Preparation method of high-temperature-resistant ABS material

Abstract

The application relates to the technical field of acrylonitrile-butadiene-styrene, and discloses a preparation method of a high-temperature-resistant ABS material, wherein acrylonitrile-butadiene-styrene resin, carboxyl polyarylether sulfone, AN-PS-GMA copolymer and the like are mixed, melt extruded, water-cooled and cut into particles to obtain the high-temperature-resistant ABS material. The AN-PS-GMA copolymer plays the role of a reactive compatilizer, improves the compatibility between the carboxyl polyarylether sulfone and the ABS resin, and makes the ABS material show higher tensile strength and impact strength. The carboxyl polyarylether sulfone introduces the heat-resistant terphenyl structure into a molecular main chain, is favorable for improving the high-temperature-resistant performance of the ABS material, and after high-temperature heat treatment, the material still has higher tensile strength and impact strength. And the material shows lower surface resistivity and good antistatic performance.

Description

Technical Field

[0001] This invention relates to the field of acrylonitrile-butadiene-styrene technology, specifically a method for preparing high-temperature resistant ABS material. Background Technology

[0002] Polyarylene ether sulfone (PAESK) is a novel polymer resin with high mechanical strength, good dimensional stability, and excellent heat resistance. It has important applications in materials such as epoxy resin, ABS resin, nylon, polyvinylidene fluoride (PVDF), and polyimide, improving their strength, toughness, and high-temperature resistance. Chinese patent CN109777032B discloses the production and application of granulated reinforcing materials for injection molding from recycled waste circuit boards and copper-clad laminates. Using ABS resin, functional allyl-side-group or vinyl-containing diazanaphthone biphenyl-structured polyarylene ether sulfone ketone (PPESK) resin, waste circuit boards, and copper-clad laminates as raw materials, the prepared granulated reinforcing material exhibits good tensile properties, flame retardancy, and high and low temperature resistance. Therefore, the development of functional PAESK materials is of great significance. ABS resin is a terpolymer of acrylonitrile, butadiene, and styrene, widely used in electromechanical, instrumentation, automotive, and building materials industries. However, traditional ABS resin suffers from poor high-temperature resistance, low mechanical strength, and poor antistatic properties, limiting the practical application of ASB materials. Summary of the Invention

[0003] (I) Technical problem to be solved: In view of the shortcomings of the existing technology, the present invention provides an ABS material with antistatic and high temperature resistance properties.

[0004] (II) Technical Solution: A method for preparing high-temperature resistant ABS material, comprising the following steps:

[0005] Step (1): Toluene, 4,4'-dichlorodiphenyl sulfone (in a molar ratio of 100:(50-70):(30-50):(180-220), hydroquinone, ester-based diphenol monomer, and potassium carbonate are added to N-methylpyrrolidone. The mixture is heated to 130-140℃ under a nitrogen atmosphere and refluxed for 2-3 hours to remove water. Then, the temperature is increased to 180-190℃ and refluxed for 6-8 hours. After cooling, the solution is poured into water, filtered, and the filter cake is washed with ethanol. The product is added to a 3-4 mol / L sodium hydroxide aqueous solution, heated to 90-100℃, and refluxed for 4-6 hours. The mixture is then filtered, the filter cake is washed with water, and dried to obtain carboxylated polyarylene ether sulfone. The preparation reaction formula is as follows:

[0006]

[0007] Step (2): Mix acrylonitrile-butadiene-styrene resin, carboxylated polyarylene sulfone, AN-PS-GMA copolymer and antioxidant in a mixer, then melt extrude in a twin-screw extruder, and water-cool and pelletize to obtain high-temperature resistant ABS material.

[0008] Further, the preparation method of the ester-based diphenol monomer is as follows: 1,4-terephthalic acid, methyl 5-bromosalicylate, and palladium acetate are added to 1,4-dioxane in a molar ratio of 1:(2-2.2):(0.008-0.01). After stirring, a 0.8-1 mol / L potassium carbonate aqueous solution is added dropwise. The mixture is heated to 80-90℃ and reacted for 4-7 hours. The mixture is then rotary evaporated, filtered, washed with water, and the product is separated by column chromatography, eluted with ethyl acetate and petroleum ether solution to obtain the ester-based diphenol monomer. The preparation reaction formula is as follows:

[0009]

[0010] Furthermore, the antioxidants in step (2) include antioxidant 1076 and antioxidant 1010.

[0011] Furthermore, in step (2), the mass ratio of acrylonitrile-butadiene-styrene resin, carboxylated polyarylene ether sulfone, and AN-PS-GMA copolymer is 100:(10-40):(0.8-3).

[0012] Furthermore, the preparation method of AN-PS-GMA copolymer is as follows: sodium dodecylbenzenesulfonate, tert-dodecyl mercaptan, acrylonitrile, styrene, and glycidyl methacrylate in a mass ratio of (25-40):(55-73):(2-5) are added to water. After stirring, azobisisobutyronitrile is added under a nitrogen atmosphere. The mixture is heated to 70-75℃ and reacted for 4-5 hours. Then, the temperature is raised to 85-90℃ and reacted for 0.5-1 hours. After cooling, the mixture is filtered, the filter cake is washed with water and ethanol, and dried to obtain AN-PS-GMA copolymer.

[0013] (III) Technical Effects: This invention involves the polycondensation and hydrolysis of 4,4'-dichlorodiphenyl sulfone, hydroquinone, and ester-based bisphenol monomers to obtain carboxyl polyarylene ether sulfone. This carboxyl polyarylene ether sulfone is then melt-extruded with acrylonitrile-butadiene-styrene ABS resin and AN-PS-GMA copolymer to obtain a high-temperature resistant ABS material. During the high-temperature melting process, the epoxy groups of the AN-PS-GMA copolymer can react with the carboxyl groups of the polyarylene ether sulfone. Since the AN-PS-GMA copolymer contains styrene and acrylonitrile structural units, it exhibits excellent structural compatibility and compatibility with the ABS resin. This allows the AN-PS-GMA copolymer to act as a reactive compatibilizer, improving the compatibility between the carboxyl polyarylene ether sulfone and the ABS resin. This ensures that the polyarylene ether sulfone is uniformly dispersed in the ABS material matrix, forming a homogeneous system. Consequently, the ABS material exhibits higher tensile strength and impact strength.

[0014] The polyarylene sulfone of this invention possesses strong heat resistance, while simultaneously introducing a heat-resistant terphenyl structure into the molecular backbone. When added to ABS resin, it improves the material's high-temperature resistance; even after high-temperature heat treatment, the ABS material retains high tensile strength and impact strength.

[0015] The side chain of the carboxylated polyarylether sulfone of the present invention contains a large number of carboxylic hydrophilic groups. At the same time, some carboxyl groups react with the epoxy groups of the AN-PS-GMA copolymer to generate hydrophilic hydroxyl groups, which significantly improves the surface hydrophilicity of ABS material, reduces the surface water contact angle, and facilitates the formation of a water molecule film on the surface, thereby reducing the surface resistivity and improving the antistatic properties of the material. Detailed Implementation

[0016] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] The acrylonitrile-butadiene-styrene resin of this invention, model ABS PA-757, is from Shanghai Honglei Plastics Co., Ltd.

[0018] Example 1:

[0019] (1) Add 0.13g sodium dodecylbenzenesulfonate, 0.1g tert-dodecyl mercaptan, 2.5g acrylonitrile, 7g styrene and 0.2g glycidyl methacrylate to 50mL of water, stir, add 0.45g azobisisobutyronitrile in a nitrogen atmosphere, heat to 70℃, react for 5h, then heat to 90℃, react for 0.5h, cool, filter, wash the filter cake with water and ethanol, dry, and obtain AN-PS-GMA copolymer.

[0020] (2) Add 50 mmol of 1,4-terephthalic acid, 110 mmol of methyl 5-bromosalicylate, and 0.4 mmol of palladium acetate to 400 mL of 1,4-dioxane. After stirring, add 300 mL of 0.8 mol / L potassium carbonate aqueous solution. Heat to 90 °C and react for 4 h. Evaporate by rotary evaporation, filter and wash with water. Separate the product by column chromatography and elute with ethyl acetate and petroleum ether solution to obtain ester-based diphenol monomer.

[0021] (3) Add 300 mL of toluene, 100 mmol of 4,4'-dichlorodiphenyl sulfone, 70 mmol of hydroquinone, 30 mmol of ester-based diphenol monomer, and 200 mmol of potassium carbonate to 650 mL of N-methylpyrrolidone. Heat to 140 °C under a nitrogen atmosphere and reflux for 2 h to remove water. Then raise the temperature to 190 °C and reflux for 6 h. After cooling, pour the solution into water, filter, wash the filter cake with ethanol, add the product to 1.2 L of 3.5 mol / L sodium hydroxide aqueous solution, heat to 90 °C, reflux for 6 h, filter, wash the filter cake with water, and dry to obtain carboxylated polyarylene sulfone.

[0022] (4) Mix 5 kg of acrylonitrile-butadiene-styrene resin (brand name: Formosa Plastics AE8200, the same below), 0.5 kg of carboxylated polyarylene ether sulfone, 40 g of AN-PS-GMA copolymer, and 22 g of antioxidant 1076 in a mixer, and then melt extrude in a twin-screw extruder at an extrusion temperature of 210°C. After water cooling and pelletizing, high-temperature resistant ABS material is obtained.

[0023] Comparative Example 1:

[0024] (1) 5 kg of acrylonitrile-butadiene-styrene resin, 40 g of AN-PS-GMA copolymer (prepared according to the method of Example 1) and 22 g of antioxidant 1076 were mixed in a mixer and then melt-extruded in a twin-screw extruder at an extrusion temperature of 210°C. The mixture was then water-cooled and pelletized to obtain high-temperature resistant ABS material.

[0025] Comparative Example 2:

[0026] (1) 5 kg of acrylonitrile-butadiene-styrene resin, 0.5 kg of carboxylated polyarylene sulfone (prepared according to the method of Example 1) and 22 g of antioxidant 1076 were mixed in a mixer and then melt-extruded in a twin-screw extruder at an extrusion temperature of 210°C. The mixture was then water-cooled and pelletized to obtain high-temperature resistant ABS material.

[0027] Comparative Example 3:

[0028] (1) Add 300 mL of toluene, 100 mmol of 4,4'-dichlorodiphenyl sulfone, 70 mmol of hydroquinone, and 30 mmol of [1,1':4',1”-terphenyl]-4,4”-diol (CAS No. 4084-45-1, structural formula: ) to 650 mL of N-methylpyrrolidone. 200 mmol potassium carbonate was heated to 140 °C under a nitrogen atmosphere and refluxed for 2 hours to remove water. Then the temperature was raised to 190 °C and refluxed for 6 hours. After cooling, the solution was poured into water, filtered, the filter cake was washed with ethanol and dried to obtain polyarylether sulfone.

[0029] (2) 5 kg of acrylonitrile-butadiene-styrene resin, 0.5 kg of polyarylether sulfone, 40 g of AN-PS-GMA copolymer (prepared according to the method of Example 1) and 22 g of antioxidant 1076 were mixed in a mixer and then melt-extruded in a twin-screw extruder at an extrusion temperature of 210°C. The mixture was then water-cooled and pelletized to obtain high-temperature resistant ABS material.

[0030] Comparative Example 4:

[0031] (1) Add 300 mL of toluene, 100 mmol of 4,4'-dichlorodiphenyl sulfone, 70 mmol of hydroquinone, and 30 mmol of methyl 3,5-dihydroxybenzoate (CAS No. 2150-44-9, structural formula: [insert structural formula here]) to 650 mL of N-methylpyrrolidone. 200 mmol / L potassium carbonate was heated to 140 °C under a nitrogen atmosphere and refluxed for 2 h to remove water. Then the temperature was raised to 190 °C and refluxed for 6 h. After cooling, the solution was poured into water, filtered, and the filter cake was washed with ethanol. The product was added to a 3.5 mol / L sodium hydroxide aqueous solution, heated to 90 °C, and refluxed for 6 h. After filtration, the filter cake was washed with water and dried to obtain carboxylated polyarylene ether sulfone.

[0032] (2) 5 kg of acrylonitrile-butadiene-styrene resin, 0.5 kg of carboxylated polyarylene ether sulfone, 40 g of AN-PS-GMA copolymer (prepared according to the method of Example 1) and 22 g of antioxidant 1076 were mixed in a mixer and then melt-extruded in a twin-screw extruder at an extrusion temperature of 210°C. The mixture was then water-cooled and pelletized to obtain high-temperature resistant ABS material.

[0033] Example 2:

[0034] (1) Add 0.12g sodium dodecylbenzenesulfonate, 0.09g tert-dodecyl mercaptan, 4g acrylonitrile, 5.8g styrene, and 0.5g glycidyl methacrylate to 40mL of water. After stirring, add 0.52g azobisisobutyronitrile in a nitrogen atmosphere, heat to 75℃, react for 4h, then heat to 85℃, react for 1h, cool, filter, wash the filter cake with water and ethanol, and dry to obtain AN-PS-GMA copolymer.

[0035] (2) Add 50 mmol of 1,4-terephthalic acid, 100 mmol of methyl 5-bromosalicylate, and 0.5 mmol of palladium acetate to 350 mL of 1,4-dioxane. After stirring, add 250 mL of 1 mol / L potassium carbonate aqueous solution. Heat to 80 °C and react for 7 h. Evaporate by rotary evaporation, filter and wash with water. Separate the product by column chromatography and elute with ethyl acetate and petroleum ether solution to obtain ester-based diphenol monomer.

[0036] (3) Add 400 mL of toluene, 100 mmol of 4,4'-dichlorodiphenyl sulfone, 60 mmol of hydroquinone, 40 mmol of ester-based diphenol monomer, and 220 mmol of potassium carbonate to 700 mL of N-methylpyrrolidone. Heat to 140 °C under a nitrogen atmosphere and reflux for 2 h to remove water. Then raise the temperature to 190 °C and reflux for 6 h. After cooling, pour the solution into water, filter, wash the filter cake with ethanol, add the product to 1.2 L of 4 mol / L sodium hydroxide aqueous solution, heat to 90 °C, reflux for 6 h, filter, wash the filter cake with water, and dry to obtain carboxylated polyarylene sulfone.

[0037] (4) Mix 5 kg of acrylonitrile-butadiene-styrene resin, 1.2 kg of carboxylated polyarylether sulfone, 100 g of AN-PS-GMA copolymer, and 15 g of antioxidant 1010 in a mixer, and then melt-extrude in a twin-screw extruder at an extrusion temperature of 210°C. Water-cooled pellets are then obtained to obtain high-temperature resistant ABS material.

[0038] Example 3:

[0039] (1) Add 400 mL of toluene, 100 mmol of 4,4'-dichlorodiphenyl sulfone, 50 mmol of hydroquinone, 50 mmol of ester-based diphenol monomer (prepared in the same way as in Example 1), and 180 mmol of potassium carbonate to 700 mL of N-methylpyrrolidone. Heat to 130 °C under a nitrogen atmosphere and reflux for 3 h to remove water. Then raise the temperature to 180 °C and reflux for 8 h. After cooling, pour the solution into water, filter, wash the filter cake with ethanol, add the product to 1.2 L of 3 mol / L sodium hydroxide aqueous solution, heat to 100 °C, reflux for 4 h, filter, wash the filter cake with water, and dry to obtain carboxylated polyarylene sulfone.

[0040] (2) Mix 5 kg of acrylonitrile-butadiene-styrene resin, 2 kg of carboxylated polyarylene ether sulfone, 150 g of AN-PS-GMA copolymer (prepared in the same way as in Example 1), and 20 g of antioxidant 1076 in a mixer, and then melt extrude in a twin-screw extruder at an extrusion temperature of 210°C. After water cooling and pelletizing, high-temperature resistant ABS material is obtained.

[0041] High-temperature resistant ABS material was injection molded into specimens using an injection molding machine. Tensile strength was tested according to national standard GB / T 1040.1-2018. Impact strength was tested according to national standard GB / T 1843-2008.

[0042] The sample was placed in a heating chamber at 150°C for 48 hours, then left at room temperature for 6 hours before testing its tensile strength and impact strength.

[0043] Table 1 Mechanical property testing of ABS materials

[0044]

[0045] As can be seen from Example 1 and Comparative Example 1, the ABS material of Example 1 has higher tensile strength and impact strength, and after high temperature heat treatment, the retention rate of tensile strength and impact strength is high, at 90.72% (40.1 / 44.2) and 89.07% (28.35 / 31.83), respectively. The main reason for this is the addition of carboxyl polyarylene ether sulfone and AN-PS-GMA copolymer. During the high-temperature melting process, the epoxy groups of the AN-PS-GMA copolymer can react with the carboxyl groups of the polyarylene ether sulfone. The AN-PS-GMA copolymer contains styrene and acrylonitrile structural units, which have excellent structural and compatibility with ABS resin. This allows the AN-PS-GMA copolymer to act as a reactive compatibilizer, improving the compatibility between carboxyl polyarylene ether sulfone and ABS resin. This ensures that the polyarylene ether sulfone is uniformly dispersed in the ABS matrix, forming a homogeneous system. This results in higher tensile and impact strength in the ABS material. Furthermore, the polyarylene ether sulfone itself has strong heat resistance, and the introduction of a heat-resistant terphenyl structure into the molecular backbone further enhances its properties. Adding it to ABS resin helps improve the material's high-temperature resistance. After high-temperature heat treatment, the material still has high tensile strength and impact strength.

[0046] Comparative Example 2 did not include AN-PS-GMA copolymer, resulting in poor compatibility between carboxylated polyarylether sulfone and ABS resin, which did not significantly improve the mechanical properties of the material, and the tensile strength and impact strength were low.

[0047] Comparative Example 3 uses [1,1':4',1”-terphenyl]-4,4”-diol as raw material to prepare polyarylether sulfone. It does not contain carboxyl groups and cannot react with AN-PS-GMA copolymer. Therefore, it cannot act as a compatibilizer and does not improve the compatibility between polyarylether sulfone and ABS resin, resulting in low tensile strength and impact strength of the material.

[0048] Comparative Example 4, using methyl 3,5-dihydroxybenzoate as a reactant, prepared a carboxylated polyarylene sulfone. Under the solubilizing effect of AN-PS-GMA copolymer, it showed good compatibility with ABS resin, and the tensile strength and impact strength of the material were significantly improved. However, after high-temperature heat treatment, the retention rates of tensile strength and impact strength were low, only 88.03% (37.5 / 42.6) and 86.54% (27.85 / 32.18) respectively, which were lower than those of Example 1. This was mainly because the carboxylated polyarylene sulfone of Comparative Example 4 did not contain a heat-resistant terphenyl structure, resulting in lower heat resistance than that of the carboxylated polyarylene sulfone of Example 1. Therefore, its addition to ABS resin could not effectively improve the high-temperature resistance of the material.

[0049] The ABS material was pressed into a film, and the water contact angle was tested according to the national standard GB / T 30693-2014.

[0050] The surface resistivity of ABS material was measured using a high-resistivity meter. The test temperature was 25℃ and the relative humidity was 55%.

[0051] Table 2 Surface Resistivity Test of ABS Material

[0052] Water contact angle (°) Surface resistivity (Ω) Example 1 85.4 <![CDATA[5.13×10 14 ]]> Comparative Example 1 92.7 <![CDATA[2.05×10 16 ]]> Comparative Example 2 85.9 <![CDATA[5.79×10 14 ]]> Comparative Example 3 93.2 <![CDATA[2.16×10 16 ]]> Comparative Example 4 88.7 <![CDATA[8.24×10 14 ]]> Example 2 69.8 <![CDATA[4.86×10 12 ]]> Example 3 63.0 <![CDATA[1.21×10 11 ]]>

[0053] As shown in Example 1 and Comparative Example 1, the ABS material in Example 1 has a lower surface water contact angle and better hydrophilicity, which is beneficial for forming a water molecule film on the surface, thereby reducing surface resistivity and improving antistatic performance. This is mainly because the side chain of the added carboxyl polyarylether sulfone contains a large number of carboxyl hydrophilic groups, and some carboxyl groups react with the epoxy groups of the AN-PS-GMA copolymer to generate hydrophilic hydroxyl groups. It significantly improves the surface hydrophilicity of ABS materials.

[0054] In Comparative Example 2, the addition of carboxylated polyarylether sulfone resulted in a lower water contact angle in the ABS material, which helped to reduce surface resistivity and improve antistatic properties.

[0055] The polyarylether sulfone added in Comparative Example 3 does not contain carboxyl groups, resulting in a large water contact angle and surface resistivity of the ABS material, and poor antistatic properties.

[0056] Comparative Example 4, which incorporates carboxyl polyarylether sulfone, exhibits lower water contact angles and surface resistivity in its ABS material, resulting in better antistatic properties. However, its water contact angles and surface resistivity are higher than those of Example 1. This is primarily because the ester-based diphenol monomer contains two ester groups, which can generate two carboxyl groups upon hydrolysis. In contrast, methyl 3,5-dihydroxybenzoate contains only one ester group, which can only generate one carboxyl group upon hydrolysis. Consequently, the carboxyl content of the polyarylether sulfone in Comparative Example 4 is significantly lower than that in Example 1. Therefore, its hydrophilicity is lower than that of the polyarylether sulfone in Example 1, leading to a higher water contact angle and surface resistivity in the ABS material of Comparative Example 4 compared to Example 1.

[0057] In Examples 2-3, the ABS materials exhibited good tensile strength, impact strength, and high temperature resistance under different amounts of carboxylated polyarylether sulfone and AN-PS-GMA copolymer, and also had low surface resistivity and good antistatic properties.

Claims

1. A method for preparing a high temperature resistant ABS material, characterized in that, The preparation method comprises the following steps: Step (1), to N-methyl pyrrolidone is added toluene, 4, 4'-dichlorodiphenyl sulfone, hydroquinone, the ester group diphenol monomer of structural formula is added, heated to 130-140℃, refluxed with water for 2-3h, then heated to 180-190℃, condensation reflux reaction for 6-8h, after cooling the solution is poured into water, suction filtration, the filter cake is washed with ethanol, the product is added to sodium hydroxide aqueous solution, heated to 90-100℃, condensation reflux reaction for 4-6h, suction filtration, the filter cake is washed with water, dried, to obtain carboxyl polyarylether sulfone; Step (2), acrylonitrile-butadiene-styrene resin, carboxyl polyarylether sulfone, acrylonitrile-styrene-glycidyl methacrylate copolymer, antioxidant are mixed in a mixer, then melt-extruded in a double-screw extruder, water-cooled pelletized, to obtain a high-temperature-resistant ABS material.

2. The process for the preparation of high temperature resistant ABS material as claimed in claim 1 wherein, The molar ratio of 4,4'-dichlorodiphenyl sulfone, hydroquinone, ester-based diphenol monomer and potassium carbonate in step (1) is 100:(50-70):(30-50):(180-220).

3. The process for the preparation of high temperature resistant ABS material as claimed in claim 2 wherein, The preparation method of the ester-based diphenol monomer is: 1,4-p-benzenediol, 5-bromomethyl salicylate and palladium acetate are added to 1,4-dioxane, after stirring, potassium carbonate aqueous solution is added dropwise, heated to 80-90 DEG C, reacted for 4-7 h, rotary evaporated, filtered, washed with water, and the product is separated by column chromatography to obtain the ester-based diphenol monomer.

4. The process for the preparation of high temperature resistant ABS material as claimed in claim 3 wherein, The molar ratio of 1,4-p-benzenediol, 5-bromomethyl salicylate and palladium acetate is 1:(2-2.2):(0.008-0.01).

5. The process for the preparation of high temperature resistant ABS material as claimed in claim 3, wherein, The concentration of the potassium carbonate aqueous solution is 0.8-1 mol / L.

6. The method for preparing high-temperature resistant ABS material according to claim 1, characterized in that, The concentration of the sodium hydroxide aqueous solution in step (1) is 3-4 mol / L.

7. The method for preparing high-temperature resistant ABS material according to claim 1, characterized in that, The antioxidant in step (2) comprises antioxidant 1076 and antioxidant 1010.

8. The method for preparing high-temperature resistant ABS material according to claim 1, characterized in that, The mass ratio of acrylonitrile-butadiene-styrene resin, carboxyl polyarylether sulfone and acrylonitrile-styrene-glycidyl methacrylate copolymer in step (2) is 100:(10-40):(0.8-3).

9. The method for preparing high-temperature resistant ABS material according to claim 8, characterized in that, The preparation method of the acrylonitrile-styrene-glycidyl methacrylate copolymer is: sodium dodecylbenzenesulfonate, tert-dodecanethiol, acrylonitrile, styrene and glycidyl methacrylate with a mass ratio of (25-40):(55-73):(2-5) are added to water, after stirring, azobisisobutyronitrile is added in a nitrogen atmosphere, heated to 70-75 DEG C, reacted for 4-5 h, then heated to 85-90 DEG C, reacted for 0.5-1 h, cooled, filtered, washed and dried to obtain the acrylonitrile-styrene-glycidyl methacrylate copolymer.

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