High black and bright weatherable pmma / asa composite material for vehicle and preparation method thereof

Abstract

The application belongs to the technical field of automobile polymer materials, and particularly relates to a high black and bright weather-resistant PMMA / ASA composite material for vehicles and a preparation method. The high black and bright weather-resistant PMMA / ASA composite material for vehicles is prepared from the following raw materials in parts by weight: 70-90 parts of PMMA resin, 15-25 parts of ASA resin, 3-5 parts of a compatilizer, 1.5-2.5 parts of color powder, 4-8 parts of a lubricant, and 5-7 parts of a light stabilizer. The PMMA resin has a weight average molecular weight of 60,000-100,000. The compatilizer comprises a styrene-maleic anhydride binary random copolymer. The lubricant is prepared by mixing pentaerythritol stearate and liquid paraffin at a mass ratio of 1: (2-3). The application improves the compatibility of the PMMA resin and the ASA resin, and improves the mechanical properties, gloss and weather resistance of the PMMA / ASA composite material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of automobile polymer materials, and particularly relates to a high-black-bright weather-resistant PMMA / ASA composite material for vehicles and a preparation method. BACKGROUND

[0002] In recent years, high-black-bright automobile interior and exterior trim parts have gradually been favored by consumers. The high-gloss surface effect of automobile exterior trim parts is difficult to achieve through direct injection molding, and a spraying process needs to be performed on the automobile exterior trim parts, but the spraying cost is high and a large amount of organic solvent is used in the spraying process, causing serious environmental pollution. Meanwhile, since the use state of the automobile interior and exterior trim parts is long-term high-temperature or strong sunlight irradiation, the heat resistance and weather resistance of the automobile interior and exterior trim part materials are required to be high. Therefore, it is of great significance to develop and design a weather-resistant high-black-bright spray-free automobile interior and exterior trim part material.

[0003] Poly(methyl methacrylate) (PMMA) resin is commonly known as organic glass or acrylic, has excellent optical properties, and the light transmittance can be as high as 92%. The PMMA resin also has excellent mechanical properties, weather resistance, strong coloring power, and scratch resistance, and stable chemical properties, and can resist low-concentration acids, alkalis and other general chemicals. Due to these remarkable characteristics, the PMMA resin is widely used in automobile window glass, covers, instrument glass, vehicle lamps, signs and other parts. However, the PMMA resin is brittle, and the notched impact strength is low. Butyl acrylate-styrene-acrylonitrile terpolymer (ASA) has similar structure and properties to acrylonitrile butadiene styrene (ABS), but the butyl acrylate is used to replace butadiene in the ASA resin, and there is no residual double bond, so the weather resistance of the ASA resin is significantly better than that of the ABS resin. The ASA resin also has good impact resistance, coloring property and chemical resistance, so it is widely used in automobile canopies, triangular blocks and column plates. The PMMA resin and the ASA resin can be blended by melting to prepare a high-gloss weather-resistant spray-free PMMA / ASA material.

[0004] However, the compatibility of the PMMA resin and the ASA resin is poor, so the mechanical properties of the PMMA / ASA material are difficult to meet the needs of the automobile field. SUMMARY

[0005] In order to improve the compatibility of the PMMA resin and the ASA resin, the application provides a high-black-bright weather-resistant PMMA / ASA composite material for vehicles and a preparation method.

[0006] In a first aspect, the application provides a high-black-bright weather-resistant PMMA / ASA composite material for vehicles, which is implemented by using the following technical scheme:

[0007] The application discloses a high-black-bright weather-resistant PMMA / ASA composite material for vehicles, which is prepared from the following raw materials in parts by weight: 70-90 parts of PMMA resin, 15-25 parts of ASA resin, 3-5 parts of a compatilizer, 1.5-2.5 parts of color powder, 4-8 parts of a lubricant and 5-7 parts of a light stabilizer.

[0008] The PMMA resin has a weight average molecular weight of 60,000-100,000.

[0009] The compatilizer comprises a styrene-maleic anhydride binary random copolymer.

[0010] The lubricant is prepared by mixing pentaerythritol stearate and liquid paraffin at a mass ratio of 1: (2-3).

[0011] By adopting the above technical scheme, the styrene-maleic anhydride binary random copolymer is used as the compatilizer, the compatibility of the PMMA resin and the ASA resin can be remarkably improved, the defects of the PMMA resin being too brittle and the ASA resin being poor in scratch resistance are improved, the notched impact strength and the scratch resistance of the PMMA / ASA composite material are improved, and the gloss of the PMMA / ASA composite material is also improved to a certain extent. The liquid paraffin and the pentaerythritol stearate are compounded as the lubricant, the internal and external lubricities are good, the weather resistance and the gloss of the PMMA / ASA composite material are improved, the PMMA resin has a good flowability and is easy to be processed and molded, the compatibility of the PMMA resin and the ASA resin is improved, and the notched impact strength and the scratch resistance of the PMMA / ASA composite material are improved.

[0012] The high-black-bright weather-resistant PMMA / ASA composite material for vehicles provided by the application can effectively improve the gloss of the material, effectively reduce the paint spraying process of subsequent products, is environment-friendly and pollution-free, has excellent weather resistance and scratch resistance, has good mechanical properties, and can meet the needs of resisting external environment.

[0013] Preferably, the compatilizer is prepared by mixing the styrene-maleic anhydride binary random copolymer and the core-shell structure organic silicon compatilizer at a mass ratio of 1: (0.3-0.4).

[0014] By adopting the above technical scheme, the core-shell structure organic silicon compatilizer has a soft and elastic crosslinked organic silicon core and a hard organic polymer shell, the styrene-maleic anhydride binary random copolymer and the core-shell structure organic silicon compatilizer are compounded, the compatibility of the PMMA resin and the ASA resin is remarkably improved, the notched impact strength of the PMMA / ASA composite material is improved, and the weather resistance and the scratch resistance of the PMMA / ASA composite material are improved.

[0015] Preferably, the core-shell structure organosilicon compatible agent is composed of organosilicon core-shell particles The core-shell structure high polymer H600 composed of P52, butyl acrylate, organosilicon and methyl methacrylate is mixed in a mass ratio of 1:(0.8-1.2).

[0016] By adopting the technical scheme, the organosilicon core-shell particles The core-shell structure high polymer H600 composed of P52, butyl acrylate, organosilicon and methyl methacrylate is mixed in a mass ratio of 1:(0.8-1.2).

[0017] Preferably, the mass ratio of the PMMA resin and the ASA resin is 80:21.

[0018] By adopting the technical scheme, the PMMA resin and the ASA resin are blended in a mass ratio of 80:21, and the notched impact strength and gloss of the PMMA / ASA composite material are improved.

[0019] Preferably, the ASA resin is composed of ASA-LP2065X and ASA-XCG15 mixed in a mass ratio of (15-25):1.

[0020] By adopting the technical scheme, the ASA-LP2065X and the ASA-XCG15 are compounded in a mass ratio of (15-25):1, the refractive index is close to 1.4, the compatibility with the PMMA-CM205 is good, the gloss and the notched impact strength of the PMMA / ASA composite material are significantly improved, and the scratch resistance and the weather resistance of the PMMA / ASA composite material are also improved to a certain extent.

[0021] Preferably, the mass ratio of the ASA-LP2065X and the ASA-XCG15 is 20:1.

[0022] By adopting the technical scheme, the solubility parameters of the ASA resin and the PMMA resin are close, the compatibility is good, the refractive index is close to 1.4, and the gloss, the notched impact strength and the scratch resistance of the PMMA / ASA composite material are significantly improved.

[0023] Preferably, the light stabilizer is composed of a light stabilizer UV770 and a light stabilizer UV-P mixed in a mass ratio of (0.9-1.1):1.

[0024] By adopting the technical scheme, the light stabilizer UV770 and the light stabilizer UV-P both belong to hindered amine light stabilizers, the two have different molecular weights, and the two are compounded to belong to macromolecular light stabilizers and low-molecular-weight light stabilizers, the low-molecular-weight light stabilizer is easy to disperse but has short time efficiency when being volatile, the macromolecular light stabilizer is not easy to disperse but has long time efficiency, and the light stabilizer UV770 and the light stabilizer UV-P are compounded to make the PMMA / ASA composite material have long-term weather resistance and short-term weather resistance.

[0025] Preferably, the preparation raw material of the high black and bright weather-resistant PMMA / ASA composite material for vehicles further comprises 1.5-2.5 parts by weight of the antioxidant.

[0026] By adopting the technical scheme, the addition of the antioxidant improves the weather resistance of the PMMA / ASA composite material.

[0027] In the application, the toner C-01 is a toner for piano black prepared by using organic dyes of eight levels of light fastness according to the three primary colors of red, yellow and blue, and has the advantages of good dispersibility, high blackness and good weather resistance.

[0028] In a second aspect, the application provides a preparation method of a high black and bright weather-resistant PMMA / ASA composite material for vehicles, which adopts the following technical scheme:

[0029] The preparation method of the high black and bright weather-resistant PMMA / ASA composite material for vehicles comprises the following steps:

[0030] S1, uniformly mixing PMMA resin, ASA resin, a compatibilizer and a lubricant, then adding toner, a light stabilizer and an antioxidant, and uniformly mixing to obtain a resin mixture;

[0031] S2, melting, extruding and granulating the resin mixture in S1 to obtain the high black and bright weather-resistant PMMA / ASA composite material for vehicles.

[0032] The preparation process of the high black and bright weather-resistant PMMA / ASA composite material for vehicles is simple, is suitable for industrial production, can achieve the effect of piano black without spraying, and has excellent weather resistance, high gloss, impact resistance, scratch resistance, high toughness and dimensional stability, and can be applied to automobile grille, outer rearview mirror shell and mirror shell base, outer column trim panel, tail lamp decoration strip, interior navigation instrument frame and other parts, and has a wide application prospect.

[0033] In summary, the application has the following beneficial effects:

[0034] 1, the application adopts a styrene-maleic anhydride binary random copolymer as a compatibilizer, which can significantly improve the compatibility of PMMA resin and ASA resin, and improve the defects of brittle PMMA resin and poor scratch resistance of ASA resin.

[0035] 2、The application uses liquid paraffin and pentaerythritol stearate as a complex lubricant to improve the weather resistance and gloss of the PMMA / ASA composite material.

[0036] 3、The application uses PMMA resin with a weight average molecular weight of 60000-100000, which has good flowability and is easy to process, which is beneficial to improve the compatibility of PMMA resin and ASA resin.

[0037] 4、The application uses a complex of styrene-maleic anhydride binary random copolymer and core-shell structure silicone compatibilizer to improve the compatibility of PMMA resin and ASA resin, thereby improving the notched impact strength, weather resistance and scratch resistance of the PMMA / ASA composite material.

[0038] 5、The application uses ASA-LP2065X and ASA-XCG15 in a mass ratio of (15-25):1 to improve the compatibility of PMMA resin and ASA resin. DETAILED DESCRIPTION

[0039] The application will be further described below in combination with examples.

[0040] Preparation Example

[0041] Preparation Example 1-5 provides a compatibilizer, which is described below taking Preparation Example 1 as an example.

[0042] The compatibilizer provided by Preparation Example 1 has the following preparation steps:

[0043] Mix 10 kg of styrene-maleic anhydride binary random copolymer (maleic anhydride grafting rate is 18 wt%) and 3 kg of silicone core-shell particles P52 (purchased from Wacker, Germany) uniformly to obtain the compatibilizer.

[0044] Preparation Example 2 differs from Preparation Example 1 only in that the mass of the silicone core-shell particles P52 is 4 kg.

[0045] Preparation Example 3 differs from Preparation Example 2 only in that the silicone core-shell particles P52 is replaced by a core-shell structure polymer H600 (purchased from Dongguan Chuangzhengyuan New Material Technology Co., Ltd.) composed of butyl acrylate, silicone and methyl methacrylate in the same mass.

[0046] The compatibilizer provided by Preparation Example 4 has the following preparation steps:

[0047] Mix 10 kg of styrene-maleic anhydride binary random copolymer, 2.2 kg of silicone core-shell particles P52 and 1.8 kg of butyl acrylate, silicone, methyl methacrylate core-shell structured high molecular polymer H600 were mixed uniformly to obtain the compatilizer.

[0048] Preparation Example 5 differs from Preparation Example 4 only in that the silicone core-shell particles The mass of P52 was 1.8 kg, and the mass of butyl acrylate, silicone, methyl methacrylate core-shell structured high molecular polymer H600 was 2.2 kg.

[0049] Example

[0050] Examples 1-17 provide a high black and bright weather-resistant PMMA / ASA composite material for vehicles, which is described below by taking Example 1 as an example.

[0051] Example 1 provides a high black and bright weather-resistant PMMA / ASA composite material for vehicles, and the preparation steps are as follows:

[0052] S1, 70 kg of PMMA-CM205 (weight average molecular weight 80000, purchased from Qimei, Taiwan, China), 15 kg of ASA-LP2065X (refractive index 1.55, purchased from Guangzhou Enteng), 3 kg of styrene-maleic anhydride binary random copolymer (maleic anhydride grafting rate 18wt%), 1.3 kg of pentaerythritol stearate and 2.7 kg of liquid paraffin were mixed, stirred at 400 rpm for 5 min, then 1.5 kg of color powder C-01, 5 kg of light stabilizer UV770 and 1.5 kg of BASF antioxidant B900 were added, mixed and stirred at 400 rpm for 10 min to obtain a resin mixture;

[0053] S2, the resin mixture of S1 was added to a twin-screw extruder, melted and extruded, and the extrusion conditions of the twin-screw extruder were as follows: the temperature of the first stage of the twin-screw extruder was 180℃, the temperature of the second stage was 200℃, the temperature of the third stage was 220℃, the temperature of the fourth stage was 220℃, the temperature of the fifth stage was 225℃, the temperature of the die head was 230℃, the barrel temperature of the twin-screw extruder was controlled at 230℃, the main machine frequency was 30 Hz, the feeding frequency was 10 Hz, and the vacuum degree of the vacuum system of the twin-screw extruder was maintained at-0.05 MPa. The extruded material was cooled to 35℃ and sent to a pelletizer (pelletizer speed 400 rpm) to obtain a high black and bright weather-resistant PMMA / ASA composite material for vehicles.

[0054] Examples 2-5 differ from Example 1 only in that the mass of each preparation raw material is different, as shown in Table 1.

[0055] Table 1 Mass of each preparation raw material of Examples 1-5 / kg

[0056]

[0057] Example 6 differs from Example 5 only in that the ASA-LP 2065X is replaced by an equal mass of ASA-XCG 15 (purchased from Korea Kumho).

[0058] Example 7 differs from Example 5 only in that the ASA resin is a mixture of 19.7 kg of ASA-LP 2065X and 1.3 kg of ASA-XCG 15.

[0059] Example 8 differs from Example 7 only in that the mass of ASA-LP 2065X is 20.2 kg and the mass of ASA-XCG 15 is 0.8 kg.

[0060] Example 9 differs from Example 7 only in that the mass of ASA-LP 2065X is 20 kg and the mass of ASA-XCG 15 is 1 kg.

[0061] Example 10 differs from Example 7 only in that the mass of ASA-LP 2065X is 1 kg and the mass of ASA-XCG 15 is 21 kg.

[0062] Example 11 differs from Example 9 only in that the compatibilizer is the compatibilizer prepared in Preparation Example 1.

[0063] Examples 12-15 differ from Example 11 only in that the source of the compatibilizer is different, as shown in Table 2.

[0064] Table 2 Sources of compatibilizer for Examples 11-15

[0065] Group Example 11 Example 12 Example 13 Example 14 Example 15 Compatibilizer source Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5

[0066] Example 16 differs from Example 15 only in that the light stabilizer UV770 is replaced by an equal mass of light stabilizer UV-P.

[0067] Example 17 differs from Example 15 only in that the light stabilizer is a mixture of 3 kg of light stabilizer UV770 and 3 kg of light stabilizer UV-P.

[0068] Comparative Example

[0069] Comparative Example 1 differs from Example 1 only in that the PMMA-CM 205 is replaced by an equal mass of ultra-high molecular weight PMMA (trade designation Altuglas BS 150N, purchased from Arkema, France).

[0070] Comparative Example 2 differs from Example 1 only in that the pentaerythritol stearate is replaced by an equal mass of liquid paraffin.

[0071] Comparative Example 3 differs from Example 1 only in that the liquid paraffin is replaced by equal mass of pentaerythritol stearate.

[0072] Comparative Example 4 differs from Example 1 only in that the styrene-maleic anhydride binary random copolymer is not added.

[0073] Performance detection test

[0074] The high black and bright weather-resistant PMMA / ASA composite materials for vehicles prepared in Examples 1-17 and Comparative Examples 1-4 of the present application were respectively added into an injection molding machine to be injection molded to prepare ISO standard samples and color plates, and the following performance detection was carried out.

[0075] 1. Notched impact strength: The notched impact strength of a simple supported beam was tested according to ISO 179-1 standard, the sample size was 80x10x4mm, and the test results are shown in Table 3.

[0076] 2. Scratch resistance: The change of L value before and after scratching was tested according to the method 1 of GMW14688, the load was 10N, the smaller the △L value, the better the scratch resistance, and the test results are shown in Table 3.

[0077] 3. Weather resistance: The weather resistance test was carried out according to the test conditions in SAE J2527-2004 "Performance Standard for Accelerated Exposure of Automotive Exterior Materials by Irradiation Xenon Arc Apparatus", the test conditions were: irradiance of 0.55W / (m 2 .nm) under 340nm (radiation intensity device default light emission), total exposure energy of 2500kJ / m 2 , total test time of 1894h, and the color difference value (DE* value) before and after the test was recorded, and the test results are shown in Table 3.

[0078] 4. Gloss: The gloss was tested according to ASTM D523 standard, the test angle was 60°, and the test results are shown in Table 3.

[0079] Table 3 test results

[0080]

[0081] The following details the present application according to the test data in Table 3.

[0082] From the test data of Example 1 and Comparative Example 1, it can be seen that the ultra-high molecular weight PMMA has poor flowability, the solubility parameter of the PMMA resin and the ASA resin is quite different, which reduces the compatibility of the PMMA resin and the ASA resin, and in addition, the ultra-high molecular weight PMMA is difficult to form, which reduces the gloss, notched impact strength and scratch resistance of the PMMA / ASA composite material.

[0083] From the test data of Example 1 and Comparative Examples 2-3, it can be seen that the liquid paraffin and pentaerythritol stearate compound as a lubricant improves the notched impact strength, gloss, scratch resistance and weather resistance of the PMMA / ASA composite material.

[0084] From the test data of Example 1 and Comparative Example 4, it can be seen that the addition of the styrene-maleic anhydride binary random copolymer significantly improves the compatibility of the PMMA resin and the ASA resin, effectively improves the defects of poor impact performance of the PMMA resin and poor scratch resistance of the ASA resin, and improves the notched impact strength, scratch resistance, gloss and weather resistance of the PMMA / ASA composite material.

[0085] From the test data of Examples 4-5, it can be seen that the blending of the PMMA resin and the ASA resin with a mass ratio of 80:21 improves the notched impact strength and gloss of the PMMA / ASA composite material.

[0086] From the test data of Examples 5-7, it can be seen that the ASA-LP2065X and the ASA-XCG15 compound have a refractive index close to 1.4, which can significantly improve the light transmittance of the PMMA / ASA composite material, and the compatibility of the ASA resin with the PMMA-CM205 is good, which can significantly improve the gloss and notched impact strength of the PMMA / ASA composite material, and the scratch resistance and weather resistance are also improved to a certain extent.

[0087] From the test data of Examples 7-10, it can be seen that the mass ratio of ASA-LP2065X and ASA-XCG15 is 20:1, which makes the solubility parameter of the ASA resin close to that of the PMMA-CM205, has good compatibility, and the refractive index is close to 1.4, which significantly improves the gloss and notched impact strength of the PMMA / ASA composite material, and to a certain extent, improves the scratch resistance and weather resistance of the PMMA / ASA composite material.

[0088] From the test data of Examples 9, 11-12, it can be seen that the compatibility agent of the styrene-maleic anhydride binary random copolymer and the core-shell structure silicone compatibility agent significantly improves the compatibility of the PMMA resin and the ASA resin, thereby improving the notched impact strength, weather resistance and scratch resistance of the PMMA / ASA composite material.

[0089] From the test data of Examples 12-14, it can be seen that the core-shell structure organic silicon particle The core-shell structure polymer H600 composed of P52, butyl acrylate, organic silicon and methyl methacrylate is compounded, which improves the weather resistance and notched impact strength of the PMMA / ASA composite material.

[0090] The embodiments are only illustrative of the present application, and are not intended to limit the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A high black and bright weatherable PMMA / ASA composite material for vehicles, characterized in that, The raw materials for preparing the high black and bright weather-resistant PMMA / ASA composite material include 70-90 parts by weight of PMMA resin, 15-25 parts by weight of ASA resin, 3-5 parts by weight of compatibilizer, 1.5-2.5 parts by weight of color powder, 4-8 parts by weight of lubricant and 5-7 parts by weight of light stabilizer; The PMMA resin has a weight average molecular weight of 60000-100000; The lubricant is prepared by mixing pentaerythritol stearate and liquid paraffin at a mass ratio of 1: (2-3) ; The ASA resin is prepared by mixing ASA-LP2065X and ASA-XCG15 at a mass ratio of (15-25):1; The compatibilizer is prepared by mixing styrene-maleic anhydride binary random copolymer and core-shell structure organic silicon compatibilizer at a mass ratio of 1: (0.3-0.4) ; The core-shell structure silicone compatibilizer is prepared from the core-shell structure silicone particles GENIOPERL ® P52 and the core-shell structure high molecular polymer H600 composed of butyl acrylate, silicone and methyl methacrylate are mixed in a mass ratio of 1: (0.8-1.2); The mass ratio of the PMMA resin and the ASA resin is 80:

21.

2. The high black bright weatherable PMMA / ASA composite material for vehicles according to claim 1, characterized in that, The mass ratio of the ASA-LP2065X and the ASA-XCG15 is 20:

1. 3.The high black bright weatherable PMMA / ASA composite material for vehicles according to claim 1, characterized in that, The light stabilizer is prepared by mixing light stabilizer UV770 and light stabilizer UV-P at a mass ratio of (0.9-1.1):

1. 4.The high black bright weatherable PMMA / ASA composite material for vehicles according to any one of claims 1-3, characterized in that, The raw materials further include 1.5-2.5 parts by weight of antioxidant.

5. The preparation method of the high black-bright weatherable PMMA / ASA composite material for vehicles according to claim 4, characterized in that, The method comprises the following steps: S1, uniformly mixing the PMMA resin, the ASA resin, the compatibilizer and the lubricant, and then adding the color powder, the light stabilizer and the antioxidant, and uniformly mixing to obtain a resin mixture; S2, melting, extruding and granulating the resin mixture to obtain the high black and bright weather-resistant PMMA / ASA composite material.

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