylonitrile copolymer).

[0022] The numerical value indicated by the C subscript can be used to represent the number of carbon atoms in a compound molecule. It can be expressed as a range and, by default, does not include the contribution of substituents. For example, C... 12-40 Fatty acids are those with 12-40 carbon atoms.

[0023] 2. Implementation Plan One embodiment of this application is as follows: A long-lasting antistatic ABS composite material, composed of the following components: ABS, long-lasting antistatic agent, compatibilizer, antioxidant, and lubricant; the formula is as follows: ABS: 85-95 wt% Long-lasting antistatic agent: 2-10 wt% Compatibilizer: 0.5-5 wt% Antioxidant: 0.1-1 wt% Lubricant: 0.5-5 wt% The long-lasting antistatic agent is a polyether ester amide containing a branched polyether structure.

[0024] In some specific embodiments, the polyether ester amide contains a branched polyethylene glycol structure.

[0025] In some specific embodiments, the molecular weight of the polyether ester amide is 1000-4000 Da.

[0026] In some specific embodiments, the molecular weight of the polyether ester amide is 1500-3000 Da.

[0027] In some specific embodiments, the molecular weight of the polyether ester amide is 2000-2500 Da, including but not limited to any one of 2000 Da, 2100 Da, 2200 Da, 2300 Da, 2400 Da and 2500 Da.

[0028] In some specific embodiments, the polyether content of the polyether ester amide is 40-60 wt%.

[0029] In some specific embodiments, the polyether content of the polyether ester amide is 45-50 wt%.

[0030] In some specific embodiments, the polyamide portion of the polyether ester amide is PA10.10 or PA12.12.

[0031] In some specific implementations, the long-lasting antistatic agent is obtained by the following preparation method: Diamine, diacid, and deionized water were added to a reaction vessel purged with an inert gas. The mixture was heated to 220-230°C under normal pressure and stirred vigorously for 2-4 hours. Subsequently, the temperature was raised to 250-260°C, and branched polyether and catalyst were added. The reaction was continued at 250-260°C with stirring for 30-60 minutes. Then, the reaction was continued under reduced pressure for 3-4 hours. After the reaction was completed, the mixture was granulated and dried to obtain the long-lasting antistatic agent. The molar ratio of diamine, diacid, and branched polyether is (3-5): (4-6): (0.5-2), preferably 4:5:1.5; the amount of deionized water is 3-8 wt% of the total amount of diamine and diacid, preferably 5 wt%; and the amount of catalyst is 0.1-0.5 wt% of the total amount of diamine, diacid, and branched polyether, preferably 0.2 wt%.

[0032] In some specific implementations, the branched polyether is branched polyethylene glycol.

[0033] In some specific implementations, the branched polyether is a three-armed polyethylene glycol or a four-armed polyethylene glycol.

[0034] In some specific embodiments, the three-arm polyethylene glycol is a trimethylolpropane polyether having the following structure: ; Where n represents the degree of polymerization of each polyethylene glycol chain; each n is an independent integer from 4 to 12.

[0035] In some specific embodiments, the compatibilizer is ABS-g-MAH or SAN-g-MAH; preferably, the maleic anhydride grafting rate of the compatibilizer is 0.5-5%.

[0036] In some specific implementations, the antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant.

[0037] In some specific implementation schemes, the hindered phenolic antioxidants are antioxidant 1076 (CAS: 2082-79-3), antioxidant 1010 (CAS: 6683-19-8), or antioxidant 1790 (CAS: 40601-76-1).

[0038] In some specific implementation schemes, the phosphite antioxidant is antioxidant 168 (CAS: 31570-04-4).

[0039] In some specific implementations, the lubricant is C 12-40 Fatty acids, C 12-40 Fatty acid esters or C 12-40 Fatty acid amides.

[0040] In some specific implementations, the lubricant is stearic acid, pentaerythritol stearate, oleamide, or ethylene bis-stearamide.

[0041] One embodiment of this application is as follows: A method for preparing a long-lasting antistatic ABS composite material includes the following steps: Weigh each component according to any of the aforementioned formulations; after drying the ABS, compatibilizer, antioxidant, and lubricant, add them together with the long-lasting antistatic agent into a high-speed mixer and mix at 500-1000 rpm for 1-10 minutes to obtain a premix; continuously feed the premix into a twin-screw extruder and extrude and granulate it at 160-260°C; optionally, dry the granulated material at 80-90°C for 2-3 hours.

[0042] In some specific implementations, the extrusion granulation is carried out at 180-230°C.

[0043] In some specific implementations, the screw speed of the twin-screw extruder is 150-500 rpm.

[0044] One embodiment of this application is as follows: The application of any of the aforementioned long-lasting antistatic ABS composite materials in the preparation of plastic parts; said parts having antistatic or dustproof functions. 3. Detailed Implementation The raw materials used in this application can be purchased or synthesized in-house. The following specific embodiments are used to further describe the implementation of the present invention and do not limit the scope of the invention.

[0046] Example 1 The antistatic agent PA10.10-3-arm-PEG was prepared using the following steps: 103.2 g of decanediamine, 151.5 g of sebacic acid, and 13 mL of deionized water were added to a nitrogen-purged reactor. The mixture was heated to 230°C under normal pressure and stirred vigorously for 2 hours. Subsequently, the temperature was raised to 260°C over one hour, and 225 g of three-arm polyethylene glycol (3-arm-PEG, 1000 Da, PDI = 1.05) and 0.96 g of tetrabutyl titanate were added. The reaction was continued at 260°C with stirring for 30 minutes. The reaction was then continued for 3 hours under reduced pressure (below 140 Pa). After underwater pelleting and drying, the antistatic agent PA10.10-3-arm-PEG was obtained. GPC analysis showed that the number-average molecular weight of the copolymer was 2.4 kDa. NMR analysis showed that the copolymer contained 46.3 wt% polyethylene glycol, and the ratio of free hydroxyl groups to esterified hydroxyl groups was approximately 1.6 / 1.4.

[0047] The antistatic agent PA12.12-3-arm-PEG was prepared using the following steps: 120.0 g of dodecanediamine, 172.5 g of dodecanoic acid, and 15 mL of deionized water were added to a nitrogen-purged reactor. The mixture was heated to 230 °C under normal pressure and stirred vigorously for 2 hours. Subsequently, the temperature was raised to 260 °C over one hour, and 225 g of three-arm polyethylene glycol (3-arm-PEG, 1000 Da, PDI = 1.05) and 1.03 g of tetrabutyl titanate were added. The reaction was continued at 260 °C with stirring for 30 minutes. The reaction was then continued for 3 hours under reduced pressure (below 140 Pa). After underwater pelleting and drying, the antistatic agent PA12.12-3-arm-PEG was obtained. GPC analysis showed that the number-average molecular weight of the copolymer was 2.5 kDa. NMR analysis showed that the copolymer contained 45.5 wt% polyethylene glycol, and the ratio of free hydroxyl groups to esterified hydroxyl groups was approximately 1.7 / 1.3.

[0048] Example 2 This embodiment uses the following formulation to prepare a long-lasting antistatic ABS composite material: ABS: 92% PA10.10-3-arm-PEG: 3% MAH-g-ABS: 2% Antioxidant 1010: 0.2% Stearic acid: 2.8% The specific steps are as follows: Raw materials were weighed according to the above formula. ABS, MAH-g-ABS, antioxidant 1010, and stearic acid were dried at 80°C for 2 hours, and then added together with the antistatic agent PA10.10-3-arm-PEG prepared in Example 1 into a high-speed mixer. The mixture was mixed at 500 rpm for 5 minutes to obtain a premix. The premix was continuously fed into a twin-screw extruder for granulation. The screw zone temperatures were set as follows: Zone 1 180°C, Zone 2 190°C, Zone 3 210°C, and Zone 4 230°C. The screw speed was 150 rpm, and a cooling water bath was set at the die for pelletizing. After granulation, the pellets were dried at 80°C for 2 hours to remove residual moisture, yielding a long-lasting antistatic ABS composite material.

[0049] Example 3 This embodiment uses the following formulation to prepare a long-lasting antistatic ABS composite material: ABS: 85% PA10.10-3-arm-PEG: 10% MAH-g-ABS: 2.5% Antioxidant 1010: 0.5% Stearic acid: 2% For specific steps, please refer to Example 2.

[0050] Example 4 This embodiment uses the following formulation to prepare a long-lasting antistatic ABS composite material: ABS: 90% PA10.10-3-arm-PEG: 5% MAH-g-ABS: 2.2% Antioxidant 168: 0.6% Stearic acid: 2.2% For specific steps, please refer to Example 2.

[0051] Example 5 This embodiment uses the following formulation to prepare a long-lasting antistatic ABS composite material: ABS: 95% PA10.10-3-arm-PEG: 2% MAH-g-ABS: 1% Antioxidant 1010: 0.2% Ethylene bis-stearamide: 1.8% For specific steps, please refer to Example 2.

[0052] Example 6 This embodiment uses the following formulation to prepare a long-lasting antistatic ABS composite material: ABS: 92% PA12.12-3-arm-PEG: 3% MAH-g-ABS: 2% Antioxidant 1010: 0.2% Stearic acid: 2.8% For specific steps, please refer to Example 2.

[0053] Comparative Example This comparative example uses the commercially available antistatic agent MH1657 (Arkema) to prepare antistatic ABS composite materials according to the following formulation, with specific steps referred to Example 2.

[0054] ABS: 92% MH1657: 3% MAH-g-ABS: 2% Antioxidant 1010: 0.2% Stearic acid: 2.8% Example 7 This embodiment tests the surface resistivity, notched impact strength, tensile strength, and elongation at break of the antistatic ABS composite materials prepared in the aforementioned embodiments and comparative examples.

[0055] Surface resistivity test: Granules were injection molded into 100 mm × 100 mm × 2 mm flat samples. After treatment under different conditions, tests were conducted according to GB / T 1410-2006. Condition 1: Tested after 24 hours at 23°C and 50%RH. Condition 2: Tested after 91 days at 23°C and 50%RH. Condition 3: Tested after 90 days at 23°C and 20%RH, followed by 24 hours at 23°C and 50%RH. Condition 4: Tested after 181 days at 23°C and 50%RH. Condition 5: Tested after 180 days at 23°C and 20%RH, followed by 24 hours at 23°C and 50%RH.

[0056] Mechanical property tests were performed using injection-molded specimens, with at least five valid samples per group. Notched impact strength was tested according to GB / T1043.1-2008 standard, using 80 mm × 10 mm × 4 mm specimens with a V-notch for simply supported beam impact testing. Tensile strength and elongation at break were tested according to GB / T 1040.2-2006 standard, using I-beam specimens at a speed of 50 mm / min until fracture. All results were averaged.

[0057] Table 1. Performance testing of antistatic ABS composite materials

[0058] The tests (Table 1) show that the surface resistivity of the ABS composite materials prepared in Examples 2-6 under various conditions is 8.3 × 10⁻⁶. 6 Ω to 7.8×10 7 The values ​​of Ω were significantly lower than those of the comparative sample (3.7 × 10⁻⁶). 8 The antistatic properties of the ABS composite material provided in this application are stable and long-lasting, with an antistatic agent content of Ω or higher, and are less affected by storage time and ambient humidity. Specifically, the ABS composite material of Example 5 achieved better long-lasting antistatic properties even with a lower antistatic agent content (2%) than the comparative example (3%). On the other hand, the notched impact strength and elongation at break of the ABS composite materials prepared in Examples 2-6 are higher than those of the comparative example, while their tensile strength is close to that of the comparative example, indicating that the formulation of this application can provide good mechanical properties for antistatic ABS composite materials.

Claims

1. A long-lasting antistatic ABS composite material, characterized in that, Composed of the following components: ABS, long-lasting antistatic agent, compatibilizer, antioxidant, and lubricant; the formula is as follows: ABS: 85-95 wt% Long-lasting antistatic agent: 2-10 wt% Compatibilizer: 0.5-5 wt% Antioxidant: 0.1-1 wt% Lubricant: 0.5-5 wt% The long-lasting antistatic agent is a polyether ester amide containing a branched polyether structure.

2. The long-lasting antistatic ABS composite material according to claim 1, characterized in that, The polyether ester amide contains a branched polyethylene glycol structure.

3. The long-lasting antistatic ABS composite material according to claim 1, characterized in that, The molecular weight of the polyether ester amide is 1000-4000 Da, preferably 1500-3000 Da, and more preferably 2000-2500 Da; Optionally, the polyether content of the polyether ester amide is 40-60 wt%, preferably 45-50 wt%. Optionally, the polyamide portion of the polyether ester amide is PA10.10 or PA12.

12.

4. The long-lasting antistatic ABS composite material according to claim 1, characterized in that, The long-lasting antistatic agent is obtained by the following preparation method: Diamine, diacid, and deionized water were added to a reaction vessel purged with an inert gas. The mixture was heated to 220-230°C under normal pressure and stirred vigorously for 2-4 hours. Subsequently, the temperature was raised to 250-260°C, and branched polyether and catalyst were added. The reaction was continued at 250-260°C with stirring for 30-60 minutes. Then, the reaction was continued under reduced pressure for 3-4 hours. After the reaction was completed, the mixture was granulated and dried to obtain the long-lasting antistatic agent. The molar ratio of diamine, diacid, and branched polyether is (3-5):(4-6):(0.5-2), preferably 4:5:1.5; the amount of deionized water is 3-8 wt% of the total amount of diamine and diacid, preferably 5 wt%; the amount of catalyst is 0.1-0.5 wt% of the total amount of diamine, diacid, and branched polyether, preferably 0.2 wt%. The branched polyether is preferably branched polyethylene glycol, more preferably three-armed polyethylene glycol or four-armed polyethylene glycol; Preferably, the three-armed polyethylene glycol has the following structure: ； Where n represents the degree of polymerization of each polyethylene glycol chain; each n is an independent integer from 4 to 12.

5. The long-lasting antistatic ABS composite material according to claim 1, characterized in that, The compatibilizer is ABS-g-MAH or SAN-g-MAH.

6. The long-lasting antistatic ABS composite material according to claim 1, characterized in that, The antioxidant is a hindered phenolic antioxidant or a phosphite antioxidant; Preferably, the hindered phenolic antioxidant is antioxidant 1076, antioxidant 1010, or antioxidant 1790; Preferably, the phosphite antioxidant is antioxidant 168.

7. The long-lasting antistatic ABS composite material according to claim 1, characterized in that, The lubricant is C. 12-40 Fatty acids, C 12-40 Fatty acid esters or C 12-40 Fatty acid amides, preferably stearic acid, pentaerythritol stearate, oleamide or ethylene bis-stearamide.

8. A method for preparing the long-lasting antistatic ABS composite material according to claim 1, characterized in that, Includes the following steps: Weigh each component according to the formulation of claim 1; after drying the ABS, compatibilizer, antioxidant and lubricant, add them together with the long-lasting antistatic agent into a high-speed mixer and mix at 500-1000 rpm for 1-10 minutes to obtain a premix; continuously feed the premix into a twin-screw extruder and extrude and granulate at 160-260°C to obtain the long-lasting antistatic ABS composite material of claim 1.

9. The application of the long-lasting antistatic ABS composite material according to claim 1 in the preparation of plastic parts, characterized in that, The component has anti-static or dustproof functions.

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