CN-121991448-A - Alcohol-resistant spraying-free PMMA/ASA material for automobile exterior trim and preparation method thereof

Abstract

The invention provides an alcohol-resistant and spraying-free PMMA/ASA material for automobile exterior trim and a preparation method thereof, wherein the alcohol-resistant and spraying-free PMMA/ASA material comprises, by weight, 50-65 parts of PMMA resin, 20-30 parts of ASA rubber powder, 5-15 parts of alcohol-resistant modifier, 0.1-0.5 part of initiator, 0.3-1.0 part of antioxidant, and 0.3-1.0 part of toner, wherein the alcohol-resistant modifier is ethyl methacrylate, the alcohol-resistant modifier is in a monomer form, the weight ratio of the ethyl methacrylate to the PMMA resin is 3 (11-39), the initiator is dicumyl peroxide and is used for realizing in-situ melt grafting of the ethyl methacrylate to the PMMA resin, and the weight ratio of dicumyl peroxide to the ethyl methacrylate is 1 (30-50).

Inventors

• LIU JIAREN
• LIAO HANG
• XU SHENG
• LI CHANGLIN
• WANG XIANPENG
• LIU SHUYANG

Assignees

• 南京聚隆科技股份有限公司
• 滁州聚隆新材料科技有限公司

Dates

Publication Date

20260508

Application Date

20260130

Claims (10)

1. 1. An alcohol-resistant and spraying-free PMMA/ASA material for automobile exterior trim is characterized by comprising PMMA resin, an alcohol-resistant modifier and an initiator; Wherein the alcohol-resistant modifier is cyclic ethyl methacrylate and is in a monomer form; The weight ratio of the methyl ethyl acrylate to the PMMA resin is 3 (11-39); the initiator is dicumyl peroxide and is used for realizing in-situ melt grafting of the cycloethyl methacrylate and the PMMA resin; the weight ratio of the dicumyl peroxide to the cycloethyl methacrylate is 1 (30-50).
2. 2. The alcohol-resistant and spraying-free PMMA/ASA material for automobile exterior trim according to claim 1, wherein the weight ratio of the cyclic ethyl methacrylate to the PMMA resin is 3 (11-15).
3. 3. The alcohol-resistant, spray-free PMMA/ASA material for automobile exterior trim according to claim 1, which is characterized by comprising the following components in parts by weight: 50-65 parts of PMMA resin; 20-30 parts of ASA rubber powder; 5-15 parts of alcohol-resistant modifier; 0.1-0.5 part of initiator; 0.3-1.0 part of antioxidant; 0.3-1.0 parts of toner.
4. 4. The alcohol-resistant and spray-free PMMA/ASA material for automobile exterior trim according to claim 3, wherein the PMMA resin has a melt flow rate of 1-16 g/10min under the test conditions of 230 ℃ and 3.8 kg.
5. 5. The alcohol-resistant and spraying-free PMMA/ASA material for automobile exterior trim according to claim 3, wherein the particle size of the ASA rubber powder is 100-500 nm, and the acrylate content is 40-55%.
6. 6. A method for preparing the alcohol-resistant, spray-free PMMA/ASA material for automotive exterior trim according to any one of claims 1 to 5, comprising the steps of: s1, uniformly mixing PMMA resin, an initiator, an antioxidant and toner to obtain a premix; S2, the premix is put into a main feeding port of a double-screw extruder, in the melt extrusion process of the double-screw extruder, an alcohol-resistant modifier is metered and injected through a liquid injection system arranged on a machine barrel of the double-screw extruder, ASA rubber powder is metered and added through a lateral feeder arranged on the machine barrel of the double-screw extruder and positioned at the downstream of the liquid injection system, and the PMMA/ASA material is obtained through melt extrusion, traction, cutting and granulation.
7. 7. The method for preparing the alcohol-resistant spraying-free PMMA/ASA material for automotive exterior trim according to claim 6, wherein in the step S2, the injection point of the liquid injection system is positioned in a third heating zone of the twin-screw extruder, and the feeding point of the lateral feeder is positioned in a fourth or sixth heating zone of the twin-screw extruder.
8. 8. The method for preparing the alcohol-resistant spraying-free PMMA/ASA material for the automotive exterior trim, which is disclosed in claim 6, is characterized in that in S2, the processing temperature of the twin-screw extruder is set to be 200-250 ℃ from a feeding section to a machine head, and the screw rotating speed of the twin-screw extruder is 300-600 r/min.
9. 9. The method for preparing an alcohol-resistant, spray-free PMMA/ASA material for automotive exterior trim according to claim 8, wherein in S2, the twin-screw extruder has at least nine temperature zones; The temperature of a first area of the twin-screw extruder is 100-150 ℃, the temperature of a second area of the twin-screw extruder is 200-220 ℃, the temperature of a third area, a fourth area and a fifth area of the twin-screw extruder is 220-240 ℃, the temperature of a sixth area, a seventh area, an eighth area and a ninth area of the twin-screw extruder is 220-240 ℃, and the temperature of a machine head is 230-250 ℃.
10. 10. The method for preparing the alcohol-resistant and spraying-free PMMA/ASA material for automobile exterior trim according to claim 6, wherein in S2, the temperature of the alcohol-resistant modifier is kept at 220-240 ℃ before injection.

Description

Alcohol-resistant spraying-free PMMA/ASA material for automobile exterior trim and preparation method thereof Technical Field The invention belongs to the technical field of high polymer materials, and relates to an alcohol-resistant spraying-free PMMA/ASA material for automobile exterior trim and a preparation method thereof. Background In recent years, PMMA/ASA alloy is a polymer material which is paid attention to in the field of automobiles, and excellent complementation in performance is achieved by combining the advantages of PMMA (Chinese term of polymethyl methacrylate) and ASA (Chinese term of acrylonitrile-styrene-acrylate copolymer). The material has the most outstanding advantages of elegant appearance and excellent durability, has high surface glossiness and high hardness brought by PMMA, can exhibit piano black paint spraying effect, inherits excellent ultraviolet resistance and weather resistance of ASA resin, can effectively resist aging, discoloration and chalking even if used in outdoor severe environment for a long time, and keeps stable color and luster. Based on the characteristics, PMMA/ASA alloy is widely applied to automobile exterior trimming parts, particularly in the design of pursuing high gloss, becomes an ideal substitute for traditional paint spraying parts, and is widely applied to parts such as radiator grids of automobile front faces, pillar trim of side windows, fog lamp covers, automobile logo bases and the like. The application of the material not only meets the aesthetic requirement of the automobile appearance design, realizes light weight so as to reduce oil consumption, but also avoids the problems of environmental pollution, low production efficiency and the like of the paint spraying part. While PMMA/ASA alloys possess many advantages, they have poor chemical resistance, particularly resistance to ethanol. Ethanol, a common polar organic solvent, can have a significant erosive effect on the material. When contacted with ethanol, particularly under certain stress, the surface of PMMA/ASA alloy is prone to "stress cracking", i.e., fine silver streaks or cracks, and even to overall cracking of the part. This can lead to reduced mechanical properties of the material, such as impaired strength and toughness, while the smooth surface of the product is susceptible to blushing defects, which can affect its aesthetics. This feature limits its application to applications that may be frequently exposed to alcohol-based formulations, such as automotive care cleaners, and the like, such as automotive exterior parts. CN119752081a discloses a high-transparency ethanol-resistant PMMA material and a preparation method thereof, in particular to a high-transparency ethanol-resistant PMMA material and a preparation method thereof, comprising PMMA resin, PACM12 resin, antioxidant and lubricant, wherein the high-transparency ethanol-resistant PMMA material is prepared by mixing the components and adding the components into a double screw extruder for melting, extruding and granulating. The microcrystalline PACM12 groups are embedded into PMMA through blending modification, so that the invasion of ethanol to a PMMA matrix can be effectively prevented, the material is prevented from being invaded by high-concentration ethanol, and meanwhile, the transparency of the PMMA material is not affected after the material is added. CN120399378a discloses an ethanol-resistant, spray-free, high brightness black ASA/PMMA material and its preparation method, comprising 50% -60% of PMMA resin, 20% -30% of ASA resin, 10% -20% of AS resin, 5% -15% of toughening agent, 0.5% -1.5% of antioxidant, 1% -2% of light stabilizer, 0.1% -0.5% of lubricant and 1% -2% of toner. The ethanol-resistant PMMA or ASA/PMMA alloy prepared by the above patent adopts a physical blending method, the principle is that the diffusion speed of ethanol to a PMMA substrate is slowed down by introducing microcrystals or SAN components with better ethanol resistance, the ethanol-resistant problem of the PMMA substrate cannot be fundamentally solved, and the third components such as a toughening agent and the like are introduced, because the refractive indexes are different, the transparency of the PMMA and the blackness of the PMMA/ASA alloy can be obviously influenced along with the change of temperature, and the practical application of the PMMA/ASA alloy is obviously influenced. In view of the above, development of an alcohol-resistant, high-brightness and black-free PMMA/ASA material for automobile exterior trim has important industrial application value and technical significance. Disclosure of Invention The invention aims to solve the defects of insufficient alcohol resistance and easy blushing of a highlight black spraying-free PMMA/ASA material in the prior art, provides a PMMA/ASA alloy which is simple in processing technology, alcohol-resistant and blushing-free and has good highlight black characteristics, and particularly