Alcohol-resistant and heat-resistant PMMA composite material and preparation method thereof

Abstract

The invention relates to an alcohol-resistant and heat-resistant PMMA (polymethyl methacrylate) composite material and a preparation method thereof, and belongs to the technical field of high polymer materials. The alcohol-resistant and heat-resistant PMMA composite material is prepared from the following components in parts by weight: 30 to 60 parts of acrylonitrile-acrylate-styrene copolymer, 30 to 60 parts of polymethyl methacrylate resin, 1 to 5 parts of compatilizer, 1 to 3 parts of carbon black, 0.1 to 1.5 parts of antioxidant, 0.1 to 2 parts of lubricant, 1 to 5 parts of modified heat-resistant agent and 1 to 3 parts of modified flame retardant, the alcohol-resistant and heat-resistant PMMA composite material prepared by the invention not only has good heat-resistant and aging-resistant effects, but also has an excellent flame-retardant effect.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and particularly relates to an alcohol-resistant and heat-resistant PMMA composite material and a preparation method thereof. Background Art

[0002] PMMA (polymethyl methacrylate), commonly known as plexiglass, is an important organic transparent material with the characteristics of high light transmittance, light weight, easy processing and molding, and good dimensional stability, weather resistance, and electrical insulation. It is not easy to color and is widely used in construction, automobiles, electronics and other fields.

[0003] However, organic glass has the problem of poor heat resistance in actual application, and the short-term use temperature does not exceed 120°C. This not only makes it susceptible to thermal degradation during the production and processing process, but also easily deformed during use, seriously limiting its application range. In addition, although PMMA composite materials have a certain flame retardant effect when burning, with the continuous improvement of actual application needs, its own flame retardancy can no longer meet current needs. Therefore, the research and development of PMMA composite materials with excellent performance that are resistant to alcohol and heat has important practical significance and application value. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides an alcohol-resistant and heat-resistant PMMA composite material and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An alcohol-resistant and heat-resistant PMMA composite material and a preparation method thereof, comprising the following raw materials in parts by weight: 30-60 parts of acrylonitrile-acrylate-styrene copolymer, 30-60 parts of polymethyl methacrylate resin, 1-5 parts of a compatibilizer, 1-3 parts of carbon black, 0.1-1.5 parts of an antioxidant, 0.1-2 parts of a lubricant, 1-5 parts of a modified heat-resistant agent, and 1-3 parts of a modified flame retardant;

[0007] The compatibilizer is ethylene-methyl acrylate copolymer;

[0008] The antioxidant is antioxidant 1010;

[0009] The lubricant is pentaerythritol stearate.

[0010] The modified heat-resistant agent is prepared by the following method:

[0011] Step A1: Maleic anhydride and N,N-dimethylformamide were uniformly mixed, p-aminobenzoic acid was added, and the mixture was reacted at 25°C for 2 h. Anhydrous sodium acetate, hydroquinone, and acetic anhydride were added, and the mixture was heated to 55-60°C and reacted for 2 h. After the reaction, the mixture was cooled to room temperature, filtered, washed, and dried at 50°C to obtain the compound;

[0012] Furthermore, the usage ratio of maleic anhydride, N,N-dimethylformamide, p-aminobenzoic acid, anhydrous sodium acetate, hydroquinone, and acetic anhydride is 0.01-0.02 mol: 6-10 mL: 0.01-0.02 mol: 0.2-0.4 g: 0.17-0.34 g: 1-2 mL;

[0013] First, maleic anhydride is reacted with the amino group of p-aminobenzoic acid to prepare the compound;

[0014] Step A2: Add p-aminophenol to tetrahydrofuran and disperse evenly, then slowly add allyl isothiocyanate under stirring, raise the temperature to 45-55°C, stir and react for 3-4 hours, filter, wash, and dry, then add the compound, concentrated sulfuric acid, and dimethyl sulfoxide, mix, and react at 80°C for 2 hours. After the reaction, filter, wash, and dry to obtain a pre-product;

[0015] Furthermore, the ratio of p-aminophenol, tetrahydrofuran, allyl isothiocyanate, compound, concentrated sulfuric acid, and dimethyl sulfoxide is 0.01-0.03 mol: 10-15 mL: 0.01-0.03 mol: 0.01-0.03 mol: 0.1-0.3 mL: 5-15 mL;

[0016] Secondly, the amino group of p-aminophenol reacts with the isothiocyanate group of allyl isothiocyanate, and then the hydroxyl group of p-aminophenol reacts with the carboxyl group of the compound to prepare a pre-product;

[0017] Step A3: Triallyl isocyanurate, the pre-product, and cyclohexanone were mixed, heated in an oil bath to 80°C for 30 minutes, and benzoyl peroxide was added under nitrogen protection. The temperature was raised to 110°C and the reaction was carried out for 4 hours. After the reaction was completed, the mixture was cooled to room temperature and dried to obtain a modified heat-resistant agent.

[0018] Furthermore, the usage ratio of triallyl isocyanurate, preproduct, cyclohexanone, and benzoyl peroxide is 0.01-0.03 mol: 0.01-0.03 mol: 20-80 mL: 0.12-0.36 g;

[0019] Finally, the modified heat-resistant agent is prepared by utilizing the carbon-carbon double bond of the pre-product to react with the carbon-carbon double bond of triallyl isocyanurate.

[0020] The modified flame retardant is prepared by the following method:

[0021] Step B1: Under a nitrogen atmosphere, p-hydroxybenzaldehyde and chloroform were mixed uniformly, cooled to -6°C, and then dimethyl chlorophosphate and triethylamine were added. The temperature was raised to 60°C and the reaction was carried out for 5 hours. After the reaction was completed, the system was cooled to room temperature, washed, rotary evaporated, and dried at 60°C to obtain an intermediate;

[0022] Furthermore, the usage ratio of p-hydroxybenzaldehyde, chloroform, dimethyl chlorophosphate, and triethylamine is 0.01-0.03 mol: 40-60 mL: 0.01-0.03 mol: 8-12 g;

[0023] First, the hydroxyl group of p-hydroxybenzaldehyde reacts with the chlorine atom of dimethyl chlorophosphate to obtain an intermediate;

[0024] Step B2: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dichloromethane were mixed uniformly under ultrasonic conditions, and then the intermediate was added and mixed, reacted at 85° C. for 4 hours, and dried to obtain a modified flame retardant;

[0025] Furthermore, the ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane, and the intermediate is 0.01-0.03 mol: 5-20 mL: 0.01-0.03 mol;

[0026] Finally, the aldehyde group of the intermediate reacts with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to prepare a modified flame retardant.

[0027] A method for preparing an alcohol-resistant and heat-resistant PMMA composite material comprises the following steps:

[0028] S1, placing acrylonitrile-acrylate-styrene copolymer, polymethyl methacrylate resin, compatibilizer, carbon black, antioxidant, lubricant, modified heat-resistant agent and modified flame retardant in a high-speed batching mixer, and mixing at high speed to obtain a premix;

[0029] S2. The premix is placed in an extruder for melt extrusion and granulation. After the extruded material is cooled, it is granulated to obtain an alcohol-resistant and heat-resistant PMMA composite material; the temperature zone of the twin-screw machine is: the first stage temperature is 160-200°C, the second stage temperature is 180-220°C, the third stage temperature is 200-240°C, the fourth stage temperature is 200-240°C, the fifth stage temperature is 200-250°C, the head temperature is 200-250°C, the main engine frequency is 30-35Hz, the feeding frequency is 10-15Hz, and the pelletizer speed is 300-500r / min.

[0030] Beneficial effects of the present invention:

[0031] The alcohol-resistant and heat-resistant PMMA composite material of the present invention has good heat resistance and aging resistance effects, and also has excellent flame retardant effect, further extending the service life.

[0032] The maleimide group in the modified heat-resistant agent prepared by the present invention can enhance the intermolecular force, improve the glass transition temperature and melting point of the material, increase the rigidity and heat resistance of the molecular chain, and reduce the material aging caused by high-temperature thermal aging; triallyl isocyanurate is a multifunctional olefin monomer containing an aromatic heterocycle and three active allyl functional groups. It can form a three-dimensional cross-linked network with the PMMA molecular chain, restrict the movement of the molecular chain, and thus improve the thermal stability of the material. At the same time, the addition of triallyl isocyanurate can increase the cross-linking density of the PMMA material, make the connection of the molecular chain tighter, help to resist thermal decomposition and deformation at high temperature, and thus improve the heat resistance of the material; in addition, the thiourea in the modified heat-resistant agent has good resistance to ozone aging and thermal oxidation, can capture free radicals, terminate chain reactions, and delay the aging of the material, thereby effectively extending the service life and reducing the cost of use; in addition, the modified heat-resistant agent has good compatibility with the PMMA material, can be evenly dispersed in the PMMA matrix, and synergistically exert its heat resistance and aging resistance.

[0033] When the modified flame retardant prepared by the present invention is burned, the phosphorus element reacts with oxygen on the surface of the material, diluting the oxygen concentration and generating compounds such as phosphoric acid, which promotes the formation of carbon on the surface of the material, playing a role in heat insulation and oxygen isolation. At the same time, it generates free radicals, captures the combustion-supporting active free radicals generated during combustion, interrupts the combustion chain reaction, and prevents further combustion of the material and the spread of fire. The nitrogen element can promote the decomposition of the polymer to produce molten droplets that take away heat, decomposes itself to produce incombustible gases to dilute the oxygen concentration, and absorbs heat and cools down to achieve flame retardancy. In addition, the phosphorus element in dimethyl chlorophosphate can form a phosphate protective layer to inhibit the spread of flames. At the same time, the phosphorus-nitrogen flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, as a phosphaphenanthrene compound with high thermal stability, promotes the formation of a dense and continuous carbon layer during combustion, isolates oxygen, blocks the exchange of heat and combustible gases, enhances the flame retardant effect, and extends the service life of the material. In addition, the modified flame retardant prepared by the present invention is halogen-free, can reduce pollution to the environment and damage to the ecosystem, is harmless to human health, and achieves sustainable development. DETAILED DESCRIPTION

[0034] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0035] Example 1: A method for preparing an alcohol-resistant and heat-resistant PMMA composite material, comprising the following steps:

[0036] S1. Weigh the raw materials by weight: 30 parts of acrylonitrile-acrylate-styrene copolymer, 30 parts of polymethyl methacrylate resin, 1 part of compatibilizer, 1 part of carbon black, 0.1 part of antioxidant, 0.1 part of lubricant, 1 part of modified heat-resistant agent, and 1 part of modified flame retardant; put the acrylonitrile-acrylate-styrene copolymer, polymethyl methacrylate resin, ethylene-methyl acrylate copolymer, carbon black, antioxidant 1010, pentaerythritol stearate, modified heat-resistant agent and modified flame retardant into a high-speed batching mixer and mix them at high speed to obtain a premix;

[0037] S2. The premix is placed in an extruder for melt extrusion and granulation. After the extruded material is cooled, granulation is performed to obtain an alcohol-resistant and heat-resistant PMMA composite material; the temperature zone of the twin-screw machine is: the first stage temperature is 160°C, the second stage temperature is 180°C, the third stage temperature is 200°C, the fourth stage temperature is 200°C, the fifth stage temperature is 200°C, the head temperature is 200°C, the main engine frequency is 30Hz, the feeding frequency is 10Hz, and the pelletizer speed is 300r / min;

[0038] The modified heat-resistant agent is prepared by the following method:

[0039] Step A1: 0.01 mol of maleic anhydride and 6 mL of N,N-dimethylformamide were uniformly mixed, and then 0.01 mol of p-aminobenzoic acid was added. The mixture was reacted at 25°C for 2 h. 0.2 g of anhydrous sodium acetate, 0.17 g of hydroquinone, and 1 mL of acetic anhydride were added. The mixture was heated to 55°C and reacted for 2 h. After the reaction, the mixture was cooled to room temperature, filtered, washed, and dried at 50°C to obtain the compound.

[0040] Step A2: 0.01 mol of p-aminophenol was added to 10 mL of tetrahydrofuran and dispersed evenly. 0.01 mol of allyl isothiocyanate was slowly added under stirring, and the temperature was raised to 45°C. The mixture was stirred for 3 h, filtered, washed, and dried. 0.01 mol of the compound, 0.1 mL of concentrated sulfuric acid, and 5 mL of dimethyl sulfoxide were then added and mixed. The mixture was reacted at 80°C for 2 h. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a pre-product.

[0041] Step A3: 0.01 mol of triallyl isocyanurate, 0.01 mol of pre-product and 20 mL of cyclohexanone were mixed, heated to 80°C in an oil bath for 30 min, 0.12 g of benzoyl peroxide was added under nitrogen protection, the temperature was raised to 110°C, and the reaction was carried out for 4 h. After the reaction was completed, the mixture was cooled to room temperature and dried to obtain a modified heat-resistant agent;

[0042] The modified flame retardant is prepared by the following method:

[0043] Step B1: Under a nitrogen atmosphere, 0.01 mol of p-hydroxybenzaldehyde and 40 mL of chloroform were mixed uniformly, cooled to -6°C, and then 0.01 mol of dimethyl chlorophosphate and 8 g of triethylamine were added. The temperature was raised to 60°C and the reaction was carried out for 5 h. After the reaction was completed, the system was cooled to room temperature, washed, rotary evaporated, and dried at 60°C to obtain an intermediate;

[0044] Step B2: 0.01 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 5 mL of dichloromethane were mixed uniformly under ultrasonic conditions, and then 0.01 mol of the intermediate was added and mixed. The mixture was reacted at 85° C. for 4 h and dried to obtain a modified flame retardant.

[0045] Example 2: A method for preparing an alcohol-resistant and heat-resistant PMMA composite material, comprising the following steps:

[0046] S1. Weigh the raw materials by weight: 45 parts of acrylonitrile-acrylate-styrene copolymer, 45 parts of polymethyl methacrylate resin, 3 parts of compatibilizer, 2 parts of carbon black, 0.8 parts of antioxidant, 1.5 parts of lubricant, 3 parts of modified heat-resistant agent, and 2 parts of modified flame retardant; put acrylonitrile-acrylate-styrene copolymer, polymethyl methacrylate resin, ethylene-methyl acrylate copolymer, carbon black, antioxidant 1010, pentaerythritol stearate, modified heat-resistant agent and modified flame retardant into a high-speed batching mixer and mix them at high speed to obtain a premix;

[0047] S2. The premix is placed in an extruder for melt extrusion and granulation. After the extruded material is cooled, granulation is performed to obtain an alcohol-resistant and heat-resistant PMMA composite material; the temperature zone of the twin-screw machine is: the first stage temperature is 180°C, the second stage temperature is 200°C, the third stage temperature is 220°C, the fourth stage temperature is 220°C, the fifth stage temperature is 225°C, and the head temperature is 225°C. The main engine frequency is 32.5Hz, the feeding frequency is 12.5Hz, and the pelletizer speed is 400r / min;

[0048] The modified heat-resistant agent is prepared by the following method:

[0049] Step A1: 0.015 mol of maleic anhydride and 8 mL of N,N-dimethylformamide were mixed uniformly, and then 0.015 mol of p-aminobenzoic acid was added. The mixture was reacted at 25°C for 2 h. 0.3 g of anhydrous sodium acetate, 0.255 g of hydroquinone, and 1.5 mL of acetic anhydride were added. The mixture was heated to 57.5°C and reacted for 2 h. After the reaction, the mixture was cooled to room temperature, filtered, washed, and dried at 50°C to obtain the compound.

[0050] Step A2: 0.02 mol of p-aminophenol was added to 12.5 mL of tetrahydrofuran and dispersed evenly. 0.02 mol of allyl isothiocyanate was slowly added under stirring. The temperature was raised to 50°C and stirred for 3.5 hours. The mixture was filtered, washed, and dried. 0.02 mol of the compound, 0.2 mL of concentrated sulfuric acid, and 10 mL of dimethyl sulfoxide were then added and mixed. The mixture was reacted at 80°C for 2 hours. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a pre-product.

[0051] Step A3: 0.02 mol of triallyl isocyanurate, 0.02 mol of pre-product and 50 mL of cyclohexanone were mixed, heated to 80°C in an oil bath for 30 min, 0.24 g of benzoyl peroxide was added under nitrogen protection, the temperature was raised to 110°C, and the reaction was carried out for 4 h. After the reaction was completed, the mixture was cooled to room temperature and dried to obtain a modified heat-resistant agent;

[0052] The modified flame retardant is prepared by the following method:

[0053] Step B1: Under a nitrogen atmosphere, 0.02 mol of p-hydroxybenzaldehyde and 50 mL of chloroform were mixed uniformly, cooled to -6°C, and then 0.02 mol of dimethyl chlorophosphate and 10 g of triethylamine were added. The temperature was raised to 60°C and the reaction was carried out for 5 h. After the reaction was completed, the system was cooled to room temperature, washed, rotary evaporated, and dried at 60°C to obtain an intermediate;

[0054] Step B2: 0.02 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 12.5 mL of dichloromethane were mixed uniformly under ultrasonic conditions, and then 0.02 mol of the intermediate was added and mixed. The mixture was reacted at 85° C. for 4 h and dried to obtain a modified flame retardant.

[0055] Example 3: A method for preparing an alcohol-resistant and heat-resistant PMMA composite material, comprising the following steps:

[0056] S1. Weigh the raw materials by weight: 60 parts of acrylonitrile-acrylate-styrene copolymer, 60 parts of polymethyl methacrylate resin, 5 parts of compatibilizer, 3 parts of carbon black, 1.5 parts of antioxidant, 2 parts of lubricant, 5 parts of modified heat-resistant agent, and 3 parts of modified flame retardant; put acrylonitrile-acrylate-styrene copolymer, polymethyl methacrylate resin, ethylene-methyl acrylate copolymer, carbon black, antioxidant 1010, pentaerythritol stearate, modified heat-resistant agent and modified flame retardant into a high-speed batching mixer and mix them at high speed to obtain a premix;

[0057] S2. The premix is placed in an extruder for melt extrusion and granulation. After the extruded material is cooled, granulation is performed to obtain an alcohol-resistant and heat-resistant PMMA composite material; the temperature zone of the twin-screw machine is: the first stage temperature is 200°C, the second stage temperature is 220°C, the third stage temperature is 240°C, the fourth stage temperature is 240°C, the fifth stage temperature is 250°C, and the head temperature is 250°C. The main engine frequency is 35Hz, the feeding frequency is 15Hz, and the pelletizer speed is 500r / min;

[0058] The modified heat-resistant agent is prepared by the following method:

[0059] Step A1: 0.02 mol of maleic anhydride and 10 mL of N,N-dimethylformamide were uniformly mixed, and then 0.02 mol of p-aminobenzoic acid was added. The mixture was reacted at 25°C for 2 h. 0.4 g of anhydrous sodium acetate, 0.34 g of hydroquinone, and 2 mL of acetic anhydride were added. The mixture was heated to 60°C and reacted for 2 h. After the reaction, the mixture was cooled to room temperature, filtered, washed, and dried at 50°C to obtain the compound.

[0060] Step A2: 0.03 mol of p-aminophenol was added to 15 mL of tetrahydrofuran and dispersed evenly. 0.03 mol of allyl isothiocyanate was slowly added under stirring, and the temperature was raised to 55°C. The mixture was stirred for 4 hours, filtered, washed, and dried. 0.03 mol of the compound, 0.3 mL of concentrated sulfuric acid, and 15 mL of dimethyl sulfoxide were then added and mixed. The mixture was reacted at 80°C for 2 hours. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a pre-product.

[0061] Step A3: 0.03 mol of triallyl isocyanurate, 0.03 mol of pre-product and 80 mL of cyclohexanone were mixed, heated to 80°C in an oil bath for 30 min, and 0.36 g of benzoyl peroxide was added under nitrogen protection. The temperature was raised to 110°C and the reaction was carried out for 4 h. After the reaction was completed, the mixture was cooled to room temperature and dried to obtain a modified heat-resistant agent;

[0062] The modified flame retardant is prepared by the following method:

[0063] Step B1: Under a nitrogen atmosphere, 0.03 mol of p-hydroxybenzaldehyde and 60 mL of chloroform were mixed uniformly, cooled to -6°C, and then 0.03 mol of dimethyl chlorophosphate and 12 g of triethylamine were added. The temperature was raised to 60°C and the reaction was carried out for 5 h. After the reaction was completed, the system was cooled to room temperature, washed, rotary evaporated, and dried at 60°C to obtain an intermediate;

[0064] Step B2: 0.03 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 20 mL of dichloromethane were mixed uniformly under ultrasonic conditions, and then 0.03 mol of the intermediate was added and mixed. The mixture was reacted at 85° C. for 4 h and dried to obtain a modified flame retardant.

[0065] Comparative Example 1: This comparative example is an alcohol-resistant and heat-resistant PMMA composite material. The difference from Example 3 is that an equal amount of N-phenylmaleimide is used instead of the modified heat-resistant agent prepared in Example 3, and the rest are the same.

[0066] Comparative Example 2: This comparative example is an alcohol-resistant and heat-resistant PMMA composite material. The difference from Example 3 is that an equal amount of magnesium hydroxide is used instead of the modified flame retardant prepared in Example 3, and the rest are the same.

[0067] Performance test: The alcohol-resistant and heat-resistant PMMA composite materials prepared in Examples 1-3 and Comparative Examples 1-2 were cut into standard test sizes and tested for heat deformation temperature according to ISO 75-2; flame retardancy was tested according to standard UL-94; the alcohol-resistant and heat-resistant PMMA composite materials prepared in Examples 1-3 and Comparative Examples 1-2 were made into plates according to conventional processes, and 60 sample plates (0.3mx0.6m) were taken, with 10 plates in each group, and the aging resistance was tested by exposure for 1000 hours according to the aging resistance test method specified in the national standard; cracks, scratches, chips or deformation on the outer surface of the sample were considered to be changes in the sample surface; the test results are shown in Table 1 below:

[0068] Table 1

[0069]

[0070] It can be seen from the test data in Table 1 that the alcohol-resistant and heat-resistant PMMA composite material prepared by the present invention has good flame retardant effect. It can also be seen from Table 1 that the alcohol-resistant and heat-resistant PMMA composite material prepared by the present invention has good heat resistance and aging resistance, and extends the service life.

[0071] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A method for preparing an alcohol-resistant and heat-resistant PMMA composite material, characterized in that: The specific steps include: S1. Weigh the raw materials by weight, put 30-60 parts of acrylonitrile-acrylate-styrene copolymer, 30-60 parts of polymethyl methacrylate resin, 1-5 parts of compatibilizer, 1-3 parts of carbon black, 0.1-1.5 parts of antioxidant, 0.1-2 parts of lubricant, 1-5 parts of modified heat-resistant agent and 1-3 parts of modified flame retardant into a high-speed batching mixer, and mix them at high speed to obtain a premix; S2, placing the premix in an extruder for melt extrusion and granulation, and after the extruded material is cooled, granulation is performed to obtain an alcohol-resistant and heat-resistant PMMA composite material; the twin-screw machine temperature zone: the first stage temperature is 160-200 ° C, the second stage temperature is 180-220 ° C, the third stage temperature is 200-240 ° C, the fourth stage temperature is 200-240 ° C, the fifth stage temperature is 200-250 ° C, the head temperature is 200-250 ° C, the main engine frequency is 30-35 Hz, the feeding frequency is 10-15 Hz, and the pelletizer speed is 300-500 r / min; The modified heat-resistant agent is prepared by the following method: Step A1: Maleic anhydride and N,N-dimethylformamide were uniformly mixed, p-aminobenzoic acid was added, and the mixture was reacted at 25°C for 2 h. Anhydrous sodium acetate, hydroquinone, and acetic anhydride were added, and the mixture was heated to 55-60°C and reacted for 2 h. After the reaction, the mixture was cooled to room temperature, filtered, washed, and dried at 50°C to obtain the compound; Step A2: Add p-aminophenol to tetrahydrofuran and disperse evenly, then slowly add allyl isothiocyanate under stirring, raise the temperature to 45-55°C, stir and react for 3-4 hours, filter, wash, and dry, then add the compound, concentrated sulfuric acid, and dimethyl sulfoxide, mix, and react at 80°C for 2 hours. After the reaction, filter, wash, and dry to obtain a pre-product; Step A3: Mix triallyl isocyanurate, pre-product and cyclohexanone, heat to 80°C in an oil bath and maintain for 30 minutes, add benzoyl peroxide under nitrogen protection, raise the temperature to 110°C, react for 4 hours, and after the reaction is completed, cool to room temperature and dry to obtain a modified heat-resistant agent.

2. The method for preparing an alcohol-resistant and heat-resistant PMMA composite material according to claim 1, characterized in that: In step A1, the usage ratio of maleic anhydride, N,N-dimethylformamide, p-aminobenzoic acid, anhydrous sodium acetate, hydroquinone, and acetic anhydride is 0.01-0.02 mol: 6-10 mL: 0.01-0.02 mol: 0.2-0.4 g: 0.17-0.34 g: 1-2 mL.

3. The method for preparing an alcohol-resistant and heat-resistant PMMA composite material according to claim 1, characterized in that: In step A2, the usage ratio of p-aminophenol, tetrahydrofuran, allyl isothiocyanate, compound, concentrated sulfuric acid, and dimethyl sulfoxide is 0.01-0.03 mol: 10-15 mL: 0.01-0.03 mol: 0.01-0.03 mol: 0.1-0.3 mL: 5-15 mL.

4. The method for preparing an alcohol-resistant and heat-resistant PMMA composite material according to claim 1, characterized in that: In step A3, the usage ratio of triallyl isocyanurate, pre-product, cyclohexanone, and benzoyl peroxide is 0.01-0.03 mol: 0.01-0.03 mol: 20-80 mL: 0.12-0.36 g.

5. The method for preparing an alcohol-resistant and heat-resistant PMMA composite material according to claim 1, characterized in that: The modified flame retardant is prepared by the following method: Step B1: Under a nitrogen atmosphere, p-hydroxybenzaldehyde and chloroform were mixed uniformly, cooled to -6°C, and then dimethyl chlorophosphate and triethylamine were added. The temperature was raised to 60°C and the reaction was carried out for 5 hours. After the reaction was completed, the system was cooled to room temperature, washed, rotary evaporated, and dried at 60°C to obtain an intermediate; Step B2: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dichloromethane were mixed evenly under ultrasonic conditions, and then the intermediate was added and mixed. The mixture was reacted at 85° C. for 4 hours and dried to obtain a modified flame retardant.

6. The method for preparing an alcohol-resistant and heat-resistant PMMA composite material according to claim 5, characterized in that: In step B1, the usage ratio of p-hydroxybenzaldehyde, chloroform, dimethyl chlorophosphate, and triethylamine is 0.01-0.03 mol: 40-60 mL: 0.01-0.03 mol: 8-12 g.

7. The method for preparing an alcohol-resistant and heat-resistant PMMA composite material according to claim 5, characterized in that: In step B2, the usage ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dichloromethane, and the intermediate is 0.01-0.03 mol: 5-20 mL: 0.01-0.03 mol.

8. The method for preparing an alcohol-resistant and heat-resistant PMMA composite material according to claim 1, characterized in that: The compatibilizer is ethylene-methyl acrylate copolymer, the antioxidant is antioxidant 1010, and the lubricant is pentaerythritol stearate.

9. An alcohol-resistant and heat-resistant PMMA composite material, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 8.

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