Maleimide high-heat-resistance impact-resistance modifier and preparation method thereof

Abstract

The invention relates to a maleimide high-heat-resistance and impact-resistance modifier and a preparation method thereof, and belongs to the technical field of high polymer materials. The structure of the maleimide high-heat-resistance impact-resistance modifier is shown as a formula I, wherein R1 is a naphthalene ring, a tetrahydronaphthalene ring, a benzene ring or cyclohexyl, and R is H, Cl, F, Br, methyl, phenyl or nitro; the range of x1 is 150-250, the range of x2 is 20-60, the range of y is 25-110, and the range of z is 180-300. The ethylene-N-(1-naphthyl) maleimide-butadiene-maleic anhydride quadripolymer prepared by the invention can be used as a heat-resistant and impact-resistant modifier of materials such as ABS (Acrylonitrile Butadiene Styrene) resin and ASA (Acrylonitrile Styrene Acrylonitrile Butadiene Styrene) resin, and can also be used as a compatilizer and a heat-resistant modifier of ABS / engineering plastic alloy, and the impact resistance and the heat resistance are good at the same time. The one-kettle two-step method is simple in process, and the cost is reduced. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a maleimide-based high heat-resistant and impact-resistant modifier and a preparation method thereof, belonging to the technical field of polymer materials. Background Art

[0002] With the development of science and technology and the times, the applications of the plastic industry cover all aspects of human life and production. Among them, general plastics (PE, PP, PVC, PS, and ABS) are widely used in agriculture, light industry, textiles, electronic appliances, machinery, building materials, packaging, transportation and other fields due to their large output, wide uses, good formability, low price and other characteristics. However, compared with engineering plastics, general plastics have disadvantages such as low mechanical strength and service temperature, which limit their scope of use. Therefore, modifying general plastics to prepare high-performance general plastics has now become a popular direction in the industry and a common method to expand the application fields of general plastics. Among them, acrylonitrile-butadiene-styrene copolymer (ABS) is widely used because of its excellent electrical properties, wear resistance, dimensional stability, chemical resistance, surface gloss, and easy processing and molding. However, it has defects such as poor weather resistance, poor heat resistance, and flammability. Among them, poor heat resistance is the main problem restricting its application. Therefore, heat-resistant modification of ABS has become a hot topic and norm in the industry. Therefore, adding heat-resistant modifiers to improve the heat resistance of ABS has become an important research direction in the field of plastic modification.

[0003] With the development of the global economy and scientific and technological progress, the demand for high-performance materials is increasing continuously, and the market for heat-resistant ABS modifiers presents broad development prospects. Especially driven by the growth of automotive lightweighting, miniaturization of electronic products and the demand for high-temperature resistant materials, the market demand for heat-resistant ABS modifiers will continue to grow. At present, the mainstream ABS heat-resistant modifiers in the market are N-phenyl maleimide-based heat-resistant modifiers. These modifiers expand their application fields by increasing the heat distortion temperature and heat resistance stability of ABS. In addition, with the in-depth research and the maturity of technology, the cost of heat-resistant ABS modifiers is expected to be further reduced, which will help their application and promotion in more fields.

[0004] However, there are still some problems in the existing technology that need to be solved urgently. For example: In the invention patent CN102282183A, styrene and maleic anhydride are used as monomers to first synthesize a styrene-maleic anhydride copolymer, and then aniline is introduced for imidization reaction to prepare a maleimide copolymer. The prepared maleimide copolymer has the characteristic of improving heat resistance, but due to the special molecular structure of this modifier, there are problems such as relatively large rigidity, which has an impact on the impact performance of the prepared heat-resistant material. The styrene-N-dibenzofuranyl maleimide-maleic anhydride terpolymer disclosed in CN117143085A improves heat resistance, but the improvement of impact resistance is limited. It can be seen that the existing methods have a single function, and most of the modifiers focus on single properties such as heat resistance or flame retardancy, and it is difficult to balance impact resistance and heat resistance.

[0005] The quaternary copolymer of CN118126241A needs to introduce a flame retardant monomer, and the synthesis steps are cumbersome and the cost is relatively high.

[0006] Based on the above deficiencies of the existing technology, the present invention aims to provide a maleimide-based high heat-resistant and impact-resistant modifier to solve the problems existing in the existing technology and meet the market demand for high-performance ABS materials. Summary of the Invention

[0007] The first object of the present invention is to provide a maleimide-based high heat-resistant and impact-resistant modifier.

[0008] To achieve the first object of the present invention, the structure of the maleimide-based high heat-resistant and impact-resistant modifier of the present invention is shown in Formula I:

[0009]

[0010] Wherein R1 is a naphthalene ring, a tetrahydronaphthalene ring, a benzene ring or a cyclohexyl group, and R is H, Cl, F, Br, a methyl group, a phenyl group or a nitro group;

[0011] The range of x1 is 150-250, the range of x2 is 20-60, the range of y is 25-110, and the range of z is 180-300.

[0012] In a specific embodiment, R1 is 1-aminonaphthalene, 2-aminonaphthalene, 1-aminotetrahydronaphthalene, 3-cyclohexylaniline or 4-cyclohexylaniline;

[0013] Preferably, the maleimide-based high heat-resistant and impact-resistant modifier is a styrene-N-(1-naphthyl) maleimide-butadiene-maleic anhydride quaternary copolymer, and the general structural formula is shown in Formula II:

[0014]

[0015] Among them, the range of x1 is 178 to 216, the range of x2 is 21 to 36, the range of y is 30 to 100, and the range of z is 210 to 240.

[0016] In a specific embodiment, the preparation method of the modifier includes:

[0017] A. In a vacuum or inert gas, polymerize a styrene monomer, a butadiene monomer, and maleic anhydride in an initiator and a solvent to generate a terpolymer;

[0018] B. Add a primary amine to the terpolymer obtained in step A for an imidization reaction, and after devolatilization, obtain a maleimide-based high heat-resistant and impact-resistant modifier;

[0019] The styrene monomer described in step A is at least one of styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-phenylstyrene, p-vinylstyrene, p-tert-butylstyrene, p-chlorostyrene, p-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, p-bromostyrene, p-nitrostyrene, p-hydroxystyrene, p-chloromethylstyrene, p-dimethylaminostyrene, preferably styrene;

[0020] The butadiene monomer described in step A is at least one of butadiene, chloroprene, 2,3-dimethyl-1,3-butadiene, preferably butadiene;

[0021] The primary amine described in step B is at least one of 1-aminonaphthalene, 2-aminonaphthalene, 1-aminotetrahydronaphthalene, 1,2,3,4-tetrahydro-1-naphthylamine, 3-cyclohexylaniline, 4-cyclohexylaniline, aniline, cyclohexylamine, preferably 1-aminonaphthalene.

[0022] The inert gas is a gas that does not react with the reaction system. For example, nitrogen, the function of nitrogen is to remove oxygen in the reaction system. The function of nitrogen is similar to providing an inert atmosphere, and oxygen is removed by multiple nitrogen replacements during the synthesis process.

[0023] In a specific embodiment, the temperature of the polymerization in step A is 50°C to 70°C for a reaction of 2 to 3 hours; preferably, the reaction is carried out at 50°C for 3 hours.

[0024] In a specific embodiment, the temperature of the reaction in step B is 90°C to 110°C, and the reaction duration is 4 to 6 hours; preferably, the temperature is 90°C and the reaction duration is 5 hours.

[0025] In a specific embodiment, the mass percentages of the styrene monomer, butadiene monomer, and maleic anhydride are 45 - 60:5 - 15:35 - 40; preferably, the dosage of the initiator is 0.5% - 1.0% of the total mass of the styrene monomer, butadiene monomer, and maleic anhydride; the dosage of the solvent is 2 - 2.5 times the total mass of the styrene monomer, butadiene monomer, and maleic anhydride.

[0026] In step B, the dosage of the primary amine is 85% - 90% of the molar amount of maleic anhydride, preferably 87%.

[0027] In a specific embodiment, the solvent is at least one of cyclobutanone, acetone, acetophenone, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene, dimethyl sulfoxide, N,N - dimethylformamide, N - methylpyrrolidone, preferably methyl ethyl ketone; the initiator is at least one of benzoyl peroxide, lauroyl peroxide, di - tert - butyl peroxide, di - isopropylbenzene peroxide, tert - butyl peroxybenzoate, tert - butyl peroxypivalate, di - isopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, preferably benzoyl peroxide.

[0028] The second object of the present invention is to provide a preparation method of the above - mentioned maleimide - type high - heat - resistant and impact - resistant modifier.

[0029] To achieve the second object of the present invention, the preparation method includes:

[0030] A. In a vacuum or inert gas, polymerize the styrene monomer, butadiene monomer, and maleic anhydride in an initiator and a solvent to generate a terpolymer.

[0031] B. Add a primary amine to the terpolymer obtained in step A for an imidization reaction, and after devolatilization, obtain the maleimide - type high - heat - resistant and impact - resistant modifier.

[0032] The styrene monomer in step A is at least one of styrene, α - methylstyrene, p - methylstyrene, o - methylstyrene, p - phenylstyrene, p - vinylstyrene, p - tert - butylstyrene, p - chlorostyrene, p - fluorostyrene, 3 - fluorostyrene, 4 - fluorostyrene, p - bromostyrene, p - nitrostyrene, p - hydroxystyrene, p - chloromethylstyrene, p - dimethylaminostyrene, preferably styrene.

[0033] The butadiene monomer in step A is at least one of butadiene, chloroprene, 2,3 - dimethyl - 1,3 - butadiene, preferably butadiene.

[0034] The primary amine described in step B is at least one of 1-aminonaphthalene, 2-aminonaphthalene, 1-aminotetralin, 1,2,3,4-tetrahydro-1-naphthylamine, 3-cyclohexylaniline, 4-cyclohexylaniline, aniline, and cyclohexylamine, preferably 1-aminonaphthalene.

[0035] The inert gas is a gas that does not react with the reaction system. For example, nitrogen gas is used to remove oxygen in the reaction system. The role of nitrogen gas is similar to providing an inert atmosphere, and oxygen is removed through multiple nitrogen replacements during the synthesis process.

[0036] In a specific embodiment, the temperature of the polymerization in step A is 50°C to 70°C for 2 to 3 hours of reaction; preferably, the reaction is carried out at 50°C for 3 hours.

[0037] In a specific embodiment, the temperature of the reaction in step B is 90°C to 110°C, and the reaction duration is 4 to 6 hours; preferably, the temperature is 90°C and the reaction duration is 5 hours.

[0038] In a specific embodiment, the mass percentages of the styrene monomer, butadiene monomer, and maleic anhydride are 45 to 60:5 to 15:35 to 40; preferably, the dosage of the initiator is 0.5% to 1.0% of the total mass of the styrene monomer, butadiene monomer, and maleic anhydride; the dosage of the solvent is 2 to 2.5 times the total mass of the styrene monomer, butadiene monomer, and maleic anhydride.

[0039] The dosage of the primary amine described in step B is 85% to 90% of the molar amount of maleic anhydride, preferably 87%.

[0040] In a specific embodiment, the solvent is at least one of cyclobutanone, acetone, acetophenone, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone, preferably methyl ethyl ketone; the initiator is at least one of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, diisopropylbenzene peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy pivalate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate, preferably benzoyl peroxide.

[0041] The third object of the present invention is to provide a high-temperature resistant ABS composite material.

[0042] To achieve the third object of the present invention, the high-temperature resistant ABS composite material contains the above-mentioned maleimide-based high heat-resistant and impact-resistant modifier; preferably, the composition of the high-temperature resistant ABS composite material by mass is: 60 to 90 parts of ABS resin, 10 to 40 parts of maleimide-based high heat-resistant and impact-resistant modifier, and 0.05 to 5 parts of antioxidant; preferably, the heat distortion temperature of the high-temperature resistant ABS composite material is ≥95°C, and the notched impact strength is ≥6.9 KJ / m.2 。

[0043] Beneficial effects:

[0044] 1. The ethylene-N-(1-naphthyl) maleimide-butadiene-maleic anhydride quaternary copolymer prepared by the present invention can be used as a heat-resistant impact modifier for materials such as ABS resin and ASA resin, and can also be used as a compatibilizer and heat-resistant modifier for ABS / engineering plastic alloys, such as PA / ABS, etc. Thus, the applications of materials such as ABS resin, ASA resin, and ABS / engineering plastic alloys in the fields of electronic appliances, automotive, aerospace, industrial equipment, etc. are broadened. Examples of the present invention show that the heat distortion temperature of the modified ABS is increased to 99.6 °C, and the notched impact strength reaches 9.1 KJ / m 2 。Good impact resistance and heat resistance at the same time.

[0045] 2. The one-pot two-step process of the method of the present invention is simple and reduces costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 For the H-NMR diagram of the styrene-N-(1-naphthyl) maleimide-butadiene-maleic anhydride quaternary copolymer in the example 1 H-NMR diagram. DETAILED DESCRIPTION OF THE INVENTION

[0047] To achieve the first object of the present invention, the structure of the maleimide-based high heat-resistant impact modifier of the present invention is shown in Formula I:

[0048]

[0049] Wherein R1 is a naphthalene ring, a tetrahydronaphthalene ring, a benzene ring or a cyclohexyl group, and R is H, Cl, F, Br, a methyl group, a phenyl group or a nitro group;

[0050] The range of x1 is 150-250, the range of x2 is 20-60, the range of y is 25-110, and the range of z is 180-300.

[0051] In a specific embodiment, the R1 is 1-aminonaphthalene, 2-aminonaphthalene, 1-aminotetrahydronaphthalene, 3-cyclohexylaniline or 4-cyclohexylaniline;

[0052] Preferably, the maleimide-based high heat-resistant impact modifier is a styrene-N-(1-naphthyl) maleimide-butadiene-maleic anhydride quaternary copolymer, and the structural general formula is shown in Formula II:

[0053]

[0054] Among them, the range of x1 is 178 to 216, the range of x2 is 21 to 36, the range of y is 30 to 100, and the range of z is 210 to 240.

[0055] In a specific embodiment, the preparation method of the modifier includes:

[0056] A. In a vacuum or inert gas, polymerize a styrene monomer, a butadiene monomer, and maleic anhydride in an initiator and a solvent to generate a terpolymer;

[0057] B. Add a primary amine to the terpolymer obtained in step A for an imidization reaction, and obtain a maleimide-based high heat-resistant and impact-resistant modifier after devolatilization;

[0058] The styrene monomer described in step A is at least one of styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-phenylstyrene, p-vinylstyrene, p-tert-butylstyrene, p-chlorostyrene, p-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, p-bromostyrene, p-nitrostyrene, p-hydroxystyrene, p-chloromethylstyrene, p-dimethylaminostyrene, preferably styrene;

[0059] The butadiene monomer described in step A is at least one of butadiene, chloroprene, 2,3-dimethyl-1,3-butadiene, preferably butadiene;

[0060] The primary amine described in step B is at least one of 1-aminonaphthalene, 2-aminonaphthalene, 1-aminotetralin, 1,2,3,4-tetrahydro-1-naphthylamine, 3-cyclohexylaniline, 4-cyclohexylaniline, aniline, cyclohexylamine, preferably 1-aminonaphthalene.

[0061] The inert gas is a gas that does not react with the reaction system. For example, nitrogen, the function of nitrogen is to remove oxygen in the reaction system. The function of nitrogen is similar to providing an inert atmosphere, and oxygen is removed by multiple nitrogen replacements during the synthesis process.

[0062] In a specific embodiment, the temperature of the polymerization in step A is 50°C to 70°C for a reaction of 2 to 3 hours; preferably, the reaction is carried out at 50°C for 3 hours.

[0063] The synthesis route included in the present invention is:

[0064]

[0065] The synthesis route corresponding to 1-aminonaphthalene is:

[0066]

[0067] In a specific embodiment, the temperature of the reaction in step B is 90°C to 110°C, and the reaction duration is 4 h to 6 h; preferably, the temperature is 90°C and the reaction duration is 5 h.

[0068] In a specific embodiment, the mass percentages of the styrene monomer, butadiene monomer, and maleic anhydride are 45 - 60:5 - 15:35 - 40; preferably, the dosage of the initiator is 0.5% - 1.0% of the total mass of the styrene monomer, butadiene monomer, and maleic anhydride; the dosage of the solvent is 2 - 2.5 times the total mass of the styrene monomer, butadiene monomer, and maleic anhydride;

[0069] The dosage of the primary amine in step B is 85% - 90% of the molar amount of maleic anhydride, preferably 87%.

[0070] In a specific embodiment, the solvent is at least one of cyclobutanone, acetone, acetophenone, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene, dimethyl sulfoxide, N,N - dimethylformamide, N - methylpyrrolidone, preferably methyl ethyl ketone; the initiator is at least one of benzoyl peroxide, lauroyl peroxide, di - tert - butyl peroxide, di - isopropylbenzene peroxide, tert - butyl peroxybenzoate, tert - butyl peroxy - 2 - ethylhexanoate, di - isopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, preferably benzoyl peroxide.

[0071] To achieve the second object of the present invention, the preparation method includes:

[0072] A. In a vacuum or inert gas, polymerize a styrene monomer, a butadiene monomer, and maleic anhydride in an initiator and a solvent to form a terpolymer;

[0073] B. Add a primary amine to the terpolymer obtained in step A for an imidization reaction, and obtain a maleimide - type high - heat - resistant and impact - resistant modifier after devolatilization;

[0074] The styrene monomer in step A is at least one of styrene, α - methylstyrene, p - methylstyrene, o - methylstyrene, p - phenylstyrene, p - vinylstyrene, p - tert - butylstyrene, p - chlorostyrene, p - fluorostyrene, 3 - fluorostyrene, 4 - fluorostyrene, p - bromostyrene, p - nitrostyrene, p - hydroxystyrene, p - chloromethylstyrene, p - dimethylaminostyrene, preferably styrene;

[0075] The butadiene monomer in step A is at least one of butadiene, chloroprene, 2,3 - dimethyl - 1,3 - butadiene, preferably butadiene;

[0076] The primary amine described in step B is at least one of 1-aminonaphthalene, 2-aminonaphthalene, 1-aminotetralin, 1,2,3,4-tetrahydro-1-naphthylamine, 3-cyclohexylaniline, 4-cyclohexylaniline, aniline, and cyclohexylamine, preferably 1-aminonaphthalene.

[0077] The inert gas is a gas that does not react with the reaction system. For example, nitrogen gas is used to remove oxygen in the reaction system. The role of nitrogen gas is similar to providing an inert atmosphere, and oxygen is removed by multiple nitrogen replacements during the synthesis process.

[0078] In a specific embodiment, the temperature of the polymerization described in step A is 50°C to 70°C for a reaction time of 2 to 3 hours; preferably, the reaction is carried out at 50°C for 3 hours.

[0079] In a specific embodiment, the temperature of the reaction described in step B is 90°C to 110°C, and the reaction duration is 4 to 6 hours; preferably, the temperature is 90°C and the reaction duration is 5 hours.

[0080] In a specific embodiment, the mass percentages of the styrene monomer, butadiene monomer, and maleic anhydride are 45 to 60:5 to 15:35 to 40; preferably, the dosage of the initiator is 0.5% to 1.0% of the total mass of the styrene monomer, butadiene monomer, and maleic anhydride; the dosage of the solvent is 2 to 2.5 times the total mass of the styrene monomer, butadiene monomer, and maleic anhydride.

[0081] The dosage of the primary amine described in step B is 85% to 90% of the molar amount of maleic anhydride, preferably 87%.

[0082] In a specific embodiment, the solvent is at least one of cyclobutanone, acetone, acetophenone, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone, preferably methyl ethyl ketone; the initiator is at least one of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, diisopropylbenzene peroxide, tert-butyl perbenzoate, tert-butyl peroxyneopentanoate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate, preferably benzoyl peroxide.

[0083] To achieve the third object of the present invention, the high-temperature resistant ABS composite material contains the above-mentioned maleimide-based high heat-resistant and impact-resistant modifier; preferably, the composition of the high-temperature resistant ABS composite material by mass is: 60 to 90 parts of ABS resin, 10 to 40 parts of maleimide-based high heat-resistant and impact-resistant modifier, and 0.05 to 5 parts of antioxidant; preferably, the heat distortion temperature of the high-temperature resistant ABS composite material is ≥95°C, and the notched impact strength is ≥6.9 KJ / m 2 .

[0084] The specific embodiments of the present invention will be further described below in conjunction with the embodiments, and the present invention is not limited to the scope of the described embodiments accordingly.

[0085] Example 1

[0086] At room temperature, nitrogen was introduced into the reaction kettle for purging. First, methyl ethyl ketone was added to the reaction kettle and stirred continuously. Styrene at a certain mass percentage of 55%, butadiene at 5%, and maleic anhydride at 40% were added as three monomers. Subsequently, methyl ethyl ketone twice the mass of the total monomers was added to the reaction kettle, and the temperature was set at 60 °C for stirring and dissolution. After stirring and dissolving for 0.5 h, benzoyl peroxide at 0.5% of the total monomer mass (the total monomer mass is the sum of the total monomer masses of styrene + butadiene + maleic anhydride) was added, and the temperature was raised to 50 °C and reacted for 3 h to prepare a styrene-maleic anhydride-butadiene terpolymer using an initiator. Then, 1-aminonaphthalene was added to the reaction kettle, and the amount of 1-aminonaphthalene used accounted for 87% of the molar mass of maleic anhydride, and the temperature was raised to 90 °C for imidization reaction, and the reaction continued for 5 h. After the reaction, devolatilization was carried out using an exhaust-type screw extruder to obtain a maleimide-based high heat-resistant and impact-resistant modifier - styrene-N-(1-naphthyl)maleimide-butadiene-maleic anhydride quaternary copolymer. Its nuclear magnetic spectrum is as follows Figure 1 shown.

[0087] The 1 H-NMR of styrene-N-(1-naphthyl)maleimide-butadiene-maleic anhydride quaternary copolymer is as Figure 1 shown.

[0088] First, acrylonitrile-butadiene-styrene copolymer (ABS) and styrene-N-(1-naphthyl)maleimide-butadiene-maleic anhydride quaternary copolymer were dried in a vacuum oven at 90 - 100 °C for 4 - 5 hours; acrylonitrile-butadiene-styrene copolymer (ABS) at a mass percentage of 70% and styrene-N-(1-naphthyl)maleimide-butadiene-maleic anhydride quaternary copolymer at 30% were used, and the antioxidant (1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane) was used at 0.2% of the total mass of the total blended materials, and the materials were weighed. Subsequently, the materials were put into a high-speed mixer for mixing. Finally, melt shear blending was carried out through a twin-screw extruder at a temperature range of 270 - 310 °C, and cooled and pelletized to obtain heat-resistant and impact-resistant ABS.

[0089] Example 2

[0090] At room temperature, nitrogen was introduced into the reaction kettle for purging. First, methyl ethyl ketone was added to the reaction kettle and stirred continuously. Three monomers were added according to a certain mass percentage: styrene 50%, butadiene 10%, and maleic anhydride 40%. Subsequently, methyl ethyl ketone (twice the total mass of the monomers) was added to the reaction kettle, and the temperature was set at 60 °C for stirring and dissolution. After stirring and dissolving for 0.5 h, benzoyl peroxide (0.5% of the total mass of the monomers) was added, and the temperature was raised to 50 °C for a reaction of 3 h to prepare a styrene-maleic anhydride-butadiene terpolymer using an initiator. Then, 1-aminonaphthalene was added to the reaction kettle, and the amount of 1-aminonaphthalene accounted for 87% of the molar mass of maleic anhydride. The temperature was raised to 90 °C for imidization reaction, and the reaction continued for 5 h. After the reaction, devolatilization was carried out using an exhaust-type screw extruder to obtain a maleimide-based high heat-resistant and impact-resistant modifier - styrene-N-(1-naphthyl)maleimide-butadiene-maleic anhydride quaternary copolymer.

[0091] First, acrylonitrile-butadiene-styrene copolymer (ABS) and styrene-N-(1-naphthyl)maleimide-butadiene-maleic anhydride quaternary copolymer were dried in a vacuum oven at 90 - 100 °C for 4 - 5 hours; according to a mass percentage of 70% acrylonitrile-butadiene-styrene copolymer (ABS) and 30% styrene-N-(1-naphthyl)maleimide-butadiene-maleic anhydride quaternary copolymer, and the antioxidant (1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane) was used in an amount of 0.2% of the total mass of the total blend material, the materials were weighed. Subsequently, the materials were put into a high-speed mixer for mixing. Finally, at a temperature range of 270 - 310 °C, melt shear blending was carried out through a twin-screw extruder, and then cooled and pelletized to obtain heat-resistant and impact-resistant ABS.

[0092] Example 3

[0093] At room temperature, nitrogen was introduced into the reaction kettle for purging. First, methyl ethyl ketone was added to the reaction kettle and stirred continuously. Three monomers were added according to a certain mass percentage: styrene 45%, butadiene 15%, and maleic anhydride 40%. Subsequently, methyl ethyl ketone (twice the total mass of the monomers) was added to the reaction kettle, and the temperature was set at 60 °C for stirring and dissolution. After stirring and dissolving for 0.5 h, benzoyl peroxide (0.5% of the total mass of the monomers) was added, and the temperature was raised to 50 °C for a reaction of 3 h to prepare a styrene-maleic anhydride-butadiene terpolymer using an initiator. Then, 1-aminonaphthalene was added to the reaction kettle, and the amount of 1-aminonaphthalene accounted for 87% of the molar mass of maleic anhydride. The temperature was raised to 90 °C for imidization reaction, and the reaction continued for 5 h. After the reaction, devolatilization was carried out using an exhaust-type screw extruder to obtain a maleimide-based high heat-resistant and impact-resistant modifier - styrene-N-(1-naphthyl)maleimide-butadiene-maleic anhydride quaternary copolymer.

[0094] First, at 90 - 100 °C, acrylonitrile - butadiene - styrene copolymer (ABS) and styrene - N-(1 - naphthyl) maleimide - butadiene - maleic anhydride quaternary copolymer were dried in a vacuum oven for 4 - 5 hours. According to the mass percentage, 70% of acrylonitrile - butadiene - styrene copolymer (ABS), 30% of styrene - N-(1 - naphthyl) maleimide - butadiene - maleic anhydride quaternary copolymer, and the antioxidant (1,1,3 - tris(5 - tert - butyl - 4 - hydroxy - 2 - methylphenyl) butane) was used at 0.2% of the total mass of the total blended materials, and the materials were weighed. Subsequently, the materials were put into a high - speed mixer for mixing. Finally, at a temperature range of 270 - 310 °C, melt - shear blending was carried out through a twin - screw extruder, and then cooled and pelletized to obtain heat - resistant and impact - resistant ABS.

[0095] Example 4

[0096] At room temperature, nitrogen was introduced into the reaction kettle for purging. First, methyl ethyl ketone was added to the reaction kettle and continuously stirred. According to a certain mass percentage, 45% of α - methylstyrene, 15% of butadiene, and 40% of maleic anhydride were put into the three monomers. Subsequently, methyl ethyl ketone (2 times the total mass of the monomers) was added to the reaction kettle, and the temperature was set at 60 °C for stirring and dissolution. After stirring and dissolving for 0.5 h, benzoyl peroxide (0.5% of the total mass of the monomers) was added, and the temperature was raised to 50 °C for a reaction of 3 h to prepare α - methylstyrene - maleic anhydride - butadiene terpolymer using an initiator. Then, 1 - aminonaphthalene was added to the reaction kettle, and the amount of 1 - aminonaphthalene was 87% of the molar mass of maleic anhydride, and the temperature was raised to 90 °C for imidization reaction, and the reaction continued for 5 h. After the reaction, devolatilization was carried out using an exhaust - type screw extruder to obtain a maleimide - type high - heat - resistant and impact - resistant modifier - α - methylstyrene - N-(1 - naphthyl) maleimide - butadiene - maleic anhydride quaternary copolymer.

[0097] First, at 90 - 100 °C, acrylonitrile - butadiene - styrene copolymer (ABS) and α - methylstyrene - N-(1 - naphthyl) maleimide - butadiene - maleic anhydride quaternary copolymer were dried in a vacuum oven for 4 - 5 hours. According to the mass percentage, 70% of acrylonitrile - butadiene - styrene copolymer (ABS), 30% of α - methylstyrene - N-(1 - naphthyl) maleimide - butadiene - maleic anhydride quaternary copolymer, and the antioxidant (1,1,3 - tris(5 - tert - butyl - 4 - hydroxy - 2 - methylphenyl) butane) was used at 0.2% of the total mass of the total blended materials, and the materials were weighed. Subsequently, the materials were put into a high - speed mixer for mixing. Finally, at a temperature range of 270 - 310 °C, melt - shear blending was carried out through a twin - screw extruder, and then cooled and pelletized to obtain heat - resistant and impact - resistant ABS.

[0098] Example 5

[0099] At room temperature, nitrogen was purged into the reaction kettle. First, methyl ethyl ketone was added to the reaction kettle and stirred continuously. Styrene (45% by mass), butadiene (15% by mass), and maleic anhydride (40% by mass) were added as three monomers. Subsequently, methyl ethyl ketone (twice the total mass of the monomers) was added to the reaction kettle, and the temperature was set at 60 °C for stirring and dissolution. After stirring and dissolving for 0.5 h, benzoyl peroxide (0.5% of the total mass of the monomers) was added, and the temperature was raised to 50 °C for a reaction of 3 h to prepare a methyl styrene-maleic anhydride-butadiene terpolymer using an initiator. Then, cyclohexylamine was added to the reaction kettle, and the amount of cyclohexylamine used was 87% of the molar mass of maleic anhydride. The temperature was raised to 90 °C for an imidization reaction, and the reaction continued for 5 h. After the reaction, devolatilization was carried out using an exhaust-type screw extruder to obtain a maleimide-based high heat-resistant and impact-resistant modifier - methyl styrene-N-(cyclohexyl) maleimide-butadiene-maleic anhydride quaternary copolymer.

[0100] First, at 90 - 100 °C, acrylonitrile-butadiene-styrene copolymer (ABS) and methyl styrene-N-(cyclohexyl) maleimide-butadiene-maleic anhydride quaternary copolymer were dried in a vacuum oven for 4 - 5 hours. According to the mass percentage, 70% acrylonitrile-butadiene-styrene copolymer (ABS), 30% methyl styrene-N-(cyclohexyl) maleimide-butadiene-maleic anhydride quaternary copolymer, and antioxidant (1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane) was used in an amount of 0.2% of the total mass of the total blending materials, and the materials were weighed. Subsequently, the materials were put into a high-speed mixer for mixing. Finally, at a temperature range of 270 - 310 °C, melt shear blending was carried out through a twin-screw extruder, and then cooled and pelletized to obtain heat-resistant and impact-resistant ABS.

[0101] Comparative Example 1

[0102] At room temperature, nitrogen was purged into the reaction kettle. First, methyl ethyl ketone was added to the reaction kettle and stirred continuously. Styrene (60% by mass) and maleic anhydride (40% by mass) were added as two monomers. Subsequently, benzoyl peroxide (0.5% of the total mass of the monomers) was added, and the temperature was set at 60 °C and added to the reaction kettle together with methyl ethyl ketone (twice the total mass of the monomers) for stirring and dissolution. After stirring and dissolving for 0.5 h, benzoyl peroxide (0.5% of the total mass of the monomers) was added, and the temperature was raised to 50 °C for a reaction of 3 h to prepare a styrene-maleic anhydride copolymer using an initiator. Then, aniline was added to the reaction kettle, and the amount of aniline used was 87% of the molar mass of maleic anhydride. The temperature was raised to 90 °C for an imidization reaction, and the reaction continued for 5 h. After the reaction, devolatilization was carried out using an exhaust-type screw extruder to obtain a styrene-N-phenyl maleimide-maleic anhydride terpolymer.

[0103] First, at 90 - 100 °C, acrylonitrile - butadiene - styrene copolymer (ABS) and styrene - N - phenylmaleimide - maleic anhydride terpolymer were dried in a vacuum oven for 4 - 5 hours; according to the mass percentage of 70% acrylonitrile - butadiene - styrene copolymer (ABS), 30% styrene - N - phenylmaleimide - maleic anhydride terpolymer, and the antioxidant (1,1,3 - tris(5 - tert - butyl - 4 - hydroxy - 2 - methylphenyl)butane) dosage accounting for 0.2% of the total mass of the total blend material, the materials were weighed. Subsequently, the materials were put into a high - speed mixer for mixing. Finally, at a temperature range of 270 - 310 °C, melt - shear blending was carried out through a twin - screw extruder, followed by cooling and pelletizing to obtain heat - resistant impact - resistant ABS.

[0104] Comparative Example 2

[0105] Referring to the invention patent CN117143085A, a certain proportion of maleic anhydride, 2 - dibenzofuranamine, xylene, N,N - dimethylacetamide (DMAC), p - toluenesulfonic acid, and tert - butylphenol were weighed. The molar ratio of maleic anhydride to 2 - dibenzofuranamine was 1:1.2; the mass ratio of xylene to N,N - dimethylacetamide (DMAC) was 10:1, and the amount of xylene was 5 times the total mass of maleic anhydride and 2 - dibenzofuranamine; the inhibitor dosage was 3%; the p - toluenesulfonic acid dosage was 8%. In the temperature range of 40 °C and under a nitrogen atmosphere, half of the measured amount of xylene, solvent, inhibitor, and maleic anhydride were added to a four - necked flask of the reaction system equipped with a stirrer, a spherical condenser, a water separator, and a constant - pressure dropping funnel; and a mixture of half of the measured amount of toluene and 2 - dibenzofuranamine was added dropwise to the reaction system within 1 h. After the dropwise addition was completed, the reaction continued for 1 h, then p - toluenesulfonic acid was added and the temperature was raised to 130 °C for 3 h; then the oil temperature was set at 90 °C, and the toluene in the reaction system was evacuated under vacuum; finally, the reaction system was cooled to 30 °C, and a mixture of ethanol and water was added to precipitate N - dibenzofuranyl maleimide, denoted as N - FMI. In the temperature range of 80 °C and under a nitrogen atmosphere, the mass percentages of each component added to a four - necked flask of the reaction system equipped with a stirrer and a spherical condenser were: styrene (St) 69%, N - dibenzofuranyl maleimide 30%, and maleic anhydride 1%. The initiator dosage was 1% of the total mass of the materials, and the solvent dosage was 2 times the total mass. The reaction continued for 5 h to obtain the product styrene - N - dibenzofuranyl maleimide - maleic anhydride.

[0106] First, at 90 - 100 °C, acrylonitrile - butadiene - styrene copolymer (ABS) and styrene - N - dibenzofuranyl maleimide - maleic anhydride terpolymer were dried in a vacuum oven for 4 - 5 hours. According to the mass percentage: 70% acrylonitrile - butadiene - styrene copolymer (ABS), 30% styrene - N - dibenzofuranyl maleimide - maleic anhydride terpolymer, and the antioxidant (1,1,3 - tris(5 - tert - butyl - 4 - hydroxy - 2 - methylphenyl)butane) was used at 0.2% of the total mass of the total blended materials, and the materials were weighed. Subsequently, the materials were put into a high - speed mixer for mixing. Finally, at a temperature range of 270 - 310 °C, melt - shear blending was carried out through a twin - screw extruder, followed by cooling and pelletizing to obtain heat - resistant ABS.

[0107] Comparative Example 3

[0108] At room temperature, nitrogen was introduced into the reaction kettle for purging. First, methyl ethyl ketone was added to the reaction kettle and stirred continuously. According to a certain mass percentage: styrene 40%, butadiene 20%, and maleic anhydride 40%, the three monomers were added. Subsequently, methyl ethyl ketone (2 times the total monomer mass) was added to the reaction kettle, and the temperature was set at 60 °C for stirring and dissolving. After stirring and dissolving for 0.5 h, benzoyl peroxide (0.5% of the total monomer mass) was added, and the temperature was raised to 50 °C for a reaction of 3 h to prepare styrene - maleic anhydride - butadiene terpolymer using an initiator. Then, 1 - aminonaphthalene was added to the reaction kettle, and the amount of 1 - aminonaphthalene was 87% of the molar mass of maleic anhydride, and the temperature was raised to 90 °C for imidization reaction, and the reaction continued for 5 h. After the reaction, devolatilization was carried out using an exhaust - type screw extruder to obtain a maleimide - type high - heat - resistant and impact - resistant modifier - styrene - N - (1 - naphthyl)maleimide - butadiene - maleic anhydride quaternary copolymer.

[0109] First, at 90 - 100 °C, acrylonitrile - butadiene - styrene copolymer (ABS) and styrene - N - (1 - naphthyl)maleimide - butadiene - maleic anhydride quaternary copolymer were dried in a vacuum oven for 4 - 5 hours. According to the mass percentage: 70% acrylonitrile - butadiene - styrene copolymer (ABS), 30% styrene - N - (1 - naphthyl)maleimide - butadiene - maleic anhydride quaternary copolymer, and the antioxidant (1,1,3 - tris(5 - tert - butyl - 4 - hydroxy - 2 - methylphenyl)butane) was used at 0.2% of the total mass of the total blended materials, and the materials were weighed. Subsequently, the materials were put into a high - speed mixer for mixing. Finally, at a temperature range of 270 - 310 °C, melt - shear blending was carried out through a twin - screw extruder, followed by cooling and pelletizing to obtain heat - resistant and impact - resistant ABS.

[0110] The properties of Examples 1 - 5 and Comparative Examples 1 - 3 are shown in Table 1 below

[0111] Table 1 Mechanical properties of Examples 1-5 and Comparative Examples 1-3

[0112]

[0113] The pure ABS model is Jilin Petrochemical ABS-0215H

[0114] The heat resistance properties of Examples 1-5 and Comparative Examples 1-3 are shown in Table 2 below:

[0115] Table 2 Heat resistance properties of Examples 1-5 and Comparative Examples 1-3

[0116]

Claims

1. Maleimide high heat resistance and impact resistance modifier, characterized in that: The structure of the maleimide high heat resistance and impact resistance modifier is shown in Formula I: Wherein R1 is a naphthalene ring, a tetrahydronaphthalene ring, a benzene ring or a cyclohexyl group; R is H, Cl, F, Br, methyl, phenyl or nitro; The range of x1 is 150 to 250, the range of x2 is 20 to 60, the range of y is 25 to 110, and the range of z is 180 to 300.

2. The maleimide-based high heat-resistant and impact-resistant modifier according to claim 1, characterized in that: R1 is 1-aminonaphthalene, 2-aminonaphthalene, 1-aminotetralin, 3-cyclohexylaniline or 4-cyclohexylaniline; Preferably, the maleimide-based high heat resistance and impact resistance modifier is a styrene-N-(1-naphthyl) maleimide-butadiene-maleic anhydride tetrapolymer, and the general structural formula is shown in Formula II: Among them, the range of x1 is 178~216, the range of x2 is 21~36, the range of y is 30~100, and the range of z is 210~240.

3. The maleimide-based high heat-resistant and impact-resistant modifier according to claim 1, characterized in that: The preparation method of the modifier comprises: A. In vacuum or inert gas, styrene monomer, butadiene monomer and maleic anhydride are polymerized in an initiator and a solvent to form a terpolymer; B. adding a primary amine to the terpolymer described in step A to carry out imidization reaction, and obtaining a maleimide-based high heat-resistant and impact-resistant modifier after devolatilization; The styrene monomer in step A is at least one of styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-phenylstyrene, p-vinylstyrene, p-tert-butylstyrene, p-chlorostyrene, p-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, p-bromostyrene, p-nitrostyrene, p-hydroxystyrene, p-chloromethylstyrene and p-dimethylaminostyrene, preferably styrene; The butadiene monomer in step A is at least one of butadiene, chloroprene, and 2,3-dimethyl-1,3-butadiene, preferably butadiene; The primary amine in step B is at least one of 1-aminonaphthalene, 2-aminonaphthalene, 1-aminotetrahydronaphthalene, 1,2,3,4-tetrahydro-1-naphthylamine, 3-cyclohexylaniline, 4-cyclohexylaniline, aniline and cyclohexylamine, preferably 1-aminonaphthalene.

4. The maleimide-based high heat-resistant and impact-resistant modifier according to claim 3, characterized in that: The polymerization temperature in step A is 50°C to 70°C for 2 to 3 hours, preferably 50°C for 3 hours; The reaction temperature in step B is 90° C. to 110° C., and the reaction time is 4 h to 6 h; preferably, the temperature is 90° C., and the reaction time is 5 h.

5. The maleimide-based high heat resistance and impact resistance modifier according to claim 3 or 4, characterized in that: The mass percentage of the styrene monomer, butadiene monomer and maleic anhydride is 45-60:5-15:35-40; preferably, the amount of the initiator is 0.5%-1.0% of the total mass of the styrene monomer, butadiene monomer and maleic anhydride; the amount of the solvent is 2-2.5 times the total mass of the styrene monomer, butadiene monomer and maleic anhydride; The amount of the primary amine used in step B is 85% to 90% of the molar amount of maleic anhydride, preferably 87%.

6. The maleimide-based high heat resistance and impact resistance modifier according to claim 2 or 3, characterized in that: The solvent is at least one of cyclobutanone, acetone, acetophenone, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone, preferably butanone; the initiator is at least one of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate, preferably benzoyl peroxide.

7. The method for preparing the maleimide-based high heat-resistant and impact-resistant modifier according to any one of claims 1 to 6, characterized in that: The preparation method comprises: A. In vacuum or inert gas, styrene monomer, butadiene monomer and maleic anhydride are polymerized in an initiator and a solvent to form a terpolymer; B. adding a primary amine to the terpolymer described in step A to carry out imidization reaction, and obtaining a maleimide-based high heat-resistant and impact-resistant modifier after devolatilization; The styrene monomer in step A is at least one of styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-phenylstyrene, p-vinylstyrene, p-tert-butylstyrene, p-chlorostyrene, p-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, p-bromostyrene, p-nitrostyrene, p-hydroxystyrene, p-chloromethylstyrene and p-dimethylaminostyrene, preferably styrene; The butadiene monomer in step A is at least one of butadiene, chloroprene, and 2,3-dimethyl-1,3-butadiene, preferably butadiene; The primary amine in step B is at least one of 1-aminonaphthalene, 2-aminonaphthalene, 1-aminotetrahydronaphthalene, 1,2,3,4-tetrahydro-1-naphthylamine, 3-cyclohexylaniline, 4-cyclohexylaniline, aniline and cyclohexylamine, preferably 1-aminonaphthalene.

8. The method for preparing the maleimide-based high heat-resistant and impact-resistant modifier according to claim 7, characterized in that: The polymerization temperature in step A is 50°C to 70°C for 2 to 3 hours; preferably 50°C for 3 hours; The reaction temperature in step B is 90°C to 110°C, and the reaction time is 4h to 6h; preferably, the temperature is 90°C, and the reaction time is 5h; The mass percentage of the styrene monomer, butadiene monomer and maleic anhydride is 45-60:5-15:35-40; preferably, the amount of the initiator is 0.5%-1.0% of the total mass of the styrene monomer, butadiene monomer and maleic anhydride; the amount of the solvent is 2-2.5 times the total mass of the styrene monomer, butadiene monomer and maleic anhydride; The amount of the primary amine used in step B is 85% to 90% of the molar amount of maleic anhydride, preferably 87%.

9. The method for preparing the maleimide-based high heat-resistant and impact-resistant modifier according to claim 7, characterized in that: The solvent is at least one of cyclobutanone, acetone, acetophenone, methyl isobutyl ketone, tetrahydrofuran, toluene, xylene, dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone, preferably butanone; the initiator is at least one of benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate, preferably benzoyl peroxide.

10. High temperature resistant ABS composite material, characterized in that: The high temperature resistant ABS composite material comprises the maleimide high heat resistant impact modifier according to any one of claims 1 to 6; preferably, the composition of the high temperature resistant ABS composite material is: 60 to 90 parts by mass of ABS resin, 10 to 40 parts by mass of maleimide high heat resistant impact modifier, and 0.05 to 5 parts by mass of antioxidant; preferably, the heat deformation temperature of the high temperature resistant ABS composite material is ≥95°C, and the notched impact strength is ≥6.9KJ / m 2 .

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