PC / PMMA alloy material and preparation method and application thereof

Abstract

The invention relates to the technical field of alloy materials, in particular to a PC / PMMA (polycarbonate / polymethyl methacrylate) alloy material as well as a preparation method and application thereof, and a maleic anhydride modified ternary polymer used in the PC / PMMA alloy material comprises Acrylonitrile, Styrene, Acrylate and maleic anhydride. From the perspective of ASA molecular structure design, maleic anhydride is copolymerized on an ASA molecular structure, an ASA copolymer is uniformly dispersed between a PC phase and a PMMA phase, and maleic anhydride forms a plurality of connection points in the two phases, so that the compatibility of the whole system is greatly improved, and the material with good comprehensive performance and excellent appearance quality is obtained.

Description

Technical Field

[0001] This invention relates to the field of alloy materials technology, specifically to a PC / PMMA alloy material, its preparation method, and its applications. Background Technology

[0002] Polycarbonate (PC) is a high molecular polymer containing carbonate groups in its molecular chain. Based on the structure of the ester group, it can be divided into aliphatic, aromatic, aliphatic-aromatic and other types.

[0003] Poly(methylmethacrylate) (PMMA), also known as acrylic, plexiglass, or Lucite, is a commonly used glass substitute due to its high transparency, low price, and ease of machining.

[0004] Acrylonitrile, styrene, and acrylic rubber (ASA) is a ternary polymer and belongs to impact-modified resins.

[0005] In existing technologies, PMMA / ASA alloys are commonly used for paint-free high-gloss exterior parts of automobiles (such as pillar trim panels, air intake grilles, rearview mirror housings, etc.), which have the characteristics of high gloss, scratch resistance, and weather resistance, but have disadvantages such as low heat deformation temperature and poor toughness.

[0006] In existing technologies, the heat resistance of the PMMA / ASA alloy is improved by adding heat-resistant agents with high glass transition temperature, such as styrene-maleic anhydride copolymer, but the toughness is not improved.

[0007] In existing technical solutions, heat resistance and toughness are improved by introducing a third component, PC, into the PMMA / ASA alloy system. However, due to the poor compatibility between PC and PMMA, the product exhibits severe pearlescent appearance. This phenomenon needs to be improved by adding compatibilizers and ester exchangers to the formulation. If the amount of compatibilizer added is too large, it will affect the blackness of the product, while if the amount added is too small, the improvement in compatibility is limited.

[0008] CN115926415 A discloses a PC / PMMA / ASA ternary alloy material, its preparation method, and its application, belonging to the field of polymer blending and modification technology. The provided material comprises the following components in parts by weight: 40-60 parts PC resin, 15-45 parts PMMA resin, 15-30 parts ASA adhesive powder, 3-6 parts toughening agent, 1-4 parts compatibilizer, 0.01-0.5 parts transesterification accelerator, 2-3 parts black masterbatch, and 1.9-6.5 parts other additives; the ASA adhesive powder has a core-shell structure, wherein the core is butyl acrylate copolymer silicon, and the shell is a styrene-acrylonitrile copolymer or a styrene-acrylonitrile-methyl methacrylate copolymer, with an average rubber particle size of 100-200 nm; the compatibilizer is a styrene-acrylate copolymer. The prepared material is high-gloss black, non-iridescent, and exhibits improved mechanical and heat resistance properties; it can be applied to the manufacture of automotive parts. This invention offers limited improvement in compatibility by adding a small amount of compatibilizer and is prone to uneven dispersion.

[0009] CN119570226 A relates to a high surface quality plastic, specifically the preparation and application of a high-gloss PMMA / PC / ASA composite material, particularly in automotive exterior trim panels. The invention uses polymethyl methacrylate resin, polycarbonate, toughening agent, compatibilizer, colorant, and additives as raw materials to prepare a high-gloss PMMA / PC / ASA composite material. However, this invention, by adding a small amount of compatibilizer, offers limited improvement in compatibility and is prone to uneven dispersion.

[0010] CN119060519 A relates to a PC / ASA / PMMA ternary alloy material with scratch resistance and self-cleaning properties, and its preparation method, comprising the following raw materials in parts by weight: PC 280-320 parts, ASA 180-220 parts, PMMA 80-120 parts, perfluoropolymer 7-11 parts, nano-silica 7-11 parts, and silicone 5-7 parts. This invention endows the material surface with superhydrophobicity, anti-fouling properties, and enhanced hardness through special additives, resulting in a high contact angle for water droplets, thus exhibiting excellent hydrophobicity and self-cleaning ability. This design not only effectively reduces the adhesion of dust and stains, achieving a self-cleaning effect, but also avoids the problems of traditional self-cleaning coatings requiring high-temperature curing and prone to aging and peeling, improving the durability of the self-cleaning effect. While this invention primarily solves the problems of scratch resistance and self-cleaning function, it also leads to poor appearance and is not suitable for exterior decoration applications. Summary of the Invention

[0011] The purpose of this invention is to provide a PC / PMMA alloy material, its preparation method, and its application, thereby solving the technical problem that existing alloy materials cannot balance performance and appearance.

[0012] This invention discloses A maleic anhydride-modified ternary polymer comprising acrylonitrile, styrene, acrylic rubber, and maleic anhydride.

[0013] Furthermore, the mass ratio of acrylonitrile, styrene, acrylic rubber, and maleic anhydride is 10-15:25-30:50-60:1-5.

[0014] A method for preparing a maleic anhydride-modified ternary polymer involves using deionized water, sodium dodecylbenzenesulfonate, potassium persulfate, butyl acrylate, and allyl methacrylate to formulate a mixed monomer one, and using the mixed monomer one to prepare a polyacrylate latex. After cooling the polyacrylate latex, potassium persulfate, styrene and acrylonitrile were added to prepare mixed monomer II. The acrylate-styrene-acrylonitrile copolymer latex was prepared using mixed monomer II. Potassium persulfate, styrene, acrylonitrile and maleic anhydride were added to acrylate-styrene-acrylonitrile copolymer latex to prepare mixed monomer 3, and maleic anhydride modified acrylate-styrene-acrylonitrile copolymer latex was prepared using mixed monomer 3. Maleic anhydride-modified acrylate-styrene-acrylonitrile copolymer latex was demulsified, coagulated, washed, and dried to obtain a maleic anhydride-modified terpolymer.

[0015] Furthermore, the method for preparing polyacrylate latex involves using 1 / 4 of the mixed monomer one to maintain the reaction, then adding the remaining mixed monomer one dropwise. After the addition is complete, the reaction continues to obtain polyacrylate latex.

[0016] Furthermore, the method for preparing the acrylate-styrene-acrylonitrile copolymer latex involves adding mixed monomers dropwise to a reaction vessel, and after the addition is complete, continuing the reaction to obtain the acrylate-styrene-acrylonitrile copolymer latex.

[0017] Furthermore, the preparation method of the maleic anhydride-modified acrylate-styrene-acrylonitrile copolymer latex involves adding mixed monomers dropwise to a three-stage reaction vessel. After the addition is complete, the reaction continues to obtain the maleic anhydride-modified acrylate-styrene-acrylonitrile copolymer latex.

[0018] A PC / PMMA alloy material, by weight, comprises the following components: 20-60 parts of polycarbonate; 20-60 parts of polymethyl methacrylate; 10-20 parts of maleic anhydride-modified ternary polymer; Antioxidant 0.1~0.3 parts Lubricant 0.3~0.5 parts; Light stabilizer 0.3~0.5 parts; 0.3-0.5 parts of ultraviolet absorber; 0.1-0.2 parts of ester exchanger; 1-2 parts of carbon black masterbatch.

[0019] Furthermore, the polycarbonate has a molecular weight of 20,000 to 35,000 and a melt flow rate (MFR, 300°C, 1.2 kg) of 10 to 25 g / 10 min.

[0020] Furthermore, the polymethyl methacrylate has a melt flow rate (MFR, 220°C, 10kg) of 2~35g / 10min.

[0021] Furthermore, the light stabilizer is UV-770, UV944, or UV3853.

[0022] Furthermore, the antioxidant is a compound of antioxidant 1076 and antioxidant 168. Furthermore, the mass ratio of antioxidant 1076 to antioxidant 168 is 1:2.

[0023] Furthermore, the ultraviolet absorber is one of UV-234, UV-360, UV-P, and UV-1164.

[0024] Furthermore, the transesterification agent is diphenyl carbonate.

[0025] Furthermore, the carbon black masterbatch is CB5593.

[0026] A method for preparing PC / PMMA alloy material, wherein a type 35 extruder is selected, the extrusion temperature is set to 200℃, 260℃, 260℃, 260℃, 250℃, 240℃, 240℃, 240℃, 240℃, 250℃, the main extruder speed is set to 350RPM, and the output is set to 35kg / h.

[0027] An application of a PC / PMMA alloy material for automotive exterior trim.

[0028] Compared with the prior art, the beneficial effects of the present invention are: 1. This invention, starting from the perspective of ASA molecular structure design, copolymerizes maleic anhydride onto the ASA molecular structure, and simultaneously disperses the ASA copolymer uniformly between the PC and PMMA phases through the strong shearing dispersion effect of the screw. Maleic anhydride forms multiple connection points between the two phases, which greatly improves the compatibility of the entire system and yields a material with good comprehensive performance and excellent appearance quality. Attached Figure Description

[0029] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0030] Figure 1 This is a sample image of the PC / PMMA alloy material in Example 1 of the present invention.

[0031] Figure 2 The images show PC / PMMA alloy material samples from the embodiments and comparative examples of the present invention, where from left to right are Example 1, Comparative Example 3, and Comparative Example 2. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0033] Example This embodiment discloses a method for synthesizing maleic anhydride-modified ternary polymers as follows: 700g of deionized water, 2g of sodium dodecylbenzenesulfonate, and 1g of potassium persulfate were added to the reactor, and the temperature was raised to 75°C. Mixed monomer one was prepared by 150g of butyl acrylate and 0.8g of allyl methacrylate. First, 1 / 4 of the mixed monomer was added to the reactor and the reaction was maintained for 1 hour. Then, the remaining mixed monomer one was added dropwise (the addition was completed in 3 hours). After the addition was completed, the reaction was continued for 2 hours to obtain polyacrylate latex. The polyacrylate latex was cooled to 60°C, and 0.4g of potassium persulfate was added. Mixed monomer II was prepared by mixing 42g of styrene and 14g of acrylonitrile. Mixed monomer II was then added dropwise (the addition was completed in 1 hour). After the addition was completed, the reaction was continued for 1 hour to obtain acrylate-styrene-acrylonitrile copolymer latex. Continue to maintain the reaction conditions at 60℃, add 0.5g of potassium persulfate, prepare mixed monomer 3 from 42g of styrene, 14g of acrylonitrile and 10g of maleic anhydride, and then add mixed monomer 3 dropwise (complete the addition in 1 hour). After the addition is completed, continue the reaction for 2 hours to obtain maleic anhydride modified acrylate-styrene-acrylonitrile copolymer latex. Maleic anhydride-modified acrylate-styrene-acrylonitrile copolymer latex was demulsified, coagulated, washed, and dried to obtain maleic anhydride-modified ASA copolymer.

[0034] Weigh each raw material according to the weight proportions shown in Table 1, mix the resin and additives in a high-speed mixer for 120 seconds, and then add them to a twin-screw extruder through the main feed inlet. After melt extrusion and granulation, the composite material is obtained.

[0035] The twin-screw extrusion temperature is set to 200℃, 260℃, 260℃, 260℃, 250℃, 240℃, 240℃, 240℃, 240℃, and 250℃, the main extruder speed is set to 350 RPM, and the output is set to 35 kg / h.

[0036] Table 1

[0037] The PC used above is Wanhua Chemical PC A1220, the PMMA used is Mitsubishi Chemical PMMA VH001, the compatibilizer SMA used is Guangzhou Shangneng ASA LP2068, the ASA-2 used is Mitsubishi ASA SX-006, the ASA-3 is a self-made maleic anhydride modified ASA copolymer (maleic anhydride content 10%), and the ASA-4 is a self-made maleic anhydride modified ASA copolymer (maleic anhydride content 5%).

[0038] The composite material prepared above was injection molded into ISO standard physical property strips by single screw injection to test basic properties, and 10 high-gloss plates of 170*80*3mm were injection molded into the composite material to evaluate appearance quality.

[0039] Table 2

[0040] Notes: ☆ indicates severe pearlescent texture (pearlescent texture area exceeds 20% of a single sample), ☆☆ indicates slight pearlescent texture (pearlescent texture area 5%-20% of a single sample), ☆☆☆ indicates very little pearlescent texture (pearlescent texture area 0.5%-5% of a single sample), ☆☆☆☆ indicates no pearlescent texture (pearlescent texture area less than 0.5% of a single sample). from Figure 1 , Figure 2As can be seen from Table 2, even with the addition of a compatibilizer using existing technologies, the overall appearance still exhibits pearlescent texture. The maleic anhydride-modified ASA of this invention significantly improves compatibility, resulting in a composite material with excellent appearance quality and no pearlescent texture.

[0041] The above are the embodiments listed in this example. However, this example is not limited to the optional embodiments described above. Those skilled in the art can arbitrarily combine the above methods to obtain other various embodiments. Anyone can derive other various forms of embodiments based on the inspiration of this example. The above specific embodiments should not be construed as limiting the scope of protection of this example. The scope of protection of this example should be determined by the claims, and the specification can be used to interpret the claims.

Claims

1. A maleic anhydride modified terpolymer characterized by: The acrylonitrile, styrene, acrylic rubber and maleic anhydride are in a mass ratio of 10-15:25-30:50-60:1-5.

2. The maleic anhydride modified terpolymer of claim 1, wherein: The deionized water, sodium dodecyl benzene sulfonate, potassium persulfate, butyl acrylate and allyl methacrylate are used to prepare mixed monomers I, and the polyacrylate latex is prepared using the mixed monomers I; 3. A process for the preparation of a maleic anhydride modified terpolymer according to any one of claims 1-2, characterized in that: After the polyacrylate latex is cooled, the potassium persulfate, styrene and acrylonitrile are added to prepare mixed monomers II, and the acrylate-styrene-acrylonitrile copolymer latex is prepared using the mixed monomers II; The potassium persulfate, styrene, acrylonitrile and maleic anhydride are added to the acrylate-styrene-acrylonitrile copolymer latex to prepare mixed monomers III, and the maleic anhydride modified acrylate-styrene-acrylonitrile copolymer latex is prepared using the mixed monomers III; The maleic anhydride modified acrylate-styrene-acrylonitrile copolymer latex is subjected to demulsification, coagulation, washing and drying to obtain the maleic anhydride modified terpolymer. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3.

4. A PC / PMMA alloy material, characterized by: The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3.

5. The PC / PMMA alloy material of claim 4, wherein: The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3.

6. The PC / PMMA alloy material of claim 5, wherein: The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3.

7. The PC / PMMA alloy material of claim 5, wherein: The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3.

8. The PC / PMMA alloy material of claim 5, wherein: The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3.

9. A PC / PMMA alloy material according to any one of claims 4 to 8, characterized in that: The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3.

10. Use of a PC / PMMA alloy material according to any one of claims 4-8, characterized in that: The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified terpolymer is prepared by the method of any one of claims 1-2 or the method of claim 3. The maleic anhydride modified

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