Spraying-free ASA / PMMA alloy with long-acting antistatic property, high heat resistance and long weather resistance and preparation method of spraying-free ASA / PMMA alloy

Abstract

The invention discloses a long-acting antistatic, high-heat-resistant and long-weather-resistant spraying-free ASA / PMMA (Acrylonitrile Styrene Acrylate / Polymethyl Methacrylate) alloy and a preparation method thereof, and the alloy comprises the following components in parts by weight: 40-70 parts of polymethyl methacrylate (PMMA) resin, 10-20 parts of acrylonitrile-styrene-acrylate (ASA) resin, 10-20 parts of ACR resin, 1-10 parts of antistatic resin, 1-3 parts of modified zinc oxide and 0.5-2 parts of a compatibility accelerant. 5-10 parts of a heat-resistant agent, 0-1 part of an antioxidant, 0-1 part of a light stabilizer and 0-2 parts of toner. The ASA / PMMA alloy resin prepared by the invention solves the problem of dust absorption caused by static electricity generated by plastic characteristics in a consumer use process or a part storage process, also solves the problem of mutual restriction of basic properties such as heat resistance, blackness, weather resistance and the like, and can directly replace a product which is toned by paint spraying; the method is particularly suitable for parts such as stand columns, grilles and peripheral ornaments thereof, and rear protectors and peripheral bright decorative strips thereof.

Description

Technical Field

[0001] The present invention relates to the field of thermoplastic composites, and particularly to a long-lasting antistatic, highly heat-resistant, long-weather-resistant spray-free ASA / PMMA alloy and a preparation method thereof. Background Art

[0002] PMMA resin has characteristics such as high weather resistance, high transparency, and high hardness, and is also particularly excellent in dyeing performance; structure determines properties, so PMMA has very poor toughness under the characteristics of its structure, and its notch impact strength (ISO179) is within 3 Kj / m 2 and cannot meet the requirement for sole use in automobiles. Usually, it needs to be welded with other skeletons or double-shot injection molded, but this will increase the subsequent cost and the yield of the produced finished products will not be high either. By introducing acrylate into the styrene-acrylonitrile copolymer, ASA is endowed with high weather resistance and excellent toughness. However, due to the introduction of the third component, its dyeing performance becomes poor, which limits its application scope; as consumers' aesthetic requirements are constantly improving, there are demands for high gloss, multiple colors, etc. However, with the increasing environmental protection requirements, the previous processes such as spraying and electroplating have become more and more harmful to the environment, while the ASA / PMMA alloy material combines the advantages of the two materials and shows excellent competitive advantages in replacing processes such as painting and electroplating. However, due to the inherent characteristics of ASA / PMMA plastics, their antistatic effect is very poor. When consumers use them, they often attract dust, which affects the use effect. Therefore, it is imperative to develop antistatic, highly heat-resistant, and long-lasting spray-free ASA / PMMA.

[0003] Chinese Patent CN 116218117 A discloses a fingerprint-resistant and high-gloss black PMMA / ASA composition and a preparation method thereof. It uses PA66-g-MAH to improve the fingerprint-resistant effect. Although the fingerprint-resistant effect is improved to some extent, its heat resistance and antistatic effect are not improved. In addition, due to the introduction of PA, the weather resistance of the ASA-PMMA alloy will be significantly sacrificed.

[0004] Chinese Patent CN 111690222 A discloses the use of ultra-high molecular weight PMMA and N-phenylmaleimide to improve the heat resistance of the ASA / PMMA alloy. However, the toughness of the ASA / PMMA alloy is severely affected. In addition, the obtained alloy material still cannot solve the problem of the antistatic property of the material.

[0005] Although the above-mentioned solutions improve certain aspects of the performance of the ASA / PMMA alloy, they often sacrifice one of the properties such as the toughness, weather resistance, heat resistance, and blackness of the material to meet other properties. The obtained products have no antistatic effect and seriously affect the use of consumers. Summary of the Invention

[0006] The present invention provides a long-lasting antistatic, highly heat-resistant, long weather-resistant spray-free ASA / PMMA alloy in view of the deficiencies of the prior art, as well as a preparation method for this alloy.

[0007] The technical solution for the present invention to solve the above-mentioned technical problems is to provide a long-lasting antistatic, highly heat-resistant, long weather-resistant spray-free ASA / PMMA alloy, which is prepared from the following raw materials by weight:

[0008] 40-70 parts of polymethyl methacrylate (PMMA) resin;

[0009] 10-20 parts of acrylonitrile-styrene-acrylate (ASA) resin;

[0010] 10-20 parts of ACR resin;

[0011] 1-10 parts of antistatic resin;

[0012] 1-3 parts of modified zinc oxide;

[0013] 0.5-2 parts of compatibility promoter;

[0014] 5-10 parts of heat-resistant agent;

[0015] 0-1 part of antioxidant;

[0016] 0-1 part of light stabilizer;

[0017] 0-2 parts of color powder.

[0018] In the above ASA / PMMA alloy,

[0019] As an example, the melt index of the resin is between 1 and 5, and the polydispersity coefficient is between 1 and 2.

[0020] As an example, the ASA resin is composed of rubber powder with large and small particle sizes. The size range of the large particle size of the ASA resin is between 350 and 450 μm, and the acrylate content is between 50 and 70%. The size range of the small particle size of the ASA resin is between 150 and 200 μm, and the acrylate content is between 50 and 70%.

[0021] As an example selection, the heat-resistant agent is one or several of MMA-SMA, SAN-SMA, SAN-MMA-SMA, and AS-SMA copolymers. The molecular weight range of the SAN-MMA-SMA and AS-MMA-SMA copolymers is 70,000 - 120,000, and the polydispersity coefficient is 2 - 3, where the MMA content is 30 - 35%. The molecular weight range of the heat-resistant agents SAN-SMA and AS-SMA copolymers is 90,000 - 160,000, and the polydispersity coefficient is 1 - 3, where the SMA content is 15 - 18%.

[0022] As an example selection, the ACR core-shell structured acrylate copolymer. The ACR core-shell structured acrylate copolymer has an acrylate as the core, and the acrylate is butyl acrylate, serving as the rubber phase with a particle size of 30 - 80 μm and an acrylate content of 78 - 80%. The ACR core-shell structured acrylate copolymer has methyl methacrylate as the shell.

[0023] As an example selection, the long-lasting antistatic agent is a PA matrix, and the PA is PA11. The refractive index of PA11 is 1.52, and the molecular weight is 11,000 - 16,000. By grafting maleic anhydride onto PA11, the maleic anhydride grafting rate is 0.5 - 1%.

[0024] As an example selection, the modified zinc oxide is modified with siloxane, the silicon content is more than 5%, and the particle size of the modified zinc oxide is 60 - 80 nm

[0025] As an example selection, the compatibility promoter is a styrene-acrylonitrile-glycidyl methacrylate copolymer (SAG) resin, and the glycidyl methacrylate copolymer content is 40 - 45%. The effective epoxy content in the glycidyl methacrylate is 85 - 90%.

[0026] As an example selection, the antioxidant is a compound of phosphite or hindered phenol antioxidants.

[0027] As an example selection, the light stabilizer is one or several of ultraviolet absorbers and free radical scavengers.

[0028] As an example selection, the color powder is a compound through one or multiple compoundings other than carbon black.

[0029] The following examples include the following production steps

[0030] (1) Mix 40 - 70 parts of PMMA with 1 - 10 parts of modified antistatic resin, 5 - 10 parts of heat-resistant agent, 1 - 3 parts of modified zinc oxide, 0 - 1 part of antioxidant, and 0.5 - 2 parts of compatibility promoter in a high-speed premixer to obtain premix A;

[0031] (2) Premix 10 - 20 parts of ASA, 10 - 20 parts of ACR resin, light stabilizer, 0 - 2 parts of color powder, and 0 - 1 part of light stabilizer in a high-speed premixer to obtain premix B;

[0032] (3) Then, pass the premixed A mixed material through a twin-screw extruder, quantitatively convey B through a metering pump by side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 300 - 600 revolutions / min, and after cooling and pelletizing, under the condition that the pelletizer speed is 800 - 1000 revolutions / min, a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy can be obtained.

[0033] In the present invention, by adjusting the proportions of ASA, PMMA, and heat-resistant agent, a basic ASA / PMMA alloy material is formed through compounding of different proportions of ASA. Meanwhile, PA11 grafted maleic anhydride, compatibility promoter, and modified zinc oxide are introduced. Maleic anhydride can react with the ester groups of ASA and PMMA, and the grafted modified PA11 forms a through-network distribution in the ASA and PMMA alloy to form a conductive path. The silicon-oxygen alkane-modified oxidizing property is evenly distributed in the through-network formed by the modified PA11 to provide a stable conductive path; the styrene-acrylonitrile part in the compatibility promoter is partially embedded in ASA and the heat-resistant agent, and glycidyl methacrylate reacts with maleic anhydride, PMMA, and the acrylate of the heat-resistant agent, ultimately promoting the compatibility of the overall material; by strictly controlling the acrylate content of the ACR resin with a core-shell structure ratio, the weather resistance loss problem caused by the introduction of the modified PA11 and heat-resistant agent is significantly improved. After screw extrusion and pelletizing, an ASA / PMMA alloy material with high toughness, high heat resistance, high blackness, and high laser transmittance and applicable to laser welding can be obtained.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] 1. In the present invention, the proportions of ASA and PMMA are adjusted by means of coextrusion blending, and the dispersion effect of ASA in PMMA is improved by compounding ASA rubber powder with different particle sizes.

[0036] 2. The modified PA11 with a specific refractive index can be evenly dispersed in the ASA / PMMA alloy, providing a through-conductive path without affecting the appearance of the modified material; at the same time, the modified zinc oxide can be well dispersed in the modified resin, providing a stable conductive effect.

[0037] 3. The styrene-acrylonitrile portion in the compatibility promoter is partially embedded in ASA and the heat-resistant agent, and glycidyl methacrylate reacts with maleic anhydride, PMMA, and the acrylate of the heat-resistant agent, ultimately promoting the compatibility of the overall material.

[0038] 4. The ACR resin with a strictly controlled acrylate content in the core-shell structure significantly improves the weather resistance loss caused by the introduction of modified PA11 and the heat-resistant agent. While enhancing the weather resistance of the modified plastic, it can also be well compatible with ASA and PMMA resins without causing phase separation.

[0039] 5. By changing the processing method, more stable ASA / PMMA is obtained.

[0040] The preparation process of the present invention is very simple and low in cost, and is particularly suitable for industrial production. Specific Embodiments

[0041] The following gives specific implementation examples of the present invention. The specific embodiments are only used to further illustrate the present invention and do not limit the protection scope of the patent application.

[0042] The present invention provides a preparation method of a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy for the deficiencies of the prior art, which comprises the following components:

[0043] 40 - 70 parts of polymethyl methacrylate (PMMA) resin, the melt index of the PMMA resin is between 1 - 5, and the polydispersity coefficient is between 1 - 2.

[0044] 10 - 20 parts of acrylonitrile-styrene-acrylate (ASA) resin, the ASA resin is composed of rubber powders of large and small particle sizes. The size range of the large particle size of the ASA resin is between 350 - 450 um, and the acrylate content is between 50 - 70%; the size range of the small particle size is between 150 - 200 um, and the acrylate content is between 50 - 70%.

[0045] 10 - 20 parts of ACR resin, a core-shell structured acrylate copolymer. The core-shell structured acrylate copolymer of ACR uses acrylate as the core, and the acrylate is butyl acrylate, serving as the rubber phase with a particle size of 30 - 80 um and an acrylate content of 78 - 80%; methyl methacrylate is the shell.

[0046] 1 - 10 parts of antistatic resin, the matrix used is PA11, where the refractive index of PA11 is 1.52, the molecular weight is 11000 - 16000, and PA11 is modified with maleic anhydride, and the maleic anhydride grafting rate is 0.5 - 1%.

[0047] 1 - 3 parts of modified zinc oxide, the modified zinc oxide is siloxane - modified, with a silicon content of more than 5%, and the particle size of the modified zinc oxide is 60 - 80 nm.

[0048] 0.5 - 2 parts of compatibilizing promoter, the compatibilizer is styrene - acrylonitrile - glycidyl methacrylate copolymer (SAG) resin, with a glycidyl methacrylate copolymer content of 40 - 45% and an effective epoxy content of 85 - 90%.

[0049] 5 - 10 parts of heat - resistant agent, the heat - resistant agent is one or more of MMA - SMA, SAN - SMA, SAN - MMA - SMA, AS - SMA copolymers. For SAN - MMA - SMA and AS - MMA - SMA copolymers, the molecular weight range is 70000 - 120000 and the polydispersity index is 2 - 3, with an MMA content of 30 - 35%; for SAN - SMA and AS - SMA copolymers, the molecular weight range is 90000 - 160000 and the polydispersity index is 1 - 3, with an SMA content of 15 - 18%.

[0050] 0 - 1 part of antioxidant, the antioxidant is a compound of phosphite - type or hindered - phenol - type antioxidants.

[0051] 0 - 1 part of light stabilizer, the light stabilizer is one or more of ultraviolet absorbers and free - radical scavengers.

[0052] 0 - 2 parts of color powder, the color powder is a compound of one or more organic color powders except carbon black.

[0053] The sources of the raw materials used in the examples of the present invention are as follows: PMMA from Arkema VO40; ASA from Entropy LP2068; ACR resin from Kaneka M210; antistatic resin from Xuyang Chemical 5502MP; compatibilizing promoter from Jiayi Rong SAG002; heat - resistant agent from POLYSCOPE SO20680.

[0054] The following examples include the following production steps:

[0055] (1) Mix 40 - 70 parts of PMMA, 1 - 10 parts of modified antistatic resin, 5 - 10 parts of heat - resistant agent, 1 - 3 parts of modified zinc oxide, 0 - 1 part of antioxidant, and 0.5 - 2 parts of compatibilizing promoter in a high - speed premixer to obtain premix A;

[0056] (2) Premix 10 - 20 parts of ASA, 10 - 20 parts of ACR resin, light stabilizer, 0 - 2 parts of color powder, and 0 - 1 part of light stabilizer in a high - speed premixer to obtain premix B;

[0057] (3) Then, the premixed A mixed material is passed through a twin-screw extruder, and B is quantitatively fed through a metering pump by side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 300 - 600 revolutions / min, and after cooling and pelletizing, a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy can be obtained under the condition that the pelletizer speed is 800 - 1000 revolutions / min

[0058] Example 1

[0059] The preparation method of a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy described in this example comprises the following weight components:

[0060] (1) Mix 50 parts of PMMA with 8 parts of modified antistatic resin, 2 parts of modified zinc oxide, 10 parts of heat-resistant agent, 0.5 part of antioxidant, and 1 part of compatibility promoter in a high-speed premixer to obtain premix A;

[0061] (2) Premix 10 parts of large-particle-size ASA, 5 parts of small-particle-size ASA, 15 parts of ACR resin, light stabilizer, 0.5 part of color powder, and 0.5 part of light stabilizer in a high-speed premixer to obtain premix B;

[0062] (3) Then, the premixed A mixed material is passed through a twin-screw extruder, and B is quantitatively fed through a metering pump by side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 500 revolutions / min, and after cooling and pelletizing, a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy can be obtained under the condition that the pelletizer speed is 800 revolutions / min

[0063] Example 2

[0064] The preparation method of a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy described in the example comprises the following weight components:

[0065] (1) Mix 60 parts of PMMA with 10 parts of modified antistatic resin, 5 parts of heat-resistant agent, 3 parts of modified zinc oxide, 0.5 part of antioxidant, and 1 part of compatibility promoter in a high-speed premixer to obtain premix A;

[0066] (2) Premix 5 parts of large-particle-size ASA, 5 parts of small-particle-size ASA, 12 parts of ACR resin, light stabilizer, 1 part of color powder, and 0.5 part of light stabilizer in a high-speed premixer to obtain premix B;

[0067] (3) Then, the premixed A mixed material is passed through a twin-screw extruder, and B is quantitatively fed through a metering pump by side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 300 revolutions / min, and after cooling and pelletizing, a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy can be obtained under the condition that the pelletizer speed is 800 revolutions / min.

[0068] Example 3

[0069] A preparation method of a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy as described in the examples comprises the following weight components:

[0070] (1) Mix 70 parts of PMMA with 5 parts of modified antistatic resin, 5 parts of heat-resistant agent, 3 parts of modified zinc oxide, 0.5 part of antioxidant, and 1 part of compatibility promoter in a high-speed premixer to obtain premix A;

[0071] (2) Premix 9 parts of large-particle-size ASA, 6 parts of small-particle-size ASA, 2 parts of ACR resin, light stabilizer, 1 part of color powder, and 0.5 part of light stabilizer in a high-speed premixer to obtain premix B;

[0072] (3) Then, the premixed A mixed material is passed through a twin-screw extruder, and B is quantitatively fed through a metering pump by side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 600 revolutions / min, and after cooling and pelletizing, a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy can be obtained under the condition that the pelletizer speed is 800 revolutions / min.

[0073] Example 4

[0074] A preparation method of a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy as described in the examples comprises the following weight components:

[0075] (1) Mix 65 parts of PMMA with 10 parts of modified antistatic resin, 5 parts of heat-resistant agent, 3 parts of modified zinc oxide, 0.5 part of antioxidant, and 1 part of compatibility promoter in a high-speed premixer to obtain premix A;

[0076] (2) Premix 8 parts of large-particle-size ASA, 2 parts of small-particle-size ASA, 7 parts of ACR resin, light stabilizer, 1 part of color powder, and 0.5 part of light stabilizer in a high-speed premixer to obtain premix B;

[0077] (3) Then, the premixed A mixed material is passed through a twin-screw extruder, and B is quantitatively fed through a metering pump by side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 500 revolutions / min, and after cooling and pelletizing, a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy can be obtained under the condition that the pelletizer speed is 800 revolutions / min.

[0078] Comparative Example 1

[0079] The preparation method of an ASA / PMMA for laser welding with spray-free, high toughness, high heat resistance and high laser transmittance according to this example comprises the following weight components:

[0080] The preparation method of a long-lasting antistatic, high heat resistance, long weather resistance spray-free ASA / PMMA alloy according to the example comprises the following weight components:

[0081] (1) Mix 65 parts of PMMA with 5 parts of heat-resistant agent, 3 parts of modified zinc oxide, 0.5 part of antioxidant and 1 part of compatibility promoter in a high-speed premixer to obtain premix A;

[0082] (2) Premix 10 parts of large particle size and 10 parts of small particle size ASA with 7 parts of ACR resin, light stabilizer, 1 part of color powder and 0.5 part of light stabilizer in a high-speed premixer to obtain premix B;

[0083] (3) Then convey the premixed A mixture through a twin-screw extruder, quantitatively convey B through a metering pump by side feeding, the extrusion temperature is 190 - 250 °C, the main machine speed is 500 revolutions / min, and after cooling and pelletizing, the pelletizer speed is 800 revolutions / min, a long-lasting antistatic, high heat resistance, long weather resistance spray-free ASA / PMMA alloy can be obtained

[0084] Comparative Example 2

[0085] The preparation method of a long-lasting antistatic, high heat resistance, long weather resistance spray-free ASA / PMMA alloy according to the example comprises the following weight components:

[0086] (1) Mix 65 parts of PMMA with 10 parts of modified antistatic resin, where the modified antistatic matrix is PA6, 5 parts of heat-resistant agent, 3 parts of modified zinc oxide, 0.5 part of antioxidant and 1 part of compatibility promoter in a high-speed premixer to obtain premix A;

[0087] (2) Premix 5 parts of large particle size ASA, 5 parts of small particle size with 7 parts of ACR resin, light stabilizer, 1 part of color powder and 0.5 part of light stabilizer in a high-speed premixer to obtain premix B;

[0088] (3) Then convey the premixed A mixture through a twin-screw extruder, quantitatively convey B through a metering pump by side feeding, the extrusion temperature is 190 - 250 °C, the main machine speed is 500 revolutions / min, and after cooling and pelletizing, the pelletizer speed is 800 revolutions / min, a long-lasting antistatic, high heat resistance, long weather resistance spray-free ASA / PMMA alloy can be obtained

[0089] Comparative Example 3

[0090] A preparation method of a long - acting antistatic, highly heat - resistant, long - weather - resistant spray - free ASA / PMMA alloy described in the examples, comprising the following weight components:

[0091] (1) Mix 65 parts of PMMA with 10 parts of modified antistatic resin, 5 parts of heat - resistant agent, 0.5 part of antioxidant, and 1 part of compatibility promoter in a high - speed premixer to obtain premix A;

[0092] (2) Premix 5 parts of large - particle - size ASA, 5 parts of small - particle - size ASA, 10 parts of ACR resin, light stabilizer, 1 part of color powder, and 0.5 part of light stabilizer in a high - speed premixer to obtain premix B;

[0093] (3) Then, pass the premixed A mixed material through a twin - screw extruder, quantitatively convey B through a metering pump by side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 500 revolutions per minute. After cooling and pelletizing, under the condition that the pelletizer speed is 800 revolutions per minute, a long - acting antistatic, highly heat - resistant, long - weather - resistant spray - free ASA / PMMA alloy can be obtained

[0094] Comparative Example 4

[0095] A preparation method of a long - acting antistatic, highly heat - resistant, long - weather - resistant spray - free ASA / PMMA alloy described in the examples, comprising the following weight components:

[0096] (1) Mix 65 parts of PMMA with 10 parts of modified antistatic resin, 5 parts of heat - resistant agent, 3 parts of modified zinc oxide, 0.5 part of antioxidant, and 1 part of compatibility promoter in a high - speed premixer to obtain premix A;

[0097] (2) Premix 11 parts of large - particle - size ASA, 6 parts of small - particle - size ASA, light stabilizer, 1 part of color powder, and 0.5 part of light stabilizer in a high - speed premixer to obtain premix B;

[0098] (3) Then, pass the premixed A mixed material through a twin - screw extruder, quantitatively convey B through a metering pump by side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 500 revolutions per minute. After cooling and pelletizing, under the condition that the pelletizer speed is 800 revolutions per minute, a long - acting antistatic, highly heat - resistant, long - weather - resistant spray - free ASA / PMMA alloy can be obtained

[0099] Comparative Example 5

[0100] A preparation method of a long - acting antistatic, highly heat - resistant, long - weather - resistant spray - free ASA / PMMA alloy described in the examples, comprising the following weight components:

[0101] (1) Mix 65 parts of PMMA, 10 parts of modified antistatic resin, 3 parts of modified zinc oxide, 0.5 part of antioxidant, and 1 part of compatibility promoter in a high-speed premixer to obtain premix A;

[0102] (2) Premix 10 parts of large-particle-size ASA, 5 parts of small-particle-size ASA, 7 parts of ACR resin, light stabilizer, 1 part of color powder, and 0.5 part of light stabilizer in a high-speed premixer to obtain premix B;

[0103] (3) Then, pass the premixed A mixed material through a twin-screw extruder, quantitatively convey B through a metering pump and side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 500 revolutions per minute. Under the conditions of cooling and pelletizing with a pelletizer speed of 800 revolutions per minute, a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy can be obtained

[0104] Comparative Example 6

[0105] A preparation method of a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy described in the examples comprises the following weight components:

[0106] (1) Mix 65 parts of PMMA, 10 parts of modified antistatic resin, 5 parts of heat-resistant agent, 3 parts of modified zinc oxide, 0.5 part of antioxidant, and 1 part of compatibility promoter in a high-speed premixer to obtain premix A;

[0107] (2) Premix 10 parts of large-particle-size ASA, 7 parts of ACR resin, light stabilizer, 1 part of color powder, and 0.5 part of light stabilizer in a high-speed premixer to obtain premix B;

[0108] (3) Then, pass the premixed A mixed material through a twin-screw extruder, quantitatively convey B through a metering pump and side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 500 revolutions per minute. Under the conditions of cooling and pelletizing with a pelletizer speed of 800 revolutions per minute, a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy can be obtained

[0109] Comparative Example 7

[0110] A preparation method of a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy described in the examples comprises the following weight components:

[0111] (1) Mix 65 parts of PMMA, 10 parts of modified antistatic resin, 5 parts of heat-resistant agent, 3 parts of modified zinc oxide, 0.5 part of antioxidant, and 1 part of compatibility promoter in a high-speed premixer to obtain premix A;

[0112] (2) Premix 10 parts of small-particle-size ASA, 7 parts of ACR resin, light stabilizer, 1 part of color powder, and 0.5 part of light stabilizer in a high-speed premixer to obtain premix B;

[0113] (3) Then, pass the premixed A mixed material through a twin-screw extruder, quantitatively convey B through a metering pump by side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 500 revolutions / min, and after cooling and pelletizing, a long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA / PMMA alloy can be obtained under the condition that the pelletizer speed is 800 revolutions / min;

[0114] Dry the pelletized particles, take samples for testing. The notched impact performance is tested according to ISO 179-1 (kJ / m2); the heat distortion temperature is according to ISO 75 (1.8 MPa); the weather resistance is tested according to SAE J2527 2500 KJ energy; the blackness is in the SCE mode of an integrating sphere spectrophotometer, and the test instrument is Minolta 3600A; the antistatic test measures the surface resistance.

[0115]

[0116]

[0117] It can be seen from the above test data that: Examples 1, 2, 3, and 4 can obtain long-lasting antistatic, high heat-resistant, long weather-resistant spray-free ASA PMMA through different ratios; it can be seen from the test data of Example 4 and Comparative Example 1 that after removing the antistatic agent, the antistatic effect has a certain decline and is uneven; it can be seen from the test results of Example 4 and Comparative Example 2 that changing the polyamide matrix causes the appearance of the ASA / PMMA matrix to deteriorate and is not bright enough black; it can be seen from the test results of Example 4 and Comparative Example 3 that removing the modified zinc oxide will cause the antistatic effect to deteriorate; it can be seen from the test results of Example 4 and Comparative Example 4 that removing ACR will cause the weather resistance of ASA PMMA to fail; it can be seen from the test data of Example 4 and Comparative Example 5 that removing the heat-resistant agent will significantly reduce the heat resistance of ASA / PMMA and cannot meet the use requirements; it can be seen from the test results of Example 4 and Comparative Example 6 that only adding large-particle-size rubber powder will significantly affect the appearance of ASA / PMMA; it can be seen from the test results of Example 4 and Comparative Example 7 that only adding small-particle-size rubber powder significantly reduces the toughness of ASA / PMMA resin.

Claims

1. A long-acting antistatic, highly heat-resistant, and long weather-resistant spray-free ASA / PMMA alloy, characterized in that, It is prepared from the following raw materials by weight: 40 - 70 parts of polymethyl methacrylate (PMMA) resin; 10 - 20 parts of acrylonitrile - styrene - acrylate (ASA) resin; 10 - 20 parts of ACR resin; 1 - 10 parts of antistatic resin; 1 - 3 parts of modified zinc oxide; 0.5 - 2 parts of compatibility promoter; 5 - 10 parts of heat - resistant agent; 0 - 1 part of antioxidant; 0 - 1 part of light stabilizer; 0 - 2 parts of color powder.

2. A long-acting antistatic, highly heat-resistant, long weather-resistant spray-free ASA / PMMA alloy according to claim 1, characterized in that: The melt index of the PMMA resin is between 1 - 5, and the polydispersity coefficient is between 1 - 2.

3. A long-acting antistatic, highly heat-resistant, long-weather-resistant spray-free ASA / PMMA alloy according to claim 1, characterized in that: The ASA resin is composed of rubber powder with large and small particle sizes; the size range of the large particle size of the ASA resin is between 350 - 450 μm, and the acrylate content is between 50 - 70%; the size range of the small particle size of the ASA resin is between 150 - 200 μm, and the acrylate content is between 50 - 70%.

4. A long-acting antistatic, highly heat-resistant, long weather-resistant spray-free ASA / PMMA alloy according to claim 1, characterized in that: The heat - resistant agent is one or several of MMA - SMA, SAN - SMA, SAN - MMA - SMA, AS - SMA copolymers.

5. The long-lasting antistatic, highly heat-resistant, long weather-resistant spray-free ASA / PMMA alloy according to claim 4, characterized in that: The molecular weight range of the SAN - MMA - SMA and AS - MMA - SMA copolymers is 70000 - 120000, and the polydispersity coefficient is 2 - 3, where the MMA content is 30 - 35%.

6. A long-lasting antistatic, highly heat-resistant, long weather-resistant spray-free ASA / PMMA alloy according to claim 4, characterized in that: The molecular weight range of the heat - resistant agent SAN - SMA and AS - SMA copolymers is 90000 - 160000, and the polydispersity coefficient is 1 - 3, where the SMA content is 15 - 18%.

7. An ASA / PMMA alloy with long-lasting antistatic property, high heat resistance, and long weather resistance for spray-free applications according to claim 1, characterized in that: The ACR is a core - shell structured acrylate copolymer.

8. A long-lasting antistatic, highly heat-resistant, long weather-resistant spray-free ASA / PMMA alloy according to claim 7, characterized in that: The core - shell structured acrylate copolymer of ACR uses butyl acrylate as the core, which is used as the rubber phase, with a particle size of 30 - 80 μm and an acrylate content of 78 - 80%, and the core - shell structured acrylate copolymer of ACR uses methyl methacrylate as the shell.

9. A long-lasting antistatic, highly heat-resistant, long-lasting weather-resistant spray-free ASA / PMMA alloy according to claim 1, characterized in that: The long - acting antistatic agent is a PA matrix.

10. A long-lasting antistatic, highly heat-resistant, long weather-resistant spray-free ASA / PMMA alloy according to claim 9, characterized in that: The PA is PA11, its refractive index is 1.52, its molecular weight is 11000 - 16000, and it is modified by maleic anhydride grafting, and the maleic anhydride grafting rate is 0.5 - 1%.

11. A long-acting antistatic, highly heat-resistant, long-weather-resistant spray-free ASA / PMMA alloy according to claim 1, characterized in that: The modified zinc oxide is modified by siloxane, the silicon content is more than 5%, and the particle size of the modified zinc oxide is 60 - 80 nm.

12. A long-lasting antistatic, highly heat-resistant, long weather-resistant spray-free ASA / PMMA alloy according to claim 1, characterized in that: The compatibility promoter is a styrene - acrylonitrile - glycidyl methacrylate copolymer (SAG) resin, the glycidyl methacrylate copolymer content is 40 - 45%, and the effective epoxy content in the glycidyl methacrylate is 85 - 90%.

13. A long-acting antistatic, highly heat-resistant, long-weather-resistant spray-free ASA / PMMA alloy according to claim 1, characterized in that: The antioxidant is a compound of phosphite - type or hindered phenol - type antioxidants.

14. A long-acting antistatic, highly heat-resistant, long weather-resistant spray-free ASA / PMMA alloy according to claim 1, characterized in that: The light stabilizer is one or several of ultraviolet absorbers and free - radical scavengers.

15. A long-lasting antistatic, highly heat-resistant, long-lasting weather-resistant spray-free ASA / PMMA alloy according to claim 1, characterized in that: The color powder is prepared by one or multiple compoundings except carbon black.

16. The preparation method of the long-acting antistatic, highly heat-resistant, long weather-resistant spray-free ASA / PMMA alloy according to any one of claims 1-15, characterized in that, The steps are as follows: (1) Mix 40 - 70 parts of PMMA with 1 - 10 parts of modified antistatic resin, 5 - 10 parts of heat - resistant agent, 1 - 3 parts of modified zinc oxide, 0 - 1 part of antioxidant, and 0.5 - 2 parts of compatibility promoter in a high - speed premixer to obtain premix A; (2) Premix 10 - 20 parts of ASA, 10 - 20 parts of ACR resin, light stabilizer, 0 - 2 parts of color powder, and 0 - 1 part of light stabilizer in a high - speed premixer to obtain premix B; (3) Then, pass the premixed A mixed material through a twin - screw extruder, quantitatively convey B through a metering pump by side feeding. The extrusion temperature is 190 - 250 °C, the main machine speed is 300 - 600 revolutions / min. After cooling and pelletizing, under the condition that the pelletizer speed is 800 - 1000 revolutions / min, a long - acting antistatic, high - heat - resistant, long - weather - resistant spray - free ASA / PMMA alloy can be obtained.

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