Poly(meth)acrylate composite materials and their preparation methods, automotive lamp covers, automotive lamps, vehicles

Abstract

This invention discloses a poly(meth)acrylate composite material, its preparation method, a headlight cover, a headlight, and a vehicle. The invention involves uniformly blending poly(meth)acrylate with ethanol-resistant rubber. During dynamic vulcanization, the ethanol-resistant rubber gradually vulcanizes to form a three-dimensional network structure and is sheared into rubber microparticles under strong shear, which are uniformly dispersed within the poly(meth)acrylate. When microcracks form in the poly(meth)acrylate, the rubber microparticles can effectively absorb and dissipate energy, thereby effectively improving the toughness of the poly(meth)acrylate. Furthermore, due to the three-dimensional network structure of the vulcanized rubber microparticles and the effective resistance of the ethanol-resistant rubber to ethanol penetration and swelling, the composite material exhibits high alcohol resistance. Therefore, the composite material combines high toughness and high alcohol resistance, effectively reducing the problem of headlight cover cracking caused by ethanol-induced welding residual stress release.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a poly(meth)acrylate composite material and its preparation method, a car lamp cover, a car lamp, and a vehicle. Background Technology

[0002] Polymethyl methacrylate (PMMA) has become a commonly used material for automotive taillight covers due to its advantages such as high transparency, high weather resistance, ease of processing, and low cost. With the evolution of automotive taillight designs, the structure of the lights is gradually developing towards integration, thinner walls, irregular shapes, and precision. The most direct impact of this complex taillight structure on injection-molded products is the increased shear force on the polymer melt during injection molding, leading to severe orientation of the PMMA molecular chains and high residual internal stress. Although annealing can reduce some residual stress, the process is time-consuming and its effect is limited. When taillights come into contact with ethanol-containing car wash liquids during daily use, they are prone to cracking. Currently, taillight cracking has become an industry-wide problem plaguing almost all automakers. Taillight cover cracking not only causes numerous customer complaints, damaging brand image and incurring huge replacement costs, but it can also further damage internal light components, creating significant safety hazards. Summary of the Invention

[0003] This invention aims to at least partially solve one of the technical problems in the related art. To this end, one object of this invention is to provide a poly(meth)acrylate composite material that combines high alcohol resistance with high toughness, effectively reducing the problem of headlight cover cracking caused by the release of residual welding stress induced by ethanol.

[0004] Specifically, the first aspect of the present invention provides a poly(meth)acrylate composite material, comprising the following raw materials: 100 parts by weight of poly(meth)acrylate; 3-20 parts by weight of ethanol-resistant rubber; 0.02-0.4 parts by weight of vulcanizing agent; 0.1-0.5 parts by weight of antioxidant.

[0005] This invention uniformly blends poly(meth)acrylate (such as polymethyl methacrylate) with ethanol-resistant rubber. During dynamic vulcanization, the ethanol-resistant rubber gradually vulcanizes to form a three-dimensional network structure and is sheared into rubber particles (such as micron-sized particles) under strong shear, which are uniformly dispersed in the poly(meth)acrylate. When microcracks develop in the poly(meth)acrylate due to residual internal stress or external loads, the rubber particles can effectively absorb and dissipate energy, thereby effectively improving the toughness of the poly(meth)acrylate and reducing the risk of cracking. In addition, because the vulcanized rubber particles have a three-dimensional network structure, the ethanol-resistant rubber can effectively resist the penetration and swelling of ethanol, giving the composite material high alcohol resistance. Thus, the composite material of this invention combines high toughness and high alcohol resistance, effectively reducing the problem of headlight cover cracking caused by ethanol-induced welding residual stress release, reducing after-sales costs, maintaining brand performance, and improving driving safety. Furthermore, the amount of ethanol-resistant rubber introduced in this invention is small and will not significantly affect the mechanical and heat resistance properties of the poly(meth)acrylate.

[0006] According to some embodiments of the present invention, the volume change rate ΔV of the ethanol-resistant rubber in ethanol solvent is less than 20%.

[0007] According to some embodiments of the present invention, the ethanol-resistant rubber includes at least one of nitrile rubber and fluororubber; the nitrile rubber includes one or more of nitrile rubber, hydrogenated nitrile rubber and carboxylated nitrile rubber; the fluororubber includes one or more of type 1-5 fluororubber, perfluoroether rubber, fluoroether rubber, tetrapropylene fluororubber, nitrosofluororubber and fluorosilicone rubber.

[0008] According to some embodiments of the present invention, the amount of the ethanol-resistant rubber is 10-17 parts by weight, based on 100 parts by weight of the poly(meth)acrylate.

[0009] According to some embodiments of the present invention, the ethanol-resistant rubber is dispersed in the poly(meth)acrylate composite material in the form of micron-sized particles.

[0010] According to some embodiments of the present invention, the poly(meth)acrylate includes one or more of polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, and polyethyl acrylate; optionally, the polymethyl methacrylate includes one or more of transparent polymethyl methacrylate, toughened polymethyl methacrylate, flame-retardant polymethyl methacrylate, and optical polymethyl methacrylate; the antioxidant includes one or more of hindered phenolic antioxidants, aromatic amine antioxidants, phosphite antioxidants, and thioester antioxidants; the vulcanizing agent includes one or more of sulfur-based vulcanization systems, peroxide-based vulcanization systems, and amine-based vulcanization systems.

[0011] A second aspect of the present invention provides a method for preparing the poly(meth)acrylate composite material of the first aspect of the present invention, comprising the following steps: Poly(meth)acrylate, ethanol-resistant rubber, antioxidant and vulcanizing agent are blended to obtain a mixed raw material; The mixed raw materials are melted, dynamically vulcanized, extruded, cooled, granulated, and dried to obtain the poly(meth)acrylate composite material.

[0012] The method of this invention is simple, low-cost, and highly repeatable, making it suitable for large-scale industrial application. The poly(meth)acrylate composite material prepared by this method combines high toughness and high alcohol resistance, effectively reducing the cracking problem of automotive headlight covers caused by ethanol-induced welding residual stress release.

[0013] According to some embodiments of the present invention, the stirring speed of the blending is 5 r / min-200 r / min; the blending time is 15 seconds-10 minutes; the extrusion temperature is 150℃-250℃; the extrusion is carried out in a screw extruder with a screw speed of 60 r / min-350 r / min.

[0014] A third aspect of the present invention provides a vehicle headlight cover, comprising a poly(meth)acrylate composite material of the first aspect of the present invention or a poly(meth)acrylate composite material obtained by the method of the second aspect of the present invention.

[0015] Because of the use of the above-mentioned poly(meth)acrylate composite material, the headlight cover of the present invention has all the advantages of the poly(meth)acrylate composite material, which will not be repeated here.

[0016] According to some embodiments of the present invention, the headlight cover includes a welded rib portion; the material of the welded rib portion includes the poly(meth)acrylate composite material.

[0017] A fourth aspect of the present invention provides a vehicle lamp, including the vehicle lamp cover of the third aspect of the present invention.

[0018] Because of the use of the above-mentioned poly(meth)acrylate composite material, the vehicle lamp of the present invention has all the advantages of the poly(meth)acrylate composite material, which will not be repeated here.

[0019] The fifth aspect of the present invention provides a vehicle including the headlights of the fourth aspect of the present invention.

[0020] Because of the use of the above-mentioned poly(meth)acrylate composite material, the vehicle of the present invention has all the advantages of the poly(meth)acrylate composite material, which will not be repeated here.

[0021] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0022] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which: Figure 1 This is a scanning electron microscope (SEM) image of the polymethyl methacrylate composite material prepared in Example 7 of the present invention. Detailed Implementation

[0023] The embodiments of the present invention are described in detail below. These embodiments are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0024] In the description of this invention, unless otherwise stated, "a plurality of" means two or more. "Multiple" means two or more. Throughout this document, the terms "comprising" or "including" are open-ended expressions, meaning they include the contents specified in this invention but do not exclude other aspects.

[0025] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0026] Polymethyl methacrylate (PMMA) has become a common material for automotive taillight covers due to its advantages such as high transparency, high weather resistance, ease of processing, and low cost. However, when taillights come into contact with ethanol-containing car wash solutions during daily use, the ethanol may penetrate the PMMA and form hydrogen bonds with the PMMA molecular chains, thus reducing the interaction between the PMMA molecular chains. Furthermore, PMMA has poor toughness; even small residual stresses can cause internal stress imbalances, inducing cracking. Currently, taillight cracking has become an industry-wide problem plaguing almost all automakers. Related technologies typically focus on improving the toughness of PMMA, but there are no reports of simultaneously improving both alcohol resistance and toughness. Therefore, developing a high-alcohol-resistant and high-toughness PMMA composite material is of great significance for expanding the application of PMMA in automotive taillight covers.

[0027] To address this issue, the present invention proposes a poly(meth)acrylate composite material that combines high alcohol resistance with high toughness, effectively reducing the problem of headlight cover cracking caused by the release of residual welding stress induced by ethanol.

[0028] Specifically, the first aspect of the present invention provides a poly(meth)acrylate composite material, comprising the following raw materials: 100 parts by weight of poly(meth)acrylate; 3-20 parts by weight of ethanol-resistant rubber; 0.02-0.4 parts by weight of vulcanizing agent; 0.1-0.5 parts by weight of antioxidant.

[0029] This invention uniformly blends poly(meth)acrylate (such as polymethyl methacrylate) with ethanol-resistant rubber. During dynamic vulcanization, the ethanol-resistant rubber gradually vulcanizes to form a three-dimensional network structure and is sheared into rubber particles (such as micron-sized particles) under strong shear, which are uniformly dispersed in the poly(meth)acrylate. When microcracks develop in the poly(meth)acrylate due to residual internal stress or external loads, the rubber particles can effectively absorb and dissipate energy, thereby effectively inhibiting the propagation of microcracks, significantly improving the toughness of the poly(meth)acrylate, and effectively reducing the risk of cracking. In addition, because the vulcanized rubber particles have a three-dimensional network structure, the ethanol-resistant rubber can effectively resist the penetration and swelling of ethanol, giving the composite material high alcohol resistance. Thus, the composite material of this invention combines high toughness and high alcohol resistance, effectively reducing the problem of headlight cover cracking caused by ethanol-induced welding residual stress release, reducing after-sales costs, maintaining brand performance, and improving driving safety. Furthermore, the amount of ethanol-resistant rubber introduced in this invention is small and will not have a significant impact on the mechanical and heat resistance properties of the poly(meth)acrylate.

[0030] In some embodiments, the amount of the ethanol-resistant rubber is 3 parts by weight, 5 parts by weight, 7 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 17 parts by weight, or 20 parts by weight, based on 100 parts by weight of poly(meth)acrylate.

[0031] In some specific embodiments, based on 100 parts by weight of poly(meth)acrylate, the amount of ethanol-resistant rubber is 10-17 parts by weight. The amount of ethanol-resistant rubber affects the toughness and alcohol resistance of the poly(meth)acrylate composite material. If the amount of ethanol-resistant rubber is too small, the improvement on the toughness and alcohol resistance of the poly(meth)acrylate composite material is not significant; if the amount of ethanol-resistant rubber is too large, it will reduce the mechanical properties of the poly(meth)acrylate composite material.

[0032] In some embodiments, based on 100 parts by weight of poly(meth)acrylate, the amount of the vulcanizing agent is 0.02 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, or 0.4 parts by weight. The vulcanizing agent initiates a crosslinking reaction, transforming the linear molecular structure of the ethanol-resistant rubber into a three-dimensional network structure, thereby effectively resisting ethanol penetration and swelling. The amount of vulcanizing agent is directly proportional to the amount of ethanol-resistant rubber used.

[0033] In some embodiments, the antioxidant is used in an amount of 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, or 0.5 parts by weight, based on 100 parts by weight of poly(meth)acrylate. This prevents degradation of the poly(meth)acrylate composite material during processing.

[0034] In some embodiments, the volume change rate ΔV of the ethanol-resistant rubber in ethanol solvent is below 20%. The smaller the volume change rate, the less likely ethanol is to penetrate into the ethanol-resistant rubber, which is more beneficial in mitigating the problem of cracking in the headlight cover.

[0035] In some specific embodiments, the volume change rate ΔV of the ethanol-resistant rubber in ethanol solvent is 1%, 5%, 10%, 15%, or 20%.

[0036] In some embodiments, the solvent-resistant rubber includes at least one of nitrile rubber and fluororubber. These ethanol-resistant rubbers can resist swelling by ethanol solutions, thereby forming poly(meth)acrylate composites with high toughness and high alcohol resistance.

[0037] In some specific embodiments, the nitrile rubber includes one or more of nitrile rubber, hydrogenated nitrile rubber, and carboxylated nitrile rubber.

[0038] Optionally, the nitrile rubber may be in one or more of the following forms: block, granules, powder, and liquid.

[0039] Optionally, the acrylonitrile content in the nitrile rubber can be low (18%-24%), medium (25%-35%), or high (36%-50%). The ethanol-resistant rubber may include nitrile rubber with one acrylonitrile content or multiple nitrile rubbers with different acrylonitrile contents.

[0040] In some specific embodiments, the fluororubbers include one or more of type 1-5 fluororubbers, perfluoroether rubbers, fluoroether rubbers, tetrapropylene fluororubbers, nitrosofluororubbers, and fluorosilicone rubbers.

[0041] Optionally, the fluororubber may be in one or more of the following forms: block, granules, powder, and liquid.

[0042] In some embodiments, the ethanol-resistant rubber is dispersed in the poly(meth)acrylate composite material in the form of micron-sized particles. When the ethanol-resistant rubber is dispersed in the poly(meth)acrylate composite material in the form of micron-sized particles, the rubber dispersion effect is good, which is more conducive to improving the toughness and alcohol resistance of the composite material.

[0043] In some embodiments, the poly(meth)acrylate includes one or more of polymethyl methacrylate, polymethyl methacrylate, polyethyl methacrylate, and polyethyl methacrylate.

[0044] Optionally, the polymethyl methacrylate includes one or more of (general purpose) transparent polymethyl methacrylate, toughened polymethyl methacrylate, flame retardant polymethyl methacrylate, and optical polymethyl methacrylate.

[0045] In some embodiments, the antioxidant includes one or more of hindered phenolic antioxidants, aromatic amine antioxidants, phosphite antioxidants, and thioester antioxidants. The present invention does not have a particular limitation on the specific type of antioxidant; commonly used antioxidants in the art can be used in the present invention. As a specific example, the antioxidant includes one or more of antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), BHT (butylated hydroxytoluene), antioxidant 1076 (octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), and antioxidant 1330 (tris(2,4-di-tert-butylphenyl)phosphite), etc. This prevents the decomposition of poly(meth)acrylates during processing.

[0046] In some embodiments, the vulcanizing agent includes one or more of sulfur-based vulcanizing systems, peroxide-based vulcanizing systems, and amine-based vulcanizing systems. This invention does not impose any particular limitation on the specific type of vulcanizing agent; commonly used vulcanizing agents in the art can be used in this invention. As specific examples, the vulcanizing agent includes one or more of DCP (dicumyl peroxide), AF-BPP (bisphenol A-benzyltriphenylphosphine chloride) vulcanizing systems, sulfur vulcanizing systems, sulfur donor vulcanizing systems, and metal oxide vulcanizing systems. This enables the linear molecular chains of ethanol-resistant rubber to undergo vulcanization crosslinking, forming a three-dimensional network structure.

[0047] A second aspect of the present invention provides a method for preparing the poly(meth)acrylate composite material of the first aspect of the present invention, comprising the following steps: Poly(meth)acrylate, ethanol-resistant rubber, antioxidant and vulcanizing agent are blended to obtain a mixed raw material; The mixed raw materials are melted, dynamically vulcanized, extruded, cooled, granulated, and dried to obtain the poly(meth)acrylate composite material.

[0048] The method of this invention is simple, low-cost, and highly repeatable, making it suitable for large-scale industrial application. The poly(meth)acrylate composite material prepared by this method combines high toughness and high alcohol resistance, effectively reducing the cracking problem of automotive headlight covers caused by ethanol-induced welding residual stress release.

[0049] In some embodiments, the blending is carried out in a blending apparatus. The blending apparatus includes one or more of an open mill, a tilting mixer, and a continuous mixer. This enables uniform mixing of the raw materials.

[0050] In some embodiments, the granulation is performed in a granulation apparatus. The granulation apparatus includes one or more of a reciprocating screw extruder, a twin-screw extruder, a three-screw extruder, a planetary extruder, and a single-screw extruder.

[0051] In some embodiments, the stirring speed during blending is 5 r / min to 200 r / min, for example, 5 r / min, 10 r / min, 50 r / min, 100 r / min, 150 r / min, or 200 r / min. The blending time is 15 seconds to 10 minutes, for example, 15 seconds, 30 seconds, 1 minute, 2 minutes, 4 minutes, 6 minutes, 8 minutes, or 10 minutes. This allows for the uniform mixing of the raw materials.

[0052] In some embodiments, the extrusion temperature is 150°C-250°C, for example, 150°C, 180°C, 200°C, 220°C, or 250°C. The extrusion is carried out in a screw extruder with a screw speed of 60 r / min-350 r / min, for example, 60 r / min, 100 r / min, 150 r / min, 200 r / min, 250 r / min, 300 r / min, or 350 r / min.

[0053] In some embodiments, the drying temperature is 40°C-60°C, for example 40°C, 45°C, 50°C, 55°C, or 60°C. Drying is performed until the moisture content is below 0.1%.

[0054] A third aspect of the present invention provides a vehicle headlight cover, comprising a poly(meth)acrylate composite material of the first aspect of the present invention or a poly(meth)acrylate composite material obtained by the method of the second aspect of the present invention.

[0055] Because of the use of the above-mentioned poly(meth)acrylate composite material, the headlight cover of the present invention has all the advantages of the poly(meth)acrylate composite material, which will not be repeated here.

[0056] In some embodiments, the headlight cover includes a welded rib portion; the material of the welded rib portion includes the poly(meth)acrylate composite material.

[0057] Since the main matrix of the poly(meth)acrylate composite material is poly(meth)acrylate, only a small amount of ethanol-resistant rubber particles need to be added. Therefore, the composite material has good compatibility with conventional poly(meth)acrylate, and its properties are close to those of conventional poly(meth)acrylate. Thus, it can be used in a two-color injection molding process with conventional poly(meth)acrylate as a welding rib material for automotive headlight covers, effectively avoiding the problem of headlight cover cracking caused by ethanol-induced release of welding residual stress.

[0058] A fourth aspect of the present invention provides a vehicle lamp, including the vehicle lamp cover of the third aspect of the present invention.

[0059] Because of the use of the above-mentioned poly(meth)acrylate composite material, the vehicle lamp of the present invention has all the advantages of the poly(meth)acrylate composite material, which will not be repeated here.

[0060] The fifth aspect of the present invention provides a vehicle including the headlights of the fourth aspect of the present invention.

[0061] Because of the use of the above-mentioned poly(meth)acrylate composite material, the vehicle of the present invention has all the advantages of the poly(meth)acrylate composite material, which will not be repeated here.

[0062] The present invention will be explained below with reference to embodiments. Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0063] The test method for the volume change rate ΔV of the rubber used in the following examples and comparative examples in ethanol solution is as follows: A standard-sized sample is cut, and its volume before immersion is measured and recorded as V1; the sample is completely immersed in the ethanol solution for 24 hours while maintaining a constant temperature; the sample is removed, the residual solution on the surface is wiped off, and the volume of the sample after immersion is measured and recorded as V2; the formula for calculating the volume change rate ΔV of rubber in ethanol solution is: .

[0064] Examples 1-5 According to the dosage of each component in Examples 1-5 in Table 1, polymethyl methacrylate, fluororubber (volume change rate ΔV of 4% in ethanol solution, purchased from 3M, brand name FT 2350), antioxidant 1010 and vulcanizing agent AF / BPP were added to a high-speed mixer and mixed for 5 min until uniform.

[0065] The uniformly blended raw materials were then fed into the feed port of a high aspect ratio twin-screw extruder for melting and dynamic vulcanization. The aspect ratio of the high aspect ratio twin-screw extruder was 60, and the temperatures of each heating zone were as follows: Zones 1-2: 150℃, Zones 3-6: 180℃, Zones 7-12: 210℃, Die temperature: 220℃, Extruder screw speed: 200 r / min, and Die pressure: 20 MPa. After extrusion, cooling, and granulation, the resulting granules were dried in a 50℃ oven to obtain a high alcohol-resistant and high-toughness polymethyl methacrylate composite material.

[0066] Examples 6-9 According to the dosage of each component in Examples 6-9 in Table 1, polymethyl methacrylate, nitrile rubber NBR18 (volume change rate ΔV of 14% in ethanol solution, purchased from Hualan Technology, brand name HLN18), antioxidant 1010 and vulcanizing agent DCP were added to a high-speed mixer and mixed for 5 min until uniform.

[0067] The uniformly blended raw materials were then fed into the feed port of a high aspect ratio twin-screw extruder for melting and dynamic vulcanization. The aspect ratio of the high aspect ratio twin-screw extruder was 60, and the temperatures of each heating zone were as follows: Zones 1-2: 150℃, Zones 3-6: 180℃, Zones 7-12: 200℃, Die temperature: 200℃, Extruder screw speed: 200 r / min, and Die pressure: 20 MPa. After extrusion, cooling, and granulation, the resulting granules were dried in a 50℃ oven to obtain a high alcohol-resistant and high-toughness polymethyl methacrylate composite material.

[0068] The SEM image of the polymethyl methacrylate composite material prepared in Example 7 is shown below. Figure 1 As shown, the rubber is dispersed in the composite material in the form of micron-sized particles. SEM images of other embodiments are also available. Figure 1 similar.

[0069] Example 10 According to the dosage of each component in Example 10 in Table 1, polymethyl methacrylate, nitrile rubber NBR25 (volume change rate ΔV of 13% in ethanol solution, purchased from Hualan Technology, brand name HLN25), antioxidant 1010 and vulcanizing agent DCP were added to a high-speed mixer and mixed for 5 minutes until uniform.

[0070] The uniformly blended raw materials were then fed into the feed port of a high aspect ratio twin-screw extruder for melting and dynamic vulcanization. The aspect ratio of the high aspect ratio twin-screw extruder was 60, and the temperatures of each heating zone were as follows: Zones 1-2: 150℃, Zones 3-6: 180℃, Zones 7-12: 200℃, Die temperature: 200℃, Extruder screw speed: 200 r / min, and Die pressure: 20 MPa. After extrusion, cooling, and granulation, the resulting granules were dried in a 50℃ oven to obtain a high alcohol-resistant and high-toughness polymethyl methacrylate composite material.

[0071] Example 11 According to the dosage of each component in Example 11 in Table 1, polymethyl methacrylate, nitrile rubber NBR35 (volume change rate ΔV of 11% in ethanol solution, purchased from Hualan Technology, brand name HLN35), antioxidant 1010 and vulcanizing agent DCP were added to a high-speed mixer and mixed for 5 minutes until uniform.

[0072] The uniformly blended raw materials were then fed into the feed port of a high aspect ratio twin-screw extruder for melting and dynamic vulcanization. The aspect ratio of the high aspect ratio twin-screw extruder was 60, and the temperatures of each heating zone were as follows: Zones 1-2: 150℃, Zones 3-6: 180℃, Zones 7-12: 200℃, Die temperature: 200℃, Extruder screw speed: 200 r / min, and Die pressure: 20 MPa. After extrusion, cooling, and granulation, the resulting granules were dried in a 50℃ oven to obtain a high alcohol-resistant and high-toughness polymethyl methacrylate composite material.

[0073] Example 12 According to the dosage of each component in Example 12 in Table 1, polymethyl methacrylate, nitrile rubber NBR45 (volume change rate ΔV of 10% in ethanol solution, purchased from Hualan Technology, brand name HLN45), antioxidant 1010 and vulcanizing agent DCP were added to a high-speed mixer and mixed for 5 minutes until uniform.

[0074] The uniformly blended raw materials were then fed into the feed port of a high aspect ratio twin-screw extruder for melting and dynamic vulcanization. The aspect ratio of the high aspect ratio twin-screw extruder was 60, and the temperatures of each heating zone were as follows: Zones 1-2: 150℃, Zones 3-6: 180℃, Zones 7-12: 200℃, Die temperature: 200℃, Extruder screw speed: 200 r / min, and Die pressure: 20 MPa. After extrusion, cooling, and granulation, the resulting granules were dried in a 50℃ oven to obtain a high alcohol-resistant and high-toughness polymethyl methacrylate composite material.

[0075] Examples 13-18 According to the dosage of each component in Examples 13-18 in Table 1, the polymethyl methacrylate, nitrile rubber NBR18 (volume change rate ΔV of 14% in ethanol solution, purchased from Hualan Technology, brand name HLN18), fluororubber (volume change rate ΔV of 4% in ethanol solution, purchased from 3M, brand name FT 2350), antioxidant 1010, vulcanizing agent DCP and vulcanizing agent AF / BPP from Example 16 were added to a high-speed mixer and mixed for 5 min until uniform.

[0076] The uniformly blended raw materials were then fed into the feed port of a high aspect ratio twin-screw extruder for melting and dynamic vulcanization. The aspect ratio of the high aspect ratio twin-screw extruder was 60, and the temperatures of each heating zone were as follows: Zones 1-2: 150℃, Zones 3-6: 180℃, Zones 7-12: 210℃, Die temperature: 220℃, Extruder screw speed: 200 r / min, and Die pressure: 20 MPa. After extrusion, cooling, and granulation, the resulting granules were dried in a 50℃ oven to obtain a high alcohol-resistant and high-toughness polymethyl methacrylate composite material.

[0077] Comparative Example 1 This comparative example provides a polymethyl methacrylate material, the preparation steps of which are as follows: According to the dosage of each component in Comparative Example 1 in Table 1, polymethyl methacrylate and antioxidant 1010 were added together into a high-speed mixer and mixed for 5 minutes until uniform.

[0078] The uniformly blended raw materials were then fed into the feed port of a high aspect ratio twin-screw extruder. The aspect ratio of the high aspect ratio twin-screw extruder was 60, and the temperatures of each heating zone were as follows: Zones 1-2: 150℃, Zones 3-6: 180℃, Zones 7-12: 200℃, Die temperature: 210℃, Extruder screw speed: 200 r / min, and Die pressure: 20 MPa. After extrusion, cooling, and granulation, the resulting granules were dried in a 50℃ oven to obtain polymethyl methacrylate (PMMA) material.

[0079] Comparative Example 2 This comparative example provides a polymethyl methacrylate composite material, the preparation steps of which are as follows: According to the dosage of each component in Comparative Example 2 in Table 1, polymethyl methacrylate, fluororubber (volume change rate ΔV of 4% in ethanol solution, purchased from 3M, brand name FT 2350), antioxidant 1010, and vulcanizing agent AF / BPP were added to a high-speed mixer and mixed for 5 minutes until uniform.

[0080] The uniformly blended raw materials were then fed into the feed port of a high aspect ratio twin-screw extruder for melting and dynamic vulcanization. The aspect ratio of the high aspect ratio twin-screw extruder was 60, and the temperatures of each heating zone were as follows: Zones 1-2: 150℃, Zones 3-6: 180℃, Zones 7-12: 210℃, Die temperature: 220℃, Extruder screw speed: 200 r / min, and Die pressure: 20 MPa. After extrusion, cooling, and granulation, the resulting granules were dried in a 50℃ oven to obtain polymethyl methacrylate composite material.

[0081] Comparative Example 3 This comparative example provides a polymethyl methacrylate composite material, the preparation steps of which are as follows: According to the dosage of each component in Comparative Example 3 in Table 1, polymethyl methacrylate, nitrile rubber NBR18 (volume change rate ΔV of 14% in ethanol solution, purchased from Hualan Technology, brand name HLN18), antioxidant 1010, and vulcanizing agent DCP were added to a high-speed mixer and mixed for 5 minutes until uniform.

[0082] The uniformly blended raw materials were then fed into the feed port of a high aspect ratio twin-screw extruder for melting and dynamic vulcanization. The aspect ratio of the high aspect ratio twin-screw extruder was 60, and the temperatures of each heating zone were as follows: Zones 1-2: 150℃, Zones 3-6: 180℃, Zones 7-12: 200℃, Die temperature: 200℃, Extruder screw speed: 200 r / min, and Die pressure: 20 MPa. After extrusion, cooling, and granulation, the resulting granules were dried in a 50℃ oven to obtain polymethyl methacrylate composite material.

[0083] Comparative Example 4 This comparative example provides a polymethyl methacrylate composite material, the preparation steps of which are as follows: According to the dosage of each component in Comparative Example 4 in Table 1, polymethyl methacrylate, nitrile rubber NBR18 (volume change rate ΔV of 14% in ethanol solution, purchased from Hualan Technology, grade HLN18), fluororubber, antioxidant 1010, vulcanizing agent DCP and vulcanizing agent AF / BPP were added to a high-speed mixer and mixed for 5 minutes until uniform.

[0084] The uniformly blended raw materials were then fed into the feed port of a high aspect ratio twin-screw extruder for melting and dynamic vulcanization. The aspect ratio of the high aspect ratio twin-screw extruder was 60, and the temperatures of each heating zone were as follows: Zones 1-2: 150℃, Zones 3-6: 180℃, Zones 7-12: 210℃, Die temperature: 220℃, Extruder screw speed: 200 r / min, and Die pressure: 20 MPa. After extrusion, cooling, and granulation, the resulting granules were dried in a 50℃ oven to obtain polymethyl methacrylate composite material.

[0085] Table 1

[0086] Performance testing (1) Melt index test of polymethyl methacrylate composite material The melt flow index test was conducted in accordance with GB / T 3682.1-2018. The test results are shown in Table 2 below.

[0087] (2) Tensile strength, notched impact strength and flexural modulus tests Before the mechanical property tests, the plastic standard samples were allowed to stand for 48 hours at (23±2)℃ and (50±5)% relative humidity, according to GB / T 1040.1-2018. Tensile strength (MPa) was tested according to GB / T 1040.1-2018. Notched impact strength was tested according to GB / T 1843-2008. Flexural modulus (MPa) was tested according to GB / T 9341-2008. The test results are shown in Table 3 below.

[0088] (3) Alcohol resistance test The alcohol resistance of plastic products was tested according to ASTM D1693. A standard dumbbell specimen was subjected to a 0.5% flexural strain and heated in a 60°C oven for 2 hours. After removal, it was completely immersed in a 60% ethanol solution, and the surface cracking of the standard specimen was observed. The test results are shown in Table 4 below.

[0089] Table 2

[0090] Table 2 shows that the melt index of PMMA in Comparative Example 1 was 7.7 without the addition of ethanol-resistant rubber and vulcanizing agent. After introducing the rubber phase, the melt index of the composite material decreased, as seen in Example 1 where it dropped to 7.1. The melt index of the composite material gradually decreased with increasing rubber content. This indicates that the processing fluidity of the composite material decreases with increasing rubber content, but remains within a suitable processing range.

[0091] Table 3

[0092] Table 3 shows that the notched impact strength of Comparative Example 1 (pure PMMA) is only 17 J / m. When the content of nitrile rubber is 5 parts by weight, the notched impact strength of Example 6 is 42.7 J / m, which is more than twice that of pure PMMA. At the same time, the tensile strength of the composite material is 82.2 MPa, which is consistent with the tensile strength of pure PMMA (80.5 MPa). This indicates that the introduction of nitrile rubber effectively improves the toughness of PMMA. As the content of nitrile rubber continues to increase to 20 parts by weight, the notched impact strength of Example 9 (46.8 J / m) actually decreases, which may be due to the poor compatibility between nitrile rubber and PMMA.

[0093] Comparing Examples 6 and 10-12, as the acrylonitrile content in the nitrile rubber increases, the tensile strength, notched impact strength, and flexural modulus of the composite material all show a trend of first increasing and then decreasing, indicating that nitrile rubber with high acrylonitrile content has a better toughening effect on PMMA. However, the acrylonitrile content should not be too high, as excessively high content will worsen the compatibility between nitrile rubber and PMMA, leading to a decrease in the mechanical properties of the composite material.

[0094] Comparing Examples 1-5 and Examples 13-17, fluororubber also has a good toughening effect on PMMA, and the mixing of fluororubber and nitrile rubber does not have an adverse effect on the mechanical properties of the composite material.

[0095] Table 4

[0096] Table 4 shows that the introduction of ethanol-resistant rubber effectively improved the alcohol resistance of PMMA. Even with only 3 parts by weight of nitrile rubber, the cracking phenomenon of PMMA in ethanol solvent environment was effectively improved. Pure PMMA (Comparative Example 1) cracked instantly upon immersion in ethanol solution; this may be because PMMA can swell in ethanol solution; some ethanol solution penetrates into the interstices of PMMA molecular chains, replacing the dipole-dipole interactions between the methyl acrylate side groups on the PMMA molecular chains and forming hydrogen bonds, which weakens the interactions between PMMA molecular chains, leading to stress imbalance inside PMMA, inducing residual stress release, and ultimately causing the sample to crack. After introducing ethanol-resistant nitrile rubber (volume change rate ΔV < 15% in ethanol solution) and fluororubber (volume change rate ΔV < 5% in ethanol solution), since they cannot be dissolved or swollen by ethanol solution, the rubber particles dispersed in PMMA can limit the penetration of ethanol solution into the PMMA / rubber particle composite material.

[0097] Meanwhile, when microcracks develop in PMMA due to stress imbalance, the rubber particles uniformly dispersed in the PMMA can effectively absorb and dissipate energy, preventing the microcracks from further propagating into cracks. Based on the improvement of PMMA's alcohol resistance and toughness by ethanol-resistant rubber, even adding a small amount of rubber component can effectively improve the cracking phenomenon of PMMA in ethanol solution environments.

[0098] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0099] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A poly(meth)acrylate composite material, characterized in that, The following raw materials are included in the preparation: 100 parts by weight of poly(meth)acrylate; 3-20 parts by weight of ethanol-resistant rubber; 0.02-0.4 parts by weight of vulcanizing agent; 0.1-0.5 parts by weight of antioxidant.

2. The poly(meth)acrylate composite material according to claim 1, characterized in that, The volume change rate ΔV of the ethanol-resistant rubber in ethanol solvent is below 20%.

3. The poly(meth)acrylate composite material according to claim 1 or 2, characterized in that, The ethanol-resistant rubber includes at least one of nitrile rubber and fluororubber; The nitrile rubber class includes one or more of nitrile rubber, hydrogenated nitrile rubber and carboxylated nitrile rubber; The fluororubbers include one or more of the following: type 1-5 fluororubber, perfluoroether rubber, fluoroether rubber, tetrapropylene fluororubber, nitrosofluororubber, and fluorosilicone rubber; Based on 100 parts by weight of the poly(meth)acrylate, the amount of the ethanol-resistant rubber is 10-17 parts by weight. The ethanol-resistant rubber is dispersed in the poly(meth)acrylate composite material in the form of micron-sized particles.

4. The poly(meth)acrylate composite material according to claim 1 or 2, characterized in that, The poly(meth)acrylate includes one or more of polymethyl methacrylate, polymethyl methacrylate, polyethyl methacrylate, and polyethyl methacrylate; optionally, the polymethyl methacrylate includes one or more of transparent polymethyl methacrylate, toughened polymethyl methacrylate, flame-retardant polymethyl methacrylate, and optical polymethyl methacrylate. The antioxidants include one or more of hindered phenolic antioxidants, aromatic amine antioxidants, phosphite antioxidants, and thioester antioxidants; The vulcanizing agent includes one or more of the following: sulfur-based vulcanization systems, peroxide-based vulcanization systems, and amine-based vulcanization systems.

5. A method for preparing the poly(meth)acrylate composite material according to any one of claims 1-4, characterized in that, Includes the following steps: Poly(meth)acrylate, ethanol-resistant rubber, antioxidant and vulcanizing agent are blended to obtain a mixed raw material; The mixed raw materials are melted, dynamically vulcanized, extruded, cooled, granulated, and dried to obtain the poly(meth)acrylate composite material.

6. The method according to claim 5, characterized in that, The stirring speed for blending is 5 r / min-200 r / min; the blending time is 15 seconds-10 minutes. The extrusion temperature is 150℃-250℃; The extrusion is carried out in a screw extruder with a screw speed of 60 r / min-350 r / min.

7. A vehicle headlight cover, characterized in that, The poly(meth)acrylate composite material included in any one of claims 1-4 or the poly(meth)acrylate composite material obtained by the method of claim 5 or 6.

8. The headlight cover according to claim 7, characterized in that, The headlight cover includes a welded rib portion; the material of the welded rib portion includes the poly(meth)acrylate composite material.

9. A vehicle light, characterized in that, Includes the headlight cover as described in claim 7 or 8.

10. A vehicle, characterized in that, Includes the vehicle lights as described in claim 9.

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