Preparation method of high-temperature-resistant ABS material

Abstract

The invention relates to the technical field of acrylonitrile-butadiene-styrene, and discloses a preparation method of a high-temperature-resistant ABS (acrylonitrile-butadiene-styrene) material, which comprises the following steps: mixing acrylonitrile-butadiene-styrene resin, carboxyl polyether sulfone, AN-PS-GMA copolymer and the like, carrying out melt extrusion, and carrying out water-cooling pelletizing to obtain the high-temperature-resistant ABS material. The AN-PS-GMA copolymer plays a role of a reactive compatilizer, so that the compatibility between the carboxyl polyether sulfone and the ABS resin is improved, and the ABS material shows higher tensile strength and impact strength. According to the carboxyl polyether sulphone, a heat-resistant terphenyl structure is introduced into a molecular main chain, so that the high-temperature resistance of the ABS material is improved, and the material still has relatively high tensile strength and impact strength after high-temperature heat treatment. In addition, lower surface resistivity and good antistatic performance are shown.

Description

Technical Field

[0001] The invention relates to the technical field of acrylonitrile-butadiene-styrene, in particular to a method for preparing a high-temperature resistant ABS material. Background Art

[0002] Polyarylethersulfone is a new type of 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, polyimide, etc., and can improve the strength, toughness and high temperature resistance of materials. The Chinese patent with announcement number CN109777032B discloses the use of recycled waste circuit boards and copper-clad laminates to make granulation reinforcement materials for injection molding and their applications. The granulation reinforcement materials prepared using ABS resin, functional allyl side groups or vinyl-containing diazinone biphenyl structure polyarylethersulfoneketone PPESK resin, waste circuit boards, copper-clad laminates, etc. as raw materials have good tensile properties, flame retardancy and high and low temperature resistance. Therefore, it is of great significance to develop functional polyarylethersulfone materials. ABS resin is a terpolymer of acrylonitrile, butadiene and styrene, and is widely used in the fields of electromechanics, instruments, automobiles, building materials, etc. However, traditional ABS resin has problems such as poor high temperature resistance, low mechanical strength and poor antistatic performance, which limits the practical application of ASB materials. Summary of the invention

[0003] (I) Technical problems to be solved: In view of the deficiencies in the prior art, the present invention provides an ABS material with antistatic and high temperature resistance properties.

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

[0005] Step (1), add toluene, 4,4'-dichlorodiphenyl sulfone, hydroquinone, ester diphenol monomer, potassium carbonate in a molar ratio of 100:(50-70):(30-50):(180-220) to N-methylpyrrolidone, heat to 130-140°C in a nitrogen atmosphere, reflux with water for 2-3h, then heat to 180-190°C, condense and reflux for 6-8h, cool and pour the solution into water, filter with suction, wash the filter cake with ethanol, add the product to 3-4mol / L sodium hydroxide aqueous solution, heat to 90-100°C, condense and reflux for 4-6h, filter with suction, wash the filter cake with water, and dry to obtain carboxyl polyarylethersulfone. The preparation reaction formula is as follows:

[0006]

[0007] Step (2), mixing acrylonitrile-butadiene-styrene resin, carboxyl polyarylethersulfone, AN-PS-GMA copolymer and antioxidant in a mixer, then melt-extrude in a twin-screw extruder, water-cooled and pelletized to obtain a high temperature resistant ABS material.

[0008] Further, the preparation method of the ester-based diphenol monomer is as follows: add 1,4-terephthalenediboronic acid, methyl 5-bromosalicylate, and palladium acetate in a molar ratio of 1: (2-2.2): (0.008-0.01) to 1,4-dioxane, add 0.8-1 mol / L potassium carbonate aqueous solution dropwise after stirring, heat to 80-90° C., react for 4-7 hours, rotary evaporate, filter and wash with water, separate the product by column chromatography, and elute 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 antioxidant in step (2) includes antioxidant 1076 and antioxidant 1010.

[0011] Furthermore, in step (2), the mass ratio of acrylonitrile-butadiene-styrene resin, carboxyl polyarylethersulfone, 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 dodecylbenzene sulfonate, tert-dodecyl mercaptan, acrylonitrile, styrene, and glycidyl methacrylate in a mass ratio of (25-40):(55-73):(2-5) are added to water, and after stirring, azobisisobutyronitrile is added in a nitrogen atmosphere, heated to 70-75° C., reacted for 4-5 hours, then heated to 85-90° C., reacted for 0.5-1 hour, cooled, filtered, washed the filter cake with water and ethanol, and dried to obtain AN-PS-GMA copolymer.

[0013] (III) Technical effect: The present invention conducts polycondensation reaction and hydrolysis reaction of 4,4'-dichlorodiphenyl sulfone, hydroquinone, and ester-based diphenol monomers to obtain carboxyl polyarylethersulfone, which is then melt-extruded with acrylonitrile-butadiene-styrene ABS resin and AN-PS-GMA copolymer to obtain high-temperature resistant ABS material. During the high-temperature melting process, the epoxy group of the AN-PS-GMA copolymer can react with the carboxyl group of the polyarylethersulfone, and the AN-PS-GMA copolymer contains styrene and acrylonitrile structural units, which have good structural compatibility and compatibility with the ABS resin, so that the AN-PS-GMA copolymer plays the role of a reactive compatibilizer, improves the compatibility between the carboxyl polyarylethersulfone and the ABS resin, and makes the polyarylethersulfone evenly dispersed in the ABS material matrix, and the two form a homogeneous system, so that the ABS material exhibits higher tensile strength and impact strength.

[0014] The polyarylethersulfone of the present invention has strong heat resistance itself, and a heat-resistant terphenyl structure is introduced into the main chain of the molecule. When added to ABS resin, it is beneficial to improve the high temperature resistance of the material. After high temperature heat treatment, the ABS material still has high tensile strength and impact strength.

[0015] The side chain of the carboxyl polyarylethersulfone of the present invention contains a large number of carboxyl hydrophilic groups, and part of the 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 the ABS material, reduces the surface water contact angle, is conducive to the formation of a water molecule film on the surface, thereby reducing the surface resistivity and improving the antistatic performance of the material. DETAILED DESCRIPTION

[0016] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0017] The acrylonitrile-butadiene-styrene resin of the present invention has a model of ABS PA-757 and is produced by Shanghai Honglei Plastic Chemical Co., Ltd.

[0018] Embodiment 1:

[0019] (1) 0.13 g of sodium dodecylbenzene sulfonate, 0.1 g of tert-dodecyl mercaptan, 2.5 g of acrylonitrile, 7 g of styrene, and 0.2 g of glycidyl methacrylate were added to 50 mL of water, and after stirring, 0.45 g of azobisisobutyronitrile was added in a nitrogen atmosphere. The mixture was heated to 70° C. and reacted for 5 h. The mixture was then heated to 90° C. and reacted for 0.5 h. The mixture was cooled and filtered. The filter cake was washed with water and ethanol and dried to obtain an AN-PS-GMA copolymer.

[0020] (2) Add 50 mmol 1,4-terephthalenediboronic acid, 110 mmol methyl 5-bromosalicylate, and 0.4 mmol palladium acetate to 400 mL 1,4-dioxane, and then dropwise add 300 mL 0.8 mol / L potassium carbonate aqueous solution after stirring. Heat to 90° C., react for 4 h, rotary evaporate, filter, and wash with water. The product is separated by column chromatography and eluted with ethyl acetate and petroleum ether solution to obtain an 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 diphenol monomer, and 200 mmol of potassium carbonate to 650 mL of N-methylpyrrolidone, heat to 140°C in a nitrogen atmosphere, reflux with water for 2 h, then heat to 190°C, condense and reflux for 6 h, cool the solution, pour it into water, filter it with suction, 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, condense and reflux for 6 h, filter it with suction, wash the filter cake with water, and dry it to obtain carboxyl polyarylethersulfone.

[0022] (4) 5 kg of acrylonitrile-butadiene-styrene resin (brand name: Formosa Chemical Industry AE8200, the same below), 0.5 kg of carboxyl polyarylethersulfone, 40 g of AN-PS-GMA copolymer, 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. and water-cooled and pelletized to obtain a high-temperature resistant ABS material.

[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. and water-cooled and pelletized to obtain a high-temperature resistant ABS material.

[0025] Comparative Example 2:

[0026] (1) 5 kg of acrylonitrile-butadiene-styrene resin, 0.5 kg of carboxyl polyarylethersulfone (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. and water-cooled and pelletized to obtain a 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: ), 200 mmol potassium carbonate, heated to 140 ° C in a nitrogen atmosphere, refluxed with water for 2 hours, then heated to 190 ° C, condensed and refluxed for 6 hours, after cooling, poured the solution into water, filtered, washed the filter cake with ethanol, and dried to obtain polyarylethersulfone.

[0029] (2) 5 kg of acrylonitrile-butadiene-styrene resin, 0.5 kg of polyarylethersulfone, 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. and water-cooled and pelletized to obtain a 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: ), 200 mmol potassium carbonate, heated to 140 ° C in a nitrogen atmosphere, refluxed with water for 2 hours, then heated to 190 ° C, condensed and refluxed for 6 hours, poured the solution into water after cooling, filtered with suction, washed the filter cake with ethanol, added the product to 3.5 mol / L sodium hydroxide aqueous solution, heated to 90 ° C, condensed and refluxed for 6 hours, filtered with suction, washed the filter cake with water, and dried to obtain carboxyl polyarylethersulfone.

[0032] (2) 5 kg of acrylonitrile-butadiene-styrene resin, 0.5 kg of carboxyl polyarylethersulfone, 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. and water-cooled and pelletized to obtain a high-temperature resistant ABS material.

[0033] Embodiment 2:

[0034] (1) 0.12 g of sodium dodecylbenzene sulfonate, 0.09 g of tert-dodecyl mercaptan, 4 g of acrylonitrile, 5.8 g of styrene, and 0.5 g of glycidyl methacrylate were added to 40 mL of water, and after stirring, 0.52 g of azobisisobutyronitrile was added in a nitrogen atmosphere. The mixture was heated to 75° C. and reacted for 4 h. The mixture was then heated to 85° C. and reacted for 1 h. The mixture was cooled and filtered. The filter cake was washed with water and ethanol and dried to obtain an AN-PS-GMA copolymer.

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

[0036] (3) Add 400 mL of toluene, 100 mmol of 4,4'-dichlorodiphenyl sulfone, 60 mmol of hydroquinone, 40 mmol of ester diphenol monomer, and 220 mmol of potassium carbonate to 700 mL of N-methylpyrrolidone, heat to 140°C in a nitrogen atmosphere, reflux with water for 2 h, then heat to 190°C, condense and reflux for 6 h, cool the solution, pour it into water, filter it with suction, 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, condense and reflux for 6 h, filter it with suction, wash the filter cake with water, and dry it to obtain carboxyl polyarylethersulfone.

[0037] (4) 5 kg of acrylonitrile-butadiene-styrene resin, 1.2 kg of carboxyl polyarylethersulfone, 100 g of AN-PS-GMA copolymer, and 15 g of antioxidant 1010 were mixed in a mixer, and then melt-extruded in a twin-screw extruder at an extrusion temperature of 210° C. and water-cooled and pelletized to obtain a high-temperature resistant ABS material.

[0038] Embodiment 3:

[0039] (1) 400 mL of toluene, 100 mmol of 4,4'-dichlorodiphenyl sulfone, 50 mmol of hydroquinone, 50 mmol of ester diphenol monomer (prepared in the same manner as in Example 1), and 180 mmol of potassium carbonate were added to 700 mL of N-methylpyrrolidone, and the mixture was heated to 130° C. in a nitrogen atmosphere, refluxed with water for 3 h, and then heated to 180° C., condensed and refluxed for 8 h, and after cooling, the solution was poured into water, filtered, and the filter cake was washed with ethanol. The product was added to 1.2 L of a 3 mol / L sodium hydroxide aqueous solution, heated to 100° C., condensed and refluxed for 4 h, filtered, washed with water, and dried to obtain carboxyl polyarylethersulfone.

[0040] (2) 5 kg of acrylonitrile-butadiene-styrene resin, 2 kg of carboxyl polyarylethersulfone, 150 g of AN-PS-GMA copolymer (prepared in the same manner as in Example 1), and 20 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. and water-cooled and pelletized to obtain a high-temperature resistant ABS material.

[0041] The high temperature resistant ABS material was injected into a sample by an injection molding machine, and the tensile strength was tested according to the national standard GB / T 1040.1-2018. The impact strength was tested according to the national standard GB / T 1843-2008.

[0042] The specimens were placed in a heating box at 150°C for 48 h and then at room temperature for 6 h before testing the tensile strength and impact strength.

[0043] Table 1 ABS material mechanical properties test

[0044]

[0045] It can be seen from Example 1 and Comparative Example 1 that the ABS material of Example 1 has higher tensile strength and impact strength, and after high-temperature heat treatment, the retention rates of tensile strength and impact strength are relatively high, which are 90.72% (40.1 / 44.2) and 89.07% (28.35 / 31.83), respectively. This is mainly because carboxyl polyarylethersulfone and AN-PS-GMA copolymer are added. During the high-temperature melting process, the epoxy group of the AN-PS-GMA copolymer can react with the carboxyl group of the polyarylethersulfone. The AN-PS-GMA copolymer contains styrene and acrylonitrile structural units, and has good structural compatibility and compatibility with ABS resin, so that the AN-PS-GMA copolymer plays the role of a reactive compatibilizer, improves the compatibility between the carboxyl polyarylethersulfone and the ABS resin, and makes the polyarylethersulfone evenly dispersed in the ABS material matrix. The two form a homogeneous system, so that the ABS material exhibits higher tensile strength and impact strength, and the polyarylethersulfone itself has strong heat resistance, and at the same time, a heat-resistant terphenyl structure is introduced into the main chain of the molecule. Adding it to ABS resin is beneficial to improving the high temperature resistance of the material. After high temperature heat treatment, the material still has high tensile strength and impact strength.

[0046] Comparative Example 2 did not add AN-PS-GMA copolymer, resulting in poor compatibility between carboxyl polyarylethersulfone and ABS resin, and failure to improve the mechanical properties of the material, resulting in low tensile strength and impact strength.

[0047] In Comparative Example 3, [1,1':4',1"-terphenyl]-4,4"-diol is used as a raw material. The prepared polyarylethersulfone does not contain a carboxyl group and cannot react with the AN-PS-GMA copolymer. It cannot act as a compatibilizer and does not improve the compatibility of the polyarylethersulfone with the ABS resin, resulting in lower tensile strength and impact strength of the material.

[0048] Comparative Example 4 uses 3,5-dihydroxybenzoic acid methyl ester as a reactant, and the prepared carboxyl polyarylethersulfone has good compatibility with ABS resin under the solubilization effect of AN-PS-GMA copolymer, and the tensile strength and impact strength of the material are significantly improved. However, after high-temperature heat treatment, the retention rates of tensile strength and impact strength are low, only 88.03% (37.5 / 42.6) and 86.54% (27.85 / 32.18), which are lower than those in Example 1. This is mainly because the carboxyl polyarylethersulfone of Comparative Example 4 does not contain a heat-resistant terphenyl structure, resulting in the heat resistance of the carboxyl polyarylethersulfone being lower than that of the carboxyl polyarylethersulfone of Example 1. When added to ABS resin, the high temperature resistance of the material cannot be effectively improved.

[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 tested using a high resistance meter at a test temperature of 25°C and a relative humidity of 55%.

[0051] Table 2 ABS material surface resistivity test

[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] It can be seen from Example 1 and Comparative Example 1 that the surface water contact angle of the ABS material of Example 1 is lower and the hydrophilicity is good, which is conducive to forming a water molecule film on the surface, thereby reducing the surface resistivity and improving the antistatic performance. This is mainly because the side chain of the added carboxyl polyarylethersulfone contains a large number of carboxyl hydrophilic groups, and part of the carboxyl groups react with the epoxy groups of the AN-PS-GMA copolymer to generate hydrophilic hydroxyl groups. Significantly improves the surface hydrophilicity of ABS materials.

[0054] After adding carboxyl polyarylethersulfone to Comparative Example 2, the water contact angle of the ABS material is also low, which is beneficial to reducing the surface resistivity and improving the antistatic performance.

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

[0056] Comparative Example 4 adds carboxyl polyarylethersulfone, and the water contact angle and surface resistivity of the ABS material are lower, and the antistatic performance is better, but the water contact angle and surface resistivity are higher than those of Example 1. This is mainly because the ester-based diphenol monomer contains two ester groups, which can generate two carboxyl groups after hydrolysis, while 3,5-dihydroxybenzoic acid methyl ester contains only one ester group, which can only generate one carboxyl group after hydrolysis, resulting in the carboxyl content of the polyarylethersulfone of Comparative Example 4 being much lower than that of Example 1, and therefore the hydrophilic performance is lower than that of the polyarylethersulfone of the embodiment, resulting in the water contact angle of the ABS material of Comparative Example 4 being higher than that of Example 1, and therefore the surface resistivity is larger.

[0057] In Examples 2-3, at different dosages of carboxyl polyarylethersulfone and AN-PS-GMA copolymer, the ABS material exhibited good tensile strength, impact strength and high temperature resistance, and 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), toluene, 4,4'-dichlorodiphenyl sulfone, hydroquinone, and the structural formula are added to N-methylpyrrolidone. The ester diphenol monomer and potassium carbonate are heated to 130-140°C in a nitrogen atmosphere, refluxed with water for 2-3 hours, then heated to 180-190°C, condensed and refluxed for 6-8 hours, and after cooling, the solution is poured into water, filtered, and the filter cake is washed with ethanol. The product is added to a sodium hydroxide aqueous solution, heated to 90-100°C, condensed and refluxed for 4-6 hours, filtered, washed with water, and dried to obtain carboxyl polyarylethersulfone; Step (2), mixing acrylonitrile-butadiene-styrene resin, carboxyl polyarylethersulfone, AN-PS-GMA copolymer and antioxidant in a mixer, then melt-extrude in a twin-screw extruder, water-cooled and pelletized to obtain a high temperature resistant ABS material.

2. The method for preparing high temperature resistant ABS material according to claim 1, characterized in that: In the step (1), the molar ratio of 4,4'-dichlorodiphenyl sulfone, hydroquinone, ester-based diphenol monomer, and potassium carbonate is 100:(50-70):(30-50):(180-220).

3. The method for preparing high temperature resistant ABS material according to claim 2, characterized in that: The preparation method of the ester-based diphenol monomer comprises: adding 1,4-terephthaloboric acid, methyl 5-bromosalicylate and palladium acetate to 1,4-dioxane, adding potassium carbonate aqueous solution dropwise after stirring, heating to 80-90° C., reacting for 4-7 hours, rotary evaporation, filtering and washing with water, and separating the product by column chromatography to obtain the ester-based diphenol monomer.

4. The method for preparing high temperature resistant ABS material according to claim 3, characterized in that: The molar ratio of the 1,4-terephthalenediboric acid, methyl 5-bromosalicylate and palladium acetate is 1:(2-2.2):(0.008-0.01).

5. The method for preparing high temperature resistant ABS material according to claim 3, characterized in that: The molar 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 molar 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) includes antioxidant 1076 and antioxidant 1010.

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

9. The method for preparing a high temperature resistant ABS material according to claim 8, characterized in that: The preparation method of the AN-PS-GMA copolymer comprises: adding sodium dodecylbenzene sulfonate, tert-dodecyl mercaptan, acrylonitrile, styrene and glycidyl methacrylate in a mass ratio of (25-40):(55-73):(2-5) into water, stirring, adding azobisisobutyronitrile in a nitrogen atmosphere, heating to 70-75° C., reacting for 4-5 hours, then heating to 85-90° C., reacting for 0.5-1 hour, cooling, filtering, washing and drying to obtain the AN-PS-GMA copolymer.

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