Abs heat resistant modifier, intermediate and high temperature resistant abs material and preparation method

Abstract

The present application relates to ABS heat-resistant modifier, intermediate and high-temperature-resistant ABS material and preparation method, belong to high polymer material technical field.The technical problem solved by the present application is to provide ABS heat-resistant modifier intermediate with new molecular structure, ABS heat-resistant modifier and high-temperature-resistant ABS material.The intermediate of the present application ABS heat-resistant modifier is shown in formula I.The synthesis method of the present application ABS heat-resistant modifier is simple, simple and controllable, and the cost is low.The intermediate N-dibenzofuranyl maleimide has simple synthesis process and strong stability.The prepared styrene-N-dibenzofuranyl maleimide-maleic anhydride can be used as heat-resistant modifier, and after being blended with ABS resin, the mechanical properties and high-temperature-resistant properties of ABS resin are improved.

Description

Technical Field

[0001] This invention relates to ABS heat-resistant modifiers, intermediates, high-temperature resistant ABS materials, and preparation methods, belonging to the field of polymer materials technology. Background Technology

[0002] With continuous technological innovation, the application of plastic products is becoming increasingly widespread, and their demand is also growing, with increasingly higher requirements for polymer materials. Based on their properties and uses, plastics can be divided into three main categories: general-purpose plastics, engineering plastics, and specialty plastics. Compared to engineering and specialty plastics, which possess high strength, high modulus, and high heat resistance, many general-purpose materials suffer from low heat resistance, potentially experiencing heat deformation, embrittlement, degradation, or even combustion under high-temperature conditions, limiting their application in such environments. Among these, acrylonitrile-butadiene-styrene copolymer (ABS), one of the five major general-purpose plastics, possesses excellent comprehensive properties, such as impact resistance, rigidity, and processability, and is therefore widely used in many fields. However, traditional ABS materials are prone to heat deformation and color changes at high temperatures, limiting their use in some high-temperature applications. Therefore, developing heat-resistant ABS materials is essential to meet the demands of high-temperature environments. Heat-resistant ABS materials can maintain their physical properties and appearance stability under high-temperature conditions, exhibiting a low coefficient of thermal expansion and excellent high-temperature resistance. This material has broad application prospects in high-temperature environments such as automotive engine compartments, electronic device heat dissipation modules, and water heater components. By adjusting the chemical formulation and processing technology of ABS materials, their heat resistance can be improved, enabling the development of heat-resistant ABS materials. For example, introducing high-temperature resistant additives, improving the material's crystallinity, and optimizing the filling and reinforcement systems can all enhance the heat resistance of ABS materials. This will provide design engineers and manufacturers in related fields with more options and drive development and innovation in high-temperature applications.

[0003] However, most existing ABS heat-resistant modifiers on the market are styrene-N-phenylmaleimide-maleic anhydride terpolymers, which can form amorphous regions in the resin, hindering the movement of resin molecular chains and the crystallization process. This amorphous formation gives ABS resin better melt stability and thermal stability at high temperatures, slows down thermal degradation and plasticization processes, and improves heat resistance. However, the synthesis method of this copolymer is complex and costly, and its raw material, N-phenylmaleimide, requires purification of aniline during the synthesis stage. Furthermore, aniline is easily oxidized and unstable, and is not resistant to high temperatures.

[0004] Chinese invention patent application CN202111446233.0 discloses a method to significantly improve the heat resistance of ABS materials by adding a styrene-N-phenylmaleimide-maleic anhydride terpolymer in synergy with two heat-resistant synergists. However, this method involves a wide variety of heat-resistant modifiers and a complex process, making it unsuitable for large-scale production. Summary of the Invention

[0005] To address the above deficiencies, the first technical problem solved by this invention is to provide an intermediate for ABS heat-resistant modifiers with a novel molecular structure.

[0006] The ABS heat-resistant modifier intermediate of this invention has the structural formula shown in Formula I:

[0007]

[0008] The second technical problem solved by this invention is to provide an ABS heat-resistant modifier.

[0009] The ABS heat-resistant modifier of this invention has the structural formula shown in Formula II:

[0010]

[0011] Where x is an integer between 10 and 50, y is an integer between 20 and 60, and z is an integer between 150 and 300.

[0012] Preferably, x is an integer between 35 and 38, y is an integer between 38 and 41, and z is an integer between 219 and 238.

[0013] In some specific embodiments, the number average molecular weight of the ABS heat-resistant modifier is 35,000 to 38,000.

[0014] The present invention also provides a high-temperature resistant ABS material.

[0015] The present invention relates to a high-temperature resistant ABS material comprising an acrylonitrile-butadiene-styrene copolymer, a styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer, and an antioxidant, wherein the styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer is the ABS heat-resistant modifier described in the present invention.

[0016] In one specific embodiment of the present invention, the weight ratio of acrylonitrile-butadiene-styrene copolymer to styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer is 60-90%:10-40%, and the mass of antioxidant is 0.05-5% of the mass of high-temperature resistant ABS material.

[0017] In one specific embodiment of the present invention, the antioxidants are antioxidant 168 and antioxidant 1010, preferably antioxidant 168 and antioxidant 1010 each account for 0.2% of the mass of the high-temperature resistant ABS material.

[0018] The present invention also provides a method for preparing the ABS heat-resistant modifier described herein.

[0019] The present invention provides a method for preparing high-temperature resistant ABS material, comprising the following steps: 1) Preparing an intermediate for ABS heat-resistant modification: Weigh maleic anhydride, furanamine, xylene, solvent 1, p-toluenesulfonic acid, and polymerization inhibitor; under a temperature range of 30-50°C and a protective atmosphere, add half the measured amount of xylene, solvent 1, polymerization inhibitor, and maleic anhydride to a reactor, stir and mix well, and mix the other half the measured amount of xylene and furanamine to obtain a mixture, add the mixture dropwise to the reactor within 1 hour, react for 0.5-2 hours, add p-toluenesulfonic acid and heat to 120-140°C to react for 2-5 hours; cool down and remove toluene by vacuum, then cool down to below 30°C, add a mixture of ethanol and water, precipitate, and take the precipitate, which is the intermediate for ABS heat-resistant modification;

[0020] 2) Preparation of ABS heat-resistant modifier: Styrene, ABS heat-resistant modifier intermediate, maleic anhydride, solvent 2 and initiator are mixed and reacted for 4-6 hours in a temperature range of 80-100℃ and under a protective atmosphere to obtain the product, namely ABS heat-resistant modifier (styrene-N-dibenzofuranylmaleimide-maleic anhydride).

[0021] In one specific embodiment, in step 1), the polymerization inhibitor is one of hydroquinone, resorcinol, catechol, pyrogallol, phenol, tert-butylphenol, and catechol disulfonic acid; the furanamine is at least one of 2-dibenzofuranamine, 3-dibenzofuranamine, 4-dibenzofuranamine, (2-phenyl-1-benzofuran-5-yl)amine, and 1-benzofuran-5-amine; and the solvent 1 is N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0022] In step 2), solvent 2 is at least one of toluene, xylene, cyclohexanone, butanone, acetone, N,N-dimethylformamide, and N-methylpyrrolidone; and initiator is at least one of tert-butyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, and azobisisobutyronitrile.

[0023] The preferred polymerization inhibitor is tert-butylphenol; the furanamine is 2-dibenzofuranamine; and the solvent 1 is N,N-dimethylacetamide.

[0024] The preferred solvent 2 is xylene, and the initiator is tert-butyl peroxide.

[0025] In one embodiment of the present invention, in step 1), the molar ratio of maleic anhydride to furanylamine is 1:1.1 to 1.3; the mass ratio of xylene to solvent 1 is 9 to 11:1, and the amount of xylene used is 4 to 6 times the total mass of maleic anhydride and furanylamine; the amount of polymerization inhibitor used is 2 to 5% of the mass of furanylamine; the amount of p-toluenesulfonic acid used is 5 to 10% of the mass of furanylamine; preferably, the molar ratio of maleic anhydride to furanylamine is 1:1.2; the mass ratio of xylene to solvent 1 is 10:1, and the amount of xylene used is 5 times the total mass of maleic anhydride and furanylamine; the amount of polymerization inhibitor used is 3% of the mass of furanylamine; and the amount of p-toluenesulfonic acid used is 8% of the mass of furanylamine.

[0026] In step 2), the mass ratio of styrene, ABS heat-resistant modifier intermediate, and maleic anhydride is 67-71%:28-32%:1%; the amount of initiator is 0.8-1.2% of the total mass of the materials in step 2), and the amount of solvent 2 is 1.5-3 times the total mass of the materials in step 2); preferably, the mass ratio of styrene, ABS heat-resistant modifier intermediate, and maleic anhydride is 69%:30%:1%; the amount of initiator is 1% of the total mass of the materials in step 2 excluding the solvent, and the amount of solvent 2 is twice the total mass of the materials in step 2 excluding the solvent.

[0027] This invention also provides a method for preparing high-temperature resistant ABS materials.

[0028] The present invention discloses a method for preparing high-temperature resistant ABS material, comprising the following steps: drying acrylonitrile-butadiene-styrene copolymer and ABS heat-resistant modifier, mixing with antioxidant, extruding by twin screw extrusion, cooling and granulating to obtain high-temperature resistant ABS material.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] 1) The synthesis method of the ABS heat-resistant modifier of the present invention is simple, the experiment is simple and controllable, and the cost is low.

[0031] 2) The intermediate N-dibenzofuranylmaleimide of the heat-resistant modifier of the present invention has a simple synthesis process and strong stability.

[0032] 3) The present invention prepares styrene-N-dibenzofuranylmaleimide-maleic anhydride, which can be used as a heat-resistant modifier. When blended with ABS resin, it improves the mechanical properties and high-temperature resistance of ABS resin. Attached Figure Description

[0033] Figure 1 The image shows the 1H NMR spectrum of N-dibenzofuranylmaleimide prepared in Example 1 of this invention.

[0034] Figure 2The image shows the 1H NMR spectrum of styrene-N-dibenzofuranylmaleimide-maleic anhydride prepared in Example 1 of this invention. Detailed Implementation

[0035] The ABS heat-resistant modifier intermediate of this invention has the structural formula shown in Formula I:

[0036]

[0037] The ABS heat-resistant modifier intermediate of this invention can be synthesized using conventional methods. In one specific embodiment of this invention, the synthesis route is as follows:

[0038]

[0039] Specifically, the synthesis method is as follows: Weigh maleic anhydride, furanylamine, xylene, solvent 1, p-toluenesulfonic acid, and polymerization inhibitor; under a temperature range of 30-50℃ and a protective atmosphere, add half of the measured amount of xylene, solvent 1, polymerization inhibitor, and maleic anhydride to the reactor, stir and mix well, and mix the other half of the measured amount of xylene and furanylamine to obtain a mixed solution. Add the mixed solution dropwise to the reactor within 1 hour, react for 0.5-2 hours, add p-toluenesulfonic acid and heat to 120-140℃ to react for 2-5 hours; cool down and remove toluene under vacuum, then cool down to below 30℃, add a mixture of ethanol and water, precipitate, and take the precipitate, which is the intermediate of ABS heat-resistant modifier (i.e., N-dibenzofuranylmaleimide).

[0040] In one specific embodiment, the polymerization inhibitor is one of hydroquinone, resorcinol, catechol, pyrogallol, phenol, tert-butylphenol, and catechol disulfonic acid; the furanamine is at least one of 2-dibenzofuranamine, 3-dibenzofuranamine, 4-dibenzofuranamine, (2-phenyl-1-benzofuran-5-yl)amine, and 1-benzofuran-5-amine; and the solvent 1 is N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), and N-methylpyrrolidone (NMP).

[0041] Preferably, the polymerization inhibitor is tert-butylphenol; the furanamine is 2-dibenzofuranamine; and the solvent is N,N-dimethylacetamide (DMAC).

[0042] In one specific embodiment, the molar ratio of maleic anhydride to furanylamine is 1:1.1 to 1.3; the mass ratio of xylene to solvent 1 is 9 to 11:1, and the amount of xylene used is 4 to 6 times the total mass of maleic anhydride and furanylamine; the amount of polymerization inhibitor is 2 to 5% of the mass of furanylamine; and the amount of p-toluenesulfonic acid is 5 to 10% of the mass of furanylamine. Preferably, the molar ratio of maleic anhydride to furanylamine is 1:1.2; the mass ratio of xylene to solvent 1 is 10:1, and the amount of xylene used is 5 times the total mass of maleic anhydride and furanylamine; the amount of polymerization inhibitor is 3% of the mass of furanylamine; and the amount of p-toluenesulfonic acid is 8% of the mass of furanylamine.

[0043] The ABS heat-resistant modifier of this invention has the structural formula shown in Formula II:

[0044]

[0045] Where x is an integer between 10 and 50, y is an integer between 20 and 60, and z is an integer between 150 and 300.

[0046] Preferably, x is an integer between 35 and 38, y is an integer between 38 and 41, and z is an integer between 219 and 238.

[0047] In some specific embodiments, the number average molecular weight of the ABS heat-resistant modifier is 35,000 to 38,000.

[0048] The ABS heat-resistant modifier of this invention can be synthesized using the following synthetic route:

[0049]

[0050] In one specific embodiment, the method for synthesizing the ABS heat-resistant modifier is as follows:

[0051] Styrene, ABS heat-resistant modifier intermediate, maleic anhydride, solvent 2, and initiator are mixed and reacted for 4-6 hours under a temperature range of 80-100℃ and a protective atmosphere to obtain the product, namely ABS heat-resistant modifier (also called styrene-N-dibenzofuranylmaleimide-maleic anhydride).

[0052] In one specific embodiment of the present invention, the solvent 2 is at least one selected from toluene, xylene, cyclohexanone, butanone, acetone, N,N-dimethylformamide, and N-methylpyrrolidone; the initiator is at least one selected from tert-butyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, and azobisisobutyronitrile. Preferably, the solvent 2 is xylene, and the initiator is tert-butyl peroxide.

[0053] In one specific embodiment of the present invention, the mass ratio of styrene, ABS heat-resistant modifier intermediate, and maleic anhydride is 67-71%:28-32%:1%; the amount of initiator is 0.8-1.2% of the total mass of the materials, and the amount of solvent 2 is 1.5-3 times the total mass of the materials. Preferably, the mass ratio of styrene, ABS heat-resistant modifier intermediate, and maleic anhydride is 69%:30%:1%; the amount of initiator is 1% of the total mass of the materials (excluding solvent), and the amount of solvent 2 is twice the total mass of the materials (excluding solvent).

[0054] The present invention relates to a high-temperature resistant ABS material comprising an acrylonitrile-butadiene-styrene copolymer, a styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer, and an antioxidant, wherein the styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer is the ABS heat-resistant modifier described in the present invention.

[0055] In one specific embodiment of the present invention, the weight ratio of acrylonitrile-butadiene-styrene copolymer to styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer is 60-90%:10-40%, and the mass of antioxidant is 0.05-5% of the mass of high-temperature resistant ABS material.

[0056] In one specific embodiment of the present invention, the antioxidants are antioxidant 168 and antioxidant 1010, preferably antioxidant 168 and antioxidant 1010 each account for 0.2% of the mass of the high-temperature resistant ABS material.

[0057] Among them, antioxidant 1010 has the chemical name: pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; antioxidant 168 has the chemical name: tris[2,4-di-tert-butylphenyl]phosphite.

[0058] The present invention discloses a method for preparing high-temperature resistant ABS material, comprising the following steps: drying acrylonitrile-butadiene-styrene copolymer and ABS heat-resistant modifier, mixing with antioxidant, extruding by twin screw extrusion, cooling and granulating to obtain high-temperature resistant ABS material.

[0059] In one specific embodiment, the twin-screw extrusion uses a twin-screw extruder, which is a co-rotating parallel twin-screw extruder (SHJ-20B) with a screw speed of 250-330 rpm and a temperature range of 270-280°C.

[0060] Specifically, the preparation method of the high-temperature resistant ABS material of the present invention is as follows:

[0061] 1) Weigh out a certain proportion of maleic anhydride, 2-dibenzofuranamine, xylene, solvent, p-toluenesulfonic acid, and polymerization inhibitor. Under a nitrogen atmosphere and within a temperature range of 40°C, add half the amount of xylene, solvent, polymerization inhibitor, and maleic anhydride to a four-necked flask equipped with a stirrer, spherical condenser, water separator, and constant pressure separating funnel. Add half the amount of the toluene and 2-dibenzofuranamine mixture dropwise to the reaction system over 1 hour. After the addition is complete, continue the reaction for 1 hour. Then add p-toluenesulfonic acid and raise the temperature to 130°C to react for 3 hours. Next, set the oil temperature to 90°C and vacuum the system to remove toluene from the reaction system. Finally, cool the reaction system to 30°C and add a certain proportion of a mixture of ethanol and water. N-dibenzofuranylmaleimide, denoted as N-FMI, precipitates out.

[0062] 2) Under a nitrogen atmosphere and at a temperature range of 80-100℃, a certain proportion of styrene, N-dibenzofuranylmaleimide, maleic anhydride, solvent, and initiator were added to a four-necked flask equipped with a stirrer and a spherical condenser. The reaction was continued for 5 hours to obtain the product styrene-N-dibenzofuranylmaleimide-maleic anhydride.

[0063] 3) First, acrylonitrile-butadiene-styrene copolymer (ABS) and styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer are dried at 100-110℃ for 3-4 hours. Then, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer, antioxidant 1 and antioxidant 2 are mixed evenly using a high-speed mixer. Finally, the mixture is melt-shear blended through a twin-screw extruder, cooled and granulated to obtain high-temperature resistant ABS.

[0064] This invention utilizes 2-dibenzofuranamine to synthesize a novel maleimide structure—N-dibenzofuranylmaleimide—and then uses this novel N-dibenzofuranylmaleimide to synthesize a styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer. Finally, the styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer is introduced into ABS and mechanically blended using a twin-screw extruder, thereby improving the heat resistance of ABS. Compared to N-phenylmaleimide synthesized from aniline, the synthesis process of N-dibenzofuranylmaleimide using 2-dibenzofuranamine is simpler, and the raw materials are more stable. The synthesis of N-phenylmaleimide requires purification of aniline, and aniline is easily oxidized, unstable, and not heat-resistant; the synthesis process of N-dibenzofuranylmaleimide is simple, requiring no pretreatment of the monomer, and 2-dibenzofuranamine possesses oxidation stability and heat resistance. When styrene and maleic anhydride are combined to form a terpolymer as an ABS modifier, the high-temperature resistant ABS obtained by introducing the styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer into ABS exhibits superior oxidative stability, mechanical properties, and heat resistance.

[0065] The specific embodiments of the present invention will be further described below with reference to examples, but the present invention is not limited to the scope of the examples described. The acrylonitrile-butadiene-styrene copolymer (ABS) used in the examples is commercially available, purchased from Jilin Petrochemical Company, model 0215A, with a melt index of 20 g / 10 min.

[0066] Example 1

[0067] Weigh out a certain proportion of maleic anhydride, 2-dibenzofuranamine, xylene, N,N-dimethylacetamide (DMAC), p-toluenesulfonic acid, and tert-butylphenol. The molar ratio of maleic anhydride to 2-dibenzofuranamine is 1:1.2; the mass ratio of xylene to N,N-dimethylacetamide (DMAC) is 10:1, and the amount of xylene used is 5 times the total mass of maleic anhydride and 2-dibenzofuranamine; the amount of polymerization inhibitor is 3% of the mass of furanamine; and the amount of p-toluenesulfonic acid is 8% of the mass of furanamine. Under a nitrogen atmosphere and within a temperature range of 40°C, half the measured amount of xylene, solvent, polymerization inhibitor, and maleic anhydride were added to a four-necked flask equipped with a stirrer, spherical condenser, water separator, and constant-pressure separatory funnel. Half the measured amount of a mixture of toluene and 2-dibenzofuranamine was then added dropwise to the reaction system over 1 hour. After the addition was complete, the reaction continued for 1 hour. Then, p-toluenesulfonic acid was added, and the temperature was raised to 130°C for 3 hours. Next, the oil temperature was set to 90°C, and the system was evacuated to remove toluene from the reaction system. Finally, the reaction system was cooled to 30°C, and a mixture of ethanol and water was added, precipitating N-dibenzofuranylmaleimide, denoted as N-FMI. Its NMR spectrum is shown below. Figure 1 As shown.

[0068] Under a nitrogen atmosphere and at a temperature range of 80°C, the following components were added to a four-necked flask equipped with a stirrer and a spherical condenser: 69% styrene (St), 30% N-dibenzofuranylmaleimide, and 1% maleic anhydride. The initiator was 1% of the total mass of the materials, and the solvent was twice the total mass. The reaction was continued for 5 hours to obtain the product styrene-N-dibenzofuranylmaleimide-maleic anhydride. The molecular weight (Mn) was determined to be 37824, which is within the range of 35000–38000. Its NMR spectrum is shown below. Figure 2 As shown.

[0069] First, acrylonitrile-butadiene-styrene copolymer (ABS) and styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer are dried at 100-110℃ for 3-4 hours. Then, the materials are weighed according to a certain proportion, with acrylonitrile-butadiene-styrene copolymer (ABS) accounting for 90% by mass, styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer accounting for 10% by mass, and antioxidant 1 and antioxidant 2 each accounting for 0.2% by mass of the total blending raw materials. After being mixed evenly using a high-speed mixer, the mixture is finally melt-shear blended through a twin-screw extruder, cooled and granulated to obtain high-temperature resistant ABS, denoted as HR-ABS-1.

[0070] Example 2

[0071] The synthesis of N-dibenzofuranylmaleimide (N-FMI) and styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer is the same as in Example 1.

[0072] First, acrylonitrile-butadiene-styrene copolymer (ABS) and styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer are dried at 100-110℃ for 3-4 hours. Then, the materials are weighed according to a certain proportion, with acrylonitrile-butadiene-styrene copolymer (ABS) accounting for 80% by mass, styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer accounting for 20% by mass, and antioxidant 1 and antioxidant 2 each accounting for 0.2% by mass of the total blending raw materials. After being mixed evenly using a high-speed mixer, the mixture is finally melt-shear blended through a twin-screw extruder, cooled and granulated to obtain high-temperature resistant ABS, denoted as HR-ABS-2.

[0073] Example 3

[0074] The synthesis of N-dibenzofuranylmaleimide (N-FMI) and styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer is the same as in Example 1.

[0075] First, acrylonitrile-butadiene-styrene copolymer (ABS) and styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer are dried at 100-110℃ for 3-4 hours. Then, the materials are weighed according to a certain ratio, with acrylonitrile-butadiene-styrene copolymer (ABS) accounting for 70% by mass, styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer accounting for 30% by mass, and antioxidant 1 and antioxidant 2 each accounting for 0.2% by mass of the total blending raw materials. After being mixed evenly using a high-speed mixer, the mixture is finally melt-shear blended through a twin-screw extruder, cooled and granulated to obtain high-temperature resistant ABS, denoted as HR-ABS-3.

[0076] Example 4

[0077] The synthesis of N-dibenzofuranylmaleimide (N-FMI) and styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer is the same as in Example 1.

[0078] First, acrylonitrile-butadiene-styrene copolymer (ABS) and styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer are dried at 100-110℃ for 3-4 hours. Then, the materials are weighed according to a certain proportion, with acrylonitrile-butadiene-styrene copolymer (ABS) accounting for 60% by mass, styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer accounting for 40% by mass, and antioxidant 1 and antioxidant 2 each accounting for 0.2% by mass of the total blending raw materials. After being mixed evenly using a high-speed mixer, the mixture is finally melt-shear blended through a twin-screw extruder, cooled and granulated to obtain high-temperature resistant ABS, denoted as HR-ABS-4.

[0079] Comparative Example 1

[0080] First, acrylonitrile-butadiene-styrene copolymer (ABS) and styrene-N-phenylmaleimide-maleic anhydride terpolymer are dried at 100-110℃ for 3-4 hours. Then, the materials are weighed according to a certain proportion, with acrylonitrile-butadiene-styrene copolymer (ABS) accounting for 60% by mass, styrene-N-phenylmaleimide-maleic anhydride terpolymer (N-FMI) accounting for 40% by mass, and antioxidant 1 and antioxidant 2 each accounting for 0.2% by mass of the total blending raw materials. After being mixed evenly using a high-speed mixer, the mixture is finally melt-shear blended through a twin-screw extruder, cooled and granulated to obtain high-temperature resistant ABS, denoted as D-ABS-1.

[0081] Comparative Example 2

[0082] The synthesis of N-dibenzofuranylmaleimide (N-FMI) and styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer is the same as in Example 1.

[0083] First, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-N-phenylmaleimide-maleic anhydride terpolymer, and styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer are dried at 100-110℃ for 3-4 hours. Then, the materials are weighed according to a certain proportion, with acrylonitrile-butadiene-styrene copolymer (ABS) accounting for 60% by mass, styrene-N-phenylmaleimide-maleic anhydride terpolymer accounting for 20% by mass, styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer accounting for 20% by mass, and antioxidant 1 and antioxidant 2 each accounting for 0.2% by mass of the total blending raw materials. After being mixed evenly using a high-speed mixer, the mixture is finally melt-shear blended through a twin-screw extruder, cooled and granulated to obtain high-temperature resistant ABS, denoted as D-ABS-2.

[0084] The mechanical properties and heat distortion temperatures of Examples 1-4 and Comparative Examples 1-2 were measured, and the results are shown in Table 1.

[0085] Table 1

[0086]

[0087]

[0088] As can be seen from Table 1, the styrene-N-dibenzofuranylmaleimide-maleic anhydride prepared by this invention improves the mechanical properties and high-temperature resistance of ABS resin after being blended with ABS resin.

Claims

1. An intermediate for ABS heat-resistant modifier, characterized in that, Its structural formula is shown in Formula I:

2. An ABS heat-resistant modifier, characterized in that, Its structural formula is shown in Formula II: Where x is an integer between 10 and 50, y is an integer between 20 and 60, and z is an integer between 150 and 300.

3. The ABS heat-resistant modifier according to claim 1, characterized in that: x is an integer between 35 and 38, y is an integer between 38 and 41, and z is an integer between 219 and 238.

4. The ABS heat-resistant modifier according to claim 1, characterized in that: Its number-average molecular weight is 35,000 to 38,000.

5. High-temperature resistant ABS material, characterized in that: It includes acrylonitrile-butadiene-styrene copolymer, styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer and antioxidant, wherein the styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer is the ABS heat-resistant modifier according to any one of claims 2 to 4.

6. The high-temperature resistant ABS material according to claim 5, characterized in that: The weight ratio of acrylonitrile-butadiene-styrene copolymer to styrene-N-dibenzofuranylmaleimide-maleic anhydride terpolymer is 60-90%:10-40%, and the mass of antioxidant is 0.05-5% of the mass of high-temperature resistant ABS material.

7. The high-temperature resistant ABS material according to claim 5, characterized in that: The antioxidants are antioxidant 168 and antioxidant 1010, and antioxidant 168 and antioxidant 1010 each account for 0.2% of the mass of the high-temperature resistant ABS material.

8. The method for preparing the ABS heat-resistant modifier according to any one of claims 2 to 4, characterized in that, Includes the following steps: 1) Preparation of ABS heat-resistant modifier intermediate: Weigh maleic anhydride, furanamine, xylene, solvent 1, p-toluenesulfonic acid and polymerization inhibitor; under a temperature range of 30-50℃ and a protective atmosphere, add half of the measured amount of xylene, solvent 1, polymerization inhibitor and maleic anhydride to the reactor, stir and mix well, and mix the other half of the measured amount of xylene and furanamine to obtain a mixture. Add the mixture dropwise to the reactor within 1 hour, react for 0.5-2 hours, add p-toluenesulfonic acid and heat to 120-140℃ to react for 2-5 hours; cool down and remove toluene by vacuum, then cool down to below 30℃, add a mixture of ethanol and water, precipitate, and take the precipitate, which is the ABS heat-resistant modifier intermediate; 2) Preparation of ABS heat-resistant modifier: Styrene, ABS heat-resistant modifier intermediate, maleic anhydride, solvent 2 and initiator are mixed and reacted for 4-6 hours in a temperature range of 80-100℃ and under a protective atmosphere to obtain the product, namely ABS heat-resistant modifier (styrene-N-dibenzofuranylmaleimide-maleic anhydride).

9. The method for preparing the ABS heat-resistant modifier according to claim 8, characterized in that: In step 1), the polymerization inhibitor is one of hydroquinone, resorcinol, catechol, pyrogallol, phenol, tert-butylphenol, and phenol disulfonic acid; the furanamine is at least one of 2-dibenzofuranamine, 3-dibenzofuranamine, 4-dibenzofuranamine, (2-phenyl-1-benzofuran-5-yl)amine, and 1-benzofuran-5-amine; and the solvent 1 is N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. In step 2), solvent 2 is at least one of toluene, xylene, cyclohexanone, butanone, acetone, N,N-dimethylformamide, and N-methylpyrrolidone; and initiator is at least one of tert-butyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, and azobisisobutyronitrile.

10. The method for preparing the ABS heat-resistant modifier according to claim 9, characterized in that: The polymerization inhibitor is tert-butylphenol; the furanamine is 2-dibenzofuranamine; and solvent 1 is N,N-dimethylacetamide. Solvent 2 is xylene, and the initiator is tert-butyl peroxide.

11. The method for preparing the ABS heat-resistant modifier according to claim 8, characterized in that: In step 1), the molar ratio of maleic anhydride to furanylamine is 1:1.1 to 1.3; the mass ratio of xylene to solvent 1 is 9 to 11:1, and the amount of xylene used is 4 to 6 times the total mass of maleic anhydride and furanylamine; the amount of polymerization inhibitor used is 2 to 5% of the mass of furanylamine; and the amount of p-toluenesulfonic acid used is 5 to 10% of the mass of furanylamine. In step 2), the mass ratio of styrene, ABS heat-resistant modifier intermediate and maleic anhydride is 67-71%: 28-32%: 1%; the amount of initiator is 0.8-1.2% of the total mass of the materials in step 2), and the amount of solvent 2 is 1.5-3 times the total mass of the materials in step 2).

12. The method for preparing the ABS heat-resistant modifier according to claim 11, characterized in that: In step 1), the molar ratio of maleic anhydride to furanylamine is 1:1.2; the mass ratio of xylene to solvent 1 is 10:1, and the amount of xylene used is 5 times the total mass of maleic anhydride and furanylamine; the amount of polymerization inhibitor used is 3% of the mass of furanylamine; and the amount of p-toluenesulfonic acid used is 8% of the mass of furanylamine. In step 2), the mass ratio of styrene, ABS heat-resistant modifier intermediate and maleic anhydride is 69%:30%:1%; the amount of initiator is 1% of the total mass of materials excluding solvent in step 2), and the amount of solvent 2 is twice the total mass of materials excluding solvent in step 2).

13. The method for preparing the high-temperature resistant ABS material according to any one of claims 5 to 7, characterized in that: Includes the following steps: After drying the acrylonitrile-butadiene-styrene copolymer and the ABS heat-resistant modifier, they were mixed with an antioxidant, extruded by a twin-screw extruder, cooled and granulated to obtain a high-temperature resistant ABS material.

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