High-toughness scratch-resistant PMMA multilayer composite material and preparation method thereof

Abstract

The application discloses a kind of high tough and scratch-resistant PMMA multilayer composite and preparation method thereof, it includes PMMA layer and PMMA-ABS layer, both are in the form of alternating layered structure, the PMMA-ABS layer includes the following weight parts of raw materials: PMMA resin 85-95 parts, ABS high glue powder 5-15 parts, wear-resistant agent 3-5 parts, compatible agent 2-6 parts, antioxidant 1.5-3 parts, auxiliary agent 0.5-1 part;PMMA-based multilayer composite prepared by micro-nano layered composite preparation system has the characteristics of high strength, high toughness and scratch resistance, etc., provides new ideas and new ways for designing and preparing PMMA-based high-performance composite materials for automotive interiors, electronic product housings, etc.

Description

Technical Field

[0001] This invention relates to a high-strength, tough, and scratch-resistant PMMA multilayer composite material and its preparation method, belonging to the technical field of high-performance multilayer composite materials. Background Technology

[0002] Polymethyl methacrylate (PMMA) possesses superior transparency, electrical insulation, and excellent light resistance, weather resistance, and anti-aging properties. Therefore, PMMA composites are increasingly widely used in the automotive and electronics packaging industries, and are continuously expanding into high-end supply chains. However, PMMA exhibits some brittleness and can fracture under high impact energy. Furthermore, the presence of ester groups makes PMMA prone to water absorption and significant room-temperature creep, which can lead to stress cracking during molding and use. In addition, PMMA has insufficient surface hardness, making it easily scratched by hard objects. Scratch resistance is typically improved by increasing surface hardness or reducing the surface friction coefficient. While increasing surface hardness usually involves adding resins or fillers with higher hardness than existing materials, this method reduces toughness, resulting in unsatisfactory mechanical properties. Summary of the Invention

[0003] The purpose of this invention is to provide a high-strength, tough, and scratch-resistant PMMA multilayer composite material and its preparation method to solve the above-mentioned problems.

[0004] The technical solution adopted in this invention is as follows:

[0005] A high-strength, tough, and scratch-resistant PMMA multilayer composite material, comprising alternating PMMA layers and PMMA / ABS layers, wherein the PMMA / ABS layer comprises the following raw materials in parts by weight: 85-95 parts PMMA resin, 5-15 parts ABS high-adhesion powder, 1-5 parts abrasion resistant agent, 2-6 parts compatibilizer, 1.5-3 parts antioxidant, and 0.5-1 parts additives.

[0006] The wear-resistant agent is ultra-high molecular weight polyethylene micro powder or cross-linked silica particles of zirconium hydrogen phosphate, with a particle size range of 5-200 μm.

[0007] The method for preparing the zirconium hydrogen phosphate crosslinked silica particles includes the following steps:

[0008] Step 1: Add zirconium hydroxide to an aqueous solution of phosphoric acid to react and obtain a zirconium hydrogen phosphate suspension;

[0009] Step 2: Mix silica sol, water and ammonia to obtain a silica sol mixed solution, and then add ethanol;

[0010] Step 3: Add an organic solvent containing fluorinated silane to the mixture obtained in step 2 to carry out the grafting reaction;

[0011] Step 4: Add zirconium hydrogen phosphate suspension to the mixture obtained in step 3. After the reaction, filter the product and vacuum dry it to obtain cross-linked silica particles of zirconium hydrogen phosphate.

[0012] In step 1, the concentration of the phosphoric acid aqueous solution is 40-60 wt%, the reaction conditions are 80-110℃ for 1-5 h, and the molar ratio of zirconium hydroxide to phosphoric acid is 2-6:1.

[0013] In step 2, the weight ratio of silica sol, water and ammonia is 1:3-6:3-6, the solid content of silica sol is 10-30%, and the concentration of ammonia is 5-15 wt%. The volume ratio of silica sol mixed solution and ethanol is 1:5-15.

[0014] In step 3, the fluorinated silane is 1H,1H,2H,2H-perfluorodecyltrichlorosilane with a concentration of 0.5-5 wt%, and the organic solvent is a hydrocarbon solvent or an ester solvent; the volume ratio of the organic solvent containing the fluorinated silane to ethanol is 1:0.5-1.5; the grafting reaction conditions are 30-60℃ for 1-10 h.

[0015] In step 4, the amount of zirconium hydrogen phosphate suspension added is based on a weight ratio of 1:2-5 of Zr(OH)2 in the raw materials and SiO2 converted from silica sol, and the reaction conditions are 10-40℃ for 10-30h.

[0016] The thickness ratio of the PMMA layer to the PMMA / ABS layer is 1:0.5-1.5.

[0017] The total number of layers in the modified PMMA layer and PMMA / ABS layer is 32-512.

[0018] The butadiene segment content in the ABS high-resin powder is >60%.

[0019] The antioxidant is a mixture of hindered phenolic antioxidant 1010 and complexed phosphite antioxidant 168 in a weight ratio of 1:1-3.

[0020] The preparation method of the above-mentioned high-strength, tough, and scratch-resistant PMMA multilayer composite material includes the following steps:

[0021] (1) Dry PMMA resin and ABS high-adhesion powder separately;

[0022] (2) PMMA resin, ABS high-adhesion powder, wear-resistant agent, compatibilizer, antioxidant and additives are premixed according to the weight ratio and then melt-extruded and granulated to obtain PMMA / ABS blend;

[0023] (3) The dried PMMA and PMMA / ABS blends are added to the feeders of extruder A and extruder B of the micro-nano multilayer composite preparation system, respectively. After being combined by the confluencer, they are extruded through the layer multiplier, the parallel extrusion die, and the traction device to obtain the PMMA multilayer composite material.

[0024] In step (2), the processing temperature of each zone of melt extrusion is 210-240℃, and the feed screw speed is 25-30 rpm / min.

[0025] In step (3), the feeding frequency of extruder A and extruder B is 30-60HZ; the processing temperature of single screw extruder A and extruder B is 220-275℃.

[0026] In step (3), the processing temperature of the confluencer and layer multiplier is 270-275℃, and the die temperature is 265-275℃.

[0027] Beneficial effects

[0028] The beneficial effects of this invention are as follows:

[0029] 1. This invention employs a micro-nano multilayer composite preparation system to prepare PMMA composite materials. PMMA is toughened and modified using ABS high-rubber powder with a high rubber phase, and the polymer melt is subjected to in-situ multi-stage stretching to cause the ABS high-rubber powder dispersion phase to be stretched and oriented within the PMMA matrix. Simultaneously, during the micro-nano multilayer multiplication process, the ABS high-rubber powder toughening phase undergoes phase-breakage deformation within the PMMA matrix due to both compressive and tensile stress mechanisms, thus forming a scaled-refined ABS high-rubber powder toughening phase. This organically combines the micro-nano layered interface toughening of PMMA with the blending and toughening modification of a high-elasticity rubber system, achieving highly efficient toughening of PMMA resin materials.

[0030] 2. ABS high-rubber powder contains a high content of butadiene segments (PB rubber particles) with a high rubber phase. Blending PMMA with it can yield a PMMA composite material with a balance of high rigidity and high toughness. At the same time, using core-shell copolymers, block copolymers or random copolymers as compatibilizers can effectively adjust the compatibility between PMMA and ABS high-rubber powder.

[0031] 3. The ultrafine ultra-high molecular weight polyethylene (UHMWPE) micropowder used in this invention is a wear-resistant agent. The UHMWPE micropowder with a highly physically entangled structure undergoes extremely fine microparticle processing and, through the design of a micro-nano layered structure, can be uniformly and effectively dispersed in the PMMA system, giving the PMMA composite material excellent impact resistance and abrasion resistance. The silica particles with fluorine grafting and zirconium hydrogen phosphate crosslinking on the surface used in this invention are also a wear-resistant agent. After fluorine modification of the silica surface, the problem of poor dispersion of inorganic silica wear-resistant particles in the polymer is solved, and the use of zirconium hydrogen phosphate to bond with silica nanoparticles through covalent bonds improves the wear resistance of the particles.

[0032] 4. By adjusting and controlling the morphology and structure of the aggregated phase through processing and molding conditions, a PMMA-based nano-multilayer composite structure is constructed. By inducing the forced phase deformation of dispersed phases such as toughening agents and wear-resistant agents in the multilayer confined space and the multilevel heterogeneous interface, a synergistic mechanism for efficient energy dissipation is constructed to achieve a dynamic balance of high rigidity and toughness. This allows for the preparation of a low-cost, continuously producible, high-strength, toughness, and scratch-resistant PMMA multilayer composite material, which can be applied to automotive parts and electronic product packaging, and expands its application scope in high-end industries. Attached Figure Description

[0033] Figure 1 This is a schematic diagram of the microstructure of high-strength, tough, and scratch-resistant PMMA multilayer composite material during the micro-nano multilayer co-extrusion process.

[0034] Figure 2 This is a photograph of the multilayer composite material of the present invention. Detailed Implementation

[0035] Example 1

[0036] A high-strength, tough, and scratch-resistant PMMA multilayer composite material includes alternating layers of PMMA and PMMA / ABS, with a layer thickness ratio of 1:1, and a total of 512 layers.

[0037] The PMMA / ABS layer is prepared by weight of 95 parts PMMA resin, 5 parts ABS high-rubber powder, 5 parts abrasion resistant agent, 4 parts compatibilizer, 1.5 parts antioxidant, and 0.5 parts additives, wherein the abrasion resistant agent is ultra-high molecular weight polyethylene micro powder with a mesh size of 10-30μm.

[0038] The preparation method of the high-strength, tough, and scratch-resistant PMMA multilayer composite material includes the following steps:

[0039] (1) After drying and dehumidifying PMMA resin and ABS high-rubber powder respectively, PMMA resin, ABS high-rubber powder, wear-resistant agent, compatibilizer, antioxidant and additives are premixed according to the above weight ratio and then melt extruded and granulated. The processing temperature of each zone of melt extrusion is 210-240℃ and the feed screw speed is 25-30rpm / min to obtain PMMA / ABS blend.

[0040] (2) The dried PMMA and PMMA / ABS blends were added to the feeders of extruder A and extruder B of the micro-nano multilayer composite preparation system, respectively. After being merged by the confluencer, they were extruded through the layer multiplier, the parallel extrusion die, and the traction device in sequence. The feeding frequency of extruder A and extruder B was 30-60HZ, the processing temperature of single screw extruder A and extruder B was 220-275℃, the processing temperature of the confluencer and the layer multiplier was 270-275℃, and the die temperature was 265-275℃, so as to obtain a high-strength, tough and scratch-resistant PMMA multilayer composite material.

[0041] Example 2

[0042] A high-strength, tough, and scratch-resistant PMMA multilayer composite material comprises alternating layers of PMMA and PMMA / ABS, with a layer thickness ratio of 1:1, and a total of 128 layers.

[0043] The PMMA / ABS layer is prepared by weight of 90 parts PMMA resin, 10 parts ABS high-resin powder, 3 parts abrasion resistant agent, 2 parts compatibilizer, 3 parts antioxidant, and 1 part additive.

[0044] The preparation steps of the high-strength, tough, and scratch-resistant PMMA multilayer composite material are the same as in Example 1.

[0045] Example 3

[0046] A high-strength, tough, and scratch-resistant PMMA multilayer composite material includes alternating layers of PMMA and PMMA / ABS, with a layer thickness ratio of 1:1, and a total of 32 layers.

[0047] The PMMA / ABS layer, by weight, is prepared from 85 parts PMMA resin, 15 parts ABS high-resin powder, 1 part abrasion resistant agent, 6 parts compatibilizer, 3 parts antioxidant, and 1 part additive.

[0048] The preparation steps of the high-strength, tough, and scratch-resistant PMMA multilayer composite material are the same as in Example 1.

[0049] Example 4

[0050] A high-strength, tough, and scratch-resistant PMMA multilayer composite material includes alternating layers of PMMA and PMMA / ABS, with a layer thickness ratio of 1:1, and a total of 512 layers.

[0051] The PMMA / ABS layer, by weight, is prepared from 95 parts PMMA resin, 5 parts ABS high-resin powder, 5 parts abrasion resistant agent, 4 parts compatibilizer, 1.5 parts antioxidant, and 0.5 parts additives. The abrasion resistant agent is silica particles grafted with fluorine and cross-linked with zirconium hydrogen phosphate with a mesh size of 10-30 μm.

[0052] The preparation method includes the following steps:

[0053] (1) According to the molar ratio of phosphoric acid to zirconium hydroxide 4:1, 20g of zirconium hydroxide was added to a 50wt% aqueous solution of phosphoric acid, and then reacted at 90-100℃ for 3h to obtain a zirconium hydrogen phosphate suspension.

[0054] (2) Mix silica sol, water, and ammonia in a weight ratio of 1:6:3, wherein the solid content of the silica sol is [missing information].

[0055] 25 wt% ammonia solution and 5 wt% ammonia solution were mixed with ethanol at a volume ratio of 1:8 for 15 min. Then, a cyclohexane solution of 1H,1H,2H,2H-perfluorodecyltrichlorosilane at a concentration of 1.5 wt% was added, with a volume ratio of cyclohexane solution to ethanol of 1:0.9. After reacting at 40-45℃ for 2 h, a zirconium hydrogen phosphate suspension was added (the amount added was based on a weight ratio of Zr(OH)2 in the raw materials to SiO2 calculated from the silica sol of 1:3). The reaction was carried out at room temperature for 24 h. After filtration, vacuum drying and grinding, fluorine-grafted and zirconium hydrogen phosphate crosslinked silica particles were obtained.

[0056] The preparation steps of the high-strength, tough, and scratch-resistant PMMA multilayer composite material are the same as in Example 1.

[0057] Example 5

[0058] A high-strength, tough, and scratch-resistant PMMA multilayer composite material includes alternating layers of PMMA and PMMA / ABS, with a layer thickness ratio of 1:1, and a total of 512 layers.

[0059] The PMMA / ABS layer, by weight, is prepared from 95 parts PMMA resin, 5 parts ABS high-resin powder, 5 parts abrasion resistant agent, 4 parts compatibilizer, 1.5 parts antioxidant, and 0.5 parts additives. The abrasion resistant agent is silica particles grafted with fluorine and cross-linked with zirconium hydrogen phosphate with a mesh size of 10-30 μm.

[0060] The preparation method includes the following steps:

[0061] (1) According to the molar ratio of phosphoric acid to zirconium hydroxide 3:1, 20g of zirconium hydroxide was added to a 55wt% aqueous solution of phosphoric acid, and then reacted at 90-100℃ for 2h to obtain a zirconium hydrogen phosphate suspension.

[0062] (2) Mix silica sol, water, and ammonia in a weight ratio of 1:5:4, wherein the solid content of the silica sol is [missing information].

[0063] 20 wt% ammonia solution and 8 wt% ammonia solution were mixed with ethanol at a volume ratio of 1:9 for 10 min. Then, a cyclohexane solution of 1H,1H,2H,2H-perfluorodecyltrichlorosilane at a concentration of 2 wt% was added, with a volume ratio of cyclohexane solution to ethanol of 1:0.8. The mixture was reacted at 40-45℃ for 3 h. Then, a zirconium hydrogen phosphate suspension was added (the amount added was calculated based on a weight ratio of Zr(OH)2 in the raw materials to SiO2 calculated from the silica sol of 1:4). The mixture was reacted at room temperature for 24 h. The product was filtered, vacuum dried, and ground to obtain fluorine-grafted and zirconium hydrogen phosphate crosslinked silica particles.

[0064] The preparation steps of the high-strength, tough, and scratch-resistant PMMA multilayer composite material are the same as in Example 1.

[0065] Example 6

[0066] A high-strength, tough, and scratch-resistant PMMA multilayer composite material includes alternating layers of PMMA and PMMA / ABS, with a layer thickness ratio of 1:1, and a total of 512 layers.

[0067] The PMMA / ABS layer, by weight, is prepared from 95 parts PMMA resin, 5 parts ABS high-resin powder, 5 parts abrasion resistant agent, 4 parts compatibilizer, 1.5 parts antioxidant, and 0.5 parts additives. The abrasion resistant agent is silica particles grafted with fluorine and cross-linked with zirconium hydrogen phosphate with a mesh size of 10-30 μm.

[0068] The preparation method includes the following steps:

[0069] (1) According to the molar ratio of phosphoric acid to zirconium hydroxide 5:1, 20g of zirconium hydroxide was added to a 50wt% aqueous solution of phosphoric acid, and then reacted at 90-100℃ for 1h to obtain a zirconium hydrogen phosphate suspension.

[0070] (2) Mix silica sol, water, and ammonia in a weight ratio of 1:6:3, wherein the solid content of the silica sol is [missing information].

[0071] 20 wt% ammonia solution and 10 wt% ammonia solution were mixed with ethanol at a volume ratio of 1:7 for 15 min. Then, a cyclohexane solution of 1H,1H,2H,2H-perfluorodecyltrichlorosilane at a concentration of 2.5 wt% was added, with a volume ratio of cyclohexane solution to ethanol of 1:1. The mixture was reacted at 40-45℃ for 3 h. Then, a zirconium hydrogen phosphate suspension was added (the amount added was calculated based on a weight ratio of Zr(OH)2 in the raw materials to SiO2 calculated from the silica sol of 1:5). The mixture was reacted at room temperature for 24 h. The product was filtered, vacuum dried, and ground to obtain fluorine-grafted and zirconium hydrogen phosphate crosslinked silica particles.

[0072] The preparation steps of the high-strength, tough, and scratch-resistant PMMA multilayer composite material are the same as in Example 1.

[0073] Comparative Example 1

[0074] The specific implementation method is the same as in Example 3, except that no wear-resistant agent is added to the PMMA / ABS layer.

[0075] Comparative Example 2

[0076] The specific implementation method is the same as in Example 3, except that PMMA and PMMA / ABS are two-layer composite materials with a layer thickness ratio of 1:1.

[0077] The method for preparing the PMMA two-layer composite material includes the following steps: dried PMMA is added to the feeder of a single-screw extruder A in a micro-nano multilayer composite extrusion system; dried PMMA / ABS is added to the feeder of a single-screw extruder B in the same system; and the materials are extruded through a two-layer composite runner die. The feeding frequency of extruders A and B is 30-60 Hz; the melt processing temperature of single-screw extruders A and B is 220-275℃; and the composite runner die temperature is 270℃. Finally, the two-layer composite material of PMMA and PMMA / ABS is obtained by traction using a traction device.

[0078] Comparative Example 3

[0079] The specific implementation method is the same as in Example 3, except that in the preparation of silica particles, zirconium hydrogen phosphate suspension was not added to crosslink the surface of silica particles.

[0080] The PMMA composite materials prepared in Examples 1-6 and Comparative Examples 1-3 were subjected to performance tests. The test standards for each performance are as follows: yield strength test was conducted according to GB / T 1040.2-2006 standard, with a tensile speed of 50 mm / min; flexural strength test was conducted according to GB / T 9341-2008 standard, with a flexural speed of 2 mm / min; cantilever beam unnotched impact test was conducted according to GB / T 1843-2008 standard; and scratch resistance test was conducted according to GMW 14698 (Method B).

[0081] The performance test results are shown in Table 1.

[0082] Table 1 Performance test results of Examples 1-4 and Comparative Examples 1-2

[0083]

[0084] Comparing the test results of Examples 1-6 with those of Comparative Examples 1-3, this invention utilizes a high-elasticity rubber matrix for toughening and a wear-resistant agent, with both working synergistically to toughen the matrix. By leveraging the melt shear characteristics under multilayered confined scales, the toughening and wear-resistant agent is encouraged to form a smaller-scale nano-dispersed phase. Furthermore, energy absorption and dissipation are achieved through multilayered heterogeneous interfaces. This maintains the rigidity of the PMMA matrix while achieving highly efficient toughening and wear resistance with a relatively low rubber elastomer content, thus preparing a high-strength, tough, and scratch-resistant PMMA multilayer composite material. Additionally, a comparison between Example 1 and Comparative Example 1 shows that the ultrafine, ultra-high molecular weight polyethylene powder used as the wear-resistant agent exhibits a high degree of physical entanglement. The ultra-high molecular weight polyethylene (UHMWPE) micropowder, after undergoing extremely fine microparticle processing and employing a micro-nano layered structure design, can be uniformly and effectively dispersed within the PMMA system, endowing the PMMA composite material with superior impact resistance and abrasion resistance. A comparison of Example 4 and Comparative Example 3 shows that the silica particles with fluorine grafting and zirconium hydrogen phosphate crosslinking used in this invention serve as the wear-resistant agent. Fluorine modification of the silica surface solves the problem of poor dispersion of inorganic silica wear-resistant particles in the polymer, and the use of zirconium hydrogen phosphate, through covalent bonding with the silica nanoparticles, improves the wear resistance of the particles. This provides a process route and preparation method for the low-cost, continuous preparation of high-rigidity, high-toughness, and scratch-resistant PMMA composite materials, meeting the requirements for high-rigidity, high-toughness, and scratch-resistant properties, and enabling the application of low-cost, lightweight shell and component materials.

Claims

1. A high-strength, tough, and scratch-resistant PMMA multilayer composite material, characterized in that, The multilayer composite material comprises alternating layers of PMMA and PMMA / ABS. The PMMA / ABS layer comprises the following raw materials in parts by weight: 85-95 parts PMMA resin, 5-15 parts ABS high-resin powder, 1-5 parts wear-resistant agent, 2-6 parts compatibilizer, 1.5-3 parts antioxidant, and 0.5-1 parts additives. The wear-resistant agent is cross-linked silica particles of zirconium hydrogen phosphate with a particle size range of 5-200 μm. The method for preparing the zirconium hydrogen phosphate crosslinked silica particles includes the following steps: Step 1: Add zirconium hydroxide to an aqueous solution of phosphoric acid to react and obtain a zirconium hydrogen phosphate suspension; Step 2: Mix silica sol, water and ammonia to obtain a silica sol mixed solution, and then add ethanol; Step 3: Add an organic solvent containing fluorinated silane to the mixture obtained in step 2 to carry out the grafting reaction; Step 4: Add zirconium hydrogen phosphate suspension to the mixture obtained in step 3. After the reaction, filter the product and vacuum dry it to obtain cross-linked silica particles of zirconium hydrogen phosphate. In step 1, the concentration of the phosphoric acid aqueous solution is 40-60 wt%, the reaction conditions are 80-110℃ for 1-5 h, and the molar ratio of zirconium hydroxide to phosphoric acid is 2-6:

1. In step 2, the weight ratio of silica sol, water and ammonia is 1:3-6:3-6, the solid content of silica sol is 10-30%, and the concentration of ammonia is 5-15 wt%; the volume ratio of silica sol mixed solution and ethanol is 1:5-15. In step 3, the fluorinated silane is 1H,1H,2H,2H-perfluorodecyltrichlorosilane, with a concentration of 0.5-5 wt%, and the organic solvent is a hydrocarbon solvent or an ester solvent; the volume ratio of the organic solvent containing the fluorinated silane to ethanol is 1:0.5-1.5; the grafting reaction conditions are 30-60℃ for 1-10 h; In step 4, the amount of zirconium hydrogen phosphate suspension added is based on a weight ratio of 1:2-5 of Zr(OH)2 in the raw materials and SiO2 in the silica sol, and the reaction conditions are 10-40℃ for 10-30h.

2. The high-strength, tough, and scratch-resistant PMMA multilayer composite material according to claim 1, characterized in that, The thickness ratio of the PMMA layer to the PMMA / ABS layer is 1:0.5-1.5; the total number of PMMA and PMMA / ABS layers is 32-512.

3. The high-strength, tough, and scratch-resistant PMMA multilayer composite material according to claim 1, characterized in that, The butadiene segment content in the ABS high-rubber powder is >60%; the antioxidant is a mixture of hindered phenolic antioxidant 1010 and complexed phosphite antioxidant 168 in a weight ratio of 1:1-3.

4. The method for preparing the high-strength, tough, and scratch-resistant PMMA multilayer composite material according to claim 1, characterized in that, Includes the following steps: (1) Dry PMMA resin and ABS high-adhesion powder separately; (2) PMMA resin, ABS high-rubber powder, wear-resistant agent, compatibilizer, antioxidant and additives are premixed according to the weight ratio and then melt-extruded and granulated to obtain PMMA / ABS blend; (3) The dried PMMA and PMMA / ABS blends are added to the feeders of extruder A and extruder B of the micro-nano multilayer composite preparation system, respectively. After being combined by the confluencer, they are extruded through the layer multiplier, the parallel extrusion die, and the traction device to obtain the PMMA multilayer composite material.

5. The method for preparing the high-strength, tough, and scratch-resistant PMMA multilayer composite material according to claim 4, characterized in that, In step (2), the processing temperature of each zone of melt extrusion is 210-240℃, and the feed screw speed is 25-30rpm.

6. The method for preparing the high-strength, tough, and scratch-resistant PMMA multilayer composite material according to claim 4, characterized in that, In step (3), the feeding frequency of extruder A and extruder B is 30-60Hz; the processing temperature of extruder A and extruder B is 220-275℃; in step (3), the processing temperature of the confluencer and layer multiplier is 270-275℃, and the die temperature is 265-275℃.

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