High chemical resistance, high heat stability, high impact resistance ABS / PC composite material and preparation method

Abstract

The present invention relates to a highly chemical-resistant, high heat-stable, and high impact-resistant ABS / PC composite material and a preparation method thereof; the composite material comprises the following components in parts by weight: ABS resin: 15-30 parts; SAN resin: 30-60 parts; PC resin: 20-40 parts; chemical-resistant masterbatch: 3-8 parts; high impact-resistant masterbatch: 2-6 parts; SMG copolymer: 0.5-5 parts; lubricant: 0.1-1 part; antioxidant: 0.1-1 part; the preparation method comprises the following steps: uniformly mixing the above components through a mixer, and then feeding them into a twin-screw extruder, with the temperature set in the range of 180-250°C and the screw speed of 300-600 rpm, and obtaining the product through extrusion granulation. The product prepared by the present invention has high impact resistance, good heat stability, and strong chemical resistance, and can be widely applied to fields with strict requirements for the use environment, such as kitchen appliances, automotive interior and exterior trims, and around charging piles.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer material modification, and particularly relates to a high chemical resistance, high thermal stability, and high impact resistance ABS / PC composite material and a preparation method thereof. Background Art

[0002] ABS resin is a graft copolymer of acrylonitrile, butadiene, and styrene. Due to its excellent coloring performance and gloss, and high melt strength and easy processing, it is widely used in the production of various automobiles, household appliances, and daily necessities that require beauty. PC resin is an amorphous engineering plastic with outstanding impact resistance, transparency, flame retardancy, dimensional stability, and high heat resistance. It is an engineering plastic with excellent comprehensive performance; however, it has obvious defects such as high melting temperature, poor processing fluidity, notch sensitivity, and poor chemical resistance. The blend of ABS resin and PC resin as the main raw materials is an important engineering plastic alloy, basically having the advantages of ABS resin and PC resin.

[0003] When making an ABS / PC alloy mainly based on ABS resin, due to the poor compatibility between the two, its main mechanical properties decrease significantly, far inferior to the PC / ABS system mainly based on PC resin, and the chemical resistance is poor, losing the application value of the material. Therefore, all kinds of academic researchers have mostly studied the PC / ABS alloy system and have not delved deeply into the ABS / PC alloy.

[0004] Patent document CN101508833A discloses a PC / ABS alloy with excellent chemical resistance. By adding PBT, although the chemical resistance effect is very good, but after adding too much PBT, it not only affects the impact performance of the PC / ABS alloy material, but also has a great impact on the heat distortion temperature of the material, which is the deficiency of the prior art.

[0005] Another patent document CN107118534A discloses a PC / ABS alloy with excellent resistance to automotive paint cracking and a preparation method thereof. By adding PE or EMA as a chemical cracking resistance reagent, but its addition amount cannot exceed 1%. Once it exceeds, there will be poor compatibility and delamination phenomenon, which is also the deficiency of the prior art. Summary of the Invention

[0006] The purpose of the present invention is to provide a high chemical resistance, high thermal stability, and high impact resistance ABS / PC composite material and a preparation method thereof in view of the deficiencies of the prior art.

[0007] To achieve the above purpose, the present invention is realized through the following technical solutions:

[0008] A high chemical resistance, high thermal stability, and high impact resistance ABS / PC composite material, the composite material comprising the following raw material components in parts by weight:

[0009]

[0010] The ABS resin is emulsion ABS, with a butadiene content of 40 - 60 wt%, and an acrylonitrile content of 15 - 30 wt%; more preferably, the butadiene content is 50 - 60 wt%, and the acrylonitrile content is 20 - 30 wt%.

[0011] The acrylonitrile content in the SAN resin is above 25 wt%, and the weight - average molecular weight is between 80,000 and 150,000; preferably, the acrylonitrile content is above 28 wt%, and the weight - average molecular weight is between 110,000 and 130,000; the weight - average molecular weight of the PC resin is between 18,000 and 40,000, and more preferably between 25,000 and 32,000.

[0012] The chemical - resistant masterbatch is polybutylene terephthalate - grafted styrene - acrylonitrile copolymer (PBT - g - SAN), where the PBT content is 50 - 90 wt%, the intrinsic viscosity of PBT is 0.6 - 1.2, and more preferably the intrinsic viscosity of PBT is 0.7 - 1.0; the SAN content is 10 - 50 wt%, and the acrylonitrile content in SAN of the PBT - g - SAN is above 30 wt%.

[0013] The high - impact masterbatch is a mixture of one or two masterbatches of POE - g - SAN and PCTG - g - SAN. In POE - g - SAN, the POE proportion is 40 - 80 wt%, the SAN proportion is 20 - 60 wt%, and the acrylonitrile content in SAN of the POE - g - SAN is 25 - 35 wt%; in PCTG - g - SAN, the PCTG content is 50 - 70 wt%, the SAN content is 30 - 50 wt%, and the acrylonitrile content in SAN of the PCTG - g - SAN is above 30 wt%.

[0014] As a preferred embodiment, the SMG copolymer is a styrene - methyl methacrylate - glycidyl methacrylate terpolymer, used as a high - heat - stability compatibilizer, where the methyl methacrylate monomer content is 10 - 85 wt%, the styrene monomer content is 14.5 - 70 wt%, and the remaining monomer, glycidyl methacrylate content, is 0.5 - 10 wt%.

[0015] As a preferred embodiment, the antioxidant is a complex of a hindered phenol antioxidant and a phosphite antioxidant.

[0016] As a preferred embodiment, the lubricant is one or several of fatty acid soap salts, silicones, and low - molecular - weight waxes.

[0017] As a preferred embodiment, the preparation method of the high chemical-resistant, high heat-stable, and high impact-resistant ABS / PC composite material comprises the following steps:

[0018] S1. Pre-mix 15 - 30 parts of ABS resin, 20 - 50 parts of SAN resin, 20 - 40 parts of PC resin, 3 - 8 parts of chemical-resistant masterbatch, 2 - 6 parts of high impact-resistant masterbatch, 3 - 8 parts of SMG copolymer, 0.1 - 1 part of antioxidant, and 0.1 - 1 part of lubricant;

[0019] S2. Add the pre-mixture into a twin-screw extruder for melt extrusion to obtain the high chemical-resistant, high heat-stable, and high impact-resistant ABS / PC composite material.

[0020] In step S2, the working temperature of the twin-screw extruder is 180 - 250 °C, and the screw speed is 300 - 600 rpm.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1) The present invention uses a styrene-acrylonitrile copolymer with a polyester structure grafted and a high acrylonitrile content as the chemical-resistant masterbatch, which not only improves the chemical resistance of the alloy material, but also, due to the advantages of the SAN structure, has better compatibility with ABS-based resins and will not show a delamination phenomenon even at high addition amounts. In addition, a high impact-resistant masterbatch is compounded, which can offset to a certain extent the negative effect brought by the insufficient toughness of the polyester structure and improve the situation where the mechanical properties of the original ABS / PC alloy mainly composed of ABS resin cannot meet the product requirements;

[0023] 2) The present invention uses an SMG copolymer as a high heat-stable compatibilizer, which not only improves the thermal aging performance and heat distortion temperature of the material, but also significantly improves the compatibility of the alloy material;

[0024] 3) A high impact-resistant masterbatch is added in the present invention, which not only improves the toughness of the material well, but also solves the compatibility problem with the matrix resin. More importantly, the introduced polyolefin elastomer structure and / or copolyester structure itself also has a certain anti-chemical corrosion performance, which can further improve the chemical resistance of the composite material. Description of the Drawings

[0025] By reading the detailed description of the non-limiting embodiments with reference to the following drawings, other features, objects, and advantages of the present invention will become more apparent:

[0026] Figure 1 (a), (b), (c), and (d) are respectively 200-fold electron microscope pictures of the tensile splines of Comparative Example 10, Comparative Example 6, Comparative Example 5, and Example 6 after being soaked in an ethyl acetate:ethanol solution with a mass ratio of 3:2 for 30 s.Figure 1 (e), (f), (g), and (h) are the result pictures of the material particles of Comparative Example 10, Comparative Example 1, Example 2, and Example 6, respectively, after aging for 6 hours at 200°C in a ventilation aging oven. Detailed implementation manners

[0027] The present invention will be described in detail below with reference to the examples. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several adjustments and improvements can still be made. These all fall within the protection scope of the present invention.

[0028] The materials selected for each example and comparative example of the present invention are described as follows:

[0029] ABS resin:

[0030] a) ABS resin 1: ABS HR181 (rubber content 55 - 60%), manufacturer: Kumho, Korea;

[0031] b) ABS resin 2: ABS 8391 (rubber content 13 - 15%), manufacturer: Shanghai Gaoqiao Petrochemical;

[0032] SAN resin:

[0033] a) SAN resin 1: SAN 51 (acrylonitrile content > 30%), manufacturer: Ineos Styrolution;

[0034] b) SAN resin 2: NF 2200 (acrylonitrile content > 24%), manufacturer: Formosa Plastics Corporation, Taiwan, China;

[0035] PC resin: Model: PC 1100, manufacturer: Lotte Chemical, Korea;

[0036] PBT: Model: TH6100, manufacturer: Xinjiang Tunhe Co., Ltd.;

[0037] PE: Model: LLDPE M2320, manufacturer: Guangzhou Petrochemical;

[0038] PBT-g-SAN: PBT content is 75 wt%, acrylonitrile content in SAN is 32 wt%;

[0039] POE-g-SAN: POE content is 65 wt%, acrylonitrile content in SAN is 32 wt%;

[0040] PCTG-g-SAN: PCTG content is 50 wt%, acrylonitrile content in SAN is 32 wt%;

[0041] SMG terpolymer: Manufacturer: Jiayirong Polymer (Shanghai) Co., Ltd.

[0042] a) Model: HPC-3128 (glycidyl methacrylate content 1 wt%);

[0043] b) Model: HPC-4280 (glycidyl methacrylate content 2 wt%);

[0044] AX8900: GMA content 8 wt%, SK Chemicals;

[0045] Antioxidant:

[0046] a) Model: 1076, Manufacturer: BASF;

[0047] b) Model: 168, Manufacturer: BASF;

[0048] Lubricant: Model: PETS, Manufacturer: LG, Korea.

[0049] Examples 1-10

[0050] The raw materials were put into a mixer according to the mass ratio for premixing at room temperature for 8 min, and then added into a twin-screw extruder. The temperature of the extruder was controlled at 180 - 250 °C, the screw speed was 300 rpm, and the feeding speed was 30 Hz. After extrusion and pelletization, a high chemical-resistant, high heat-stable, and high impact-resistant ABS / PC composite material was obtained.

[0051] Table 1: Raw material component table of Examples 1-10 (unit: parts)

[0052]

[0053] Comparative Examples 1-10

[0054] The preparation methods of Comparative Examples 1-10 were the same as that of Example 1.

[0055] Table 2: Raw material component table of Comparative Examples 1-10 (unit: parts)

[0056]

[0057]

[0058] Example 6 was selected for performance comparison in various aspects with the above Comparative Examples:

[0059] The difference between Comparative Example 1 and Example 6 was that only 2 parts of PBT were added to improve the chemical resistance of the material;

[0060] The difference between Comparative Example 2 and Example 6 was that only 5 parts of PBT were added to improve the chemical resistance of the material;

[0061] The difference between Comparative Example 3 and Example 6 is that only 1 part of PE is added to improve the chemical resistance of the material;

[0062] The difference between Comparative Example 4 and Example 6 is that only 3 parts of PE are added to improve the chemical resistance of the material;

[0063] The difference between Comparative Example 5 and Example 6 is that an ABS resin with a low rubber content is selected;

[0064] The difference between Comparative Example 6 and Example 6 is that an SAN resin with a lower acrylonitrile content is selected;

[0065] The difference between Comparative Example 7 and Example 6 is that AX 8900 is used instead of the SMG copolymer for comparison;

[0066] The difference between Comparative Example 8 and Example 6 is that PBT is used instead of PBT-g-SAN for comparison;

[0067] The difference between Comparative Example 9 and Example 6 is that no high impact resistance masterbatch is added;

[0068] Comparative Example 10 is a blank sample.

[0069] For the high chemical resistance, high thermal stability, and high impact resistance ABS / PC alloy materials prepared according to the above examples and comparative examples, test specimens are prepared under the same injection molding conditions, and the specific performance test items are as follows:

[0070] Tensile strength: The tensile strength is measured in accordance with ASTM D638;

[0071] Izod impact strength: The notched impact strength is measured in accordance with ASTM D256 (1 / 8″ notch, 23 °C);

[0072] Heat distortion temperature (HDT): The heat distortion temperature is measured in accordance with ASTM D648 under the condition of 1.82 MPa;

[0073] Hand cream resistance test: Hand cream is coated on the surface of the tensile specimen, and it is left at room temperature for 24 h, and the crack situation on the surface is observed;

[0074] Solvent resistance test: The tensile specimen is placed in an ethyl acetate:ethanol solution with a mass ratio of 3:2 and soaked for 30 s, and then the corrosion situation on the surface of the specimen is observed with a microscope;

[0075] Aging resistance test: The modified particles of each example and comparative example are placed in a ventilation aging oven at 200 °C and aged for 6 h, and the color change of the particles is observed.

[0076] The test results of each example and each comparative example are shown in Table 3 in detail. The test results of some examples and comparative examples can be seenFigure 1 。

[0077] Table 3: Test Results of Each Example and Comparative Example

[0078]

[0079]

[0080] From the results in Table 3, it can be seen that the ABS / PC alloy material prepared in Example 6 has the best comprehensive performance. It not only has excellent impact resistance, high heat distortion temperature, but also maintains good appearance in the ability to resist a variety of chemical reagents, and the material also maintains good color stability after aging at high temperature.

[0081] Overall, with the increase in the compounding amount of the chemical-resistant masterbatch and the high-impact masterbatch, the chemical resistance of the material also increases; and with the increase in the addition amount of the SMG terpolymer, the heat distortion temperature of the material also increases, and the color change of the material after aging becomes less obvious, indicating that the SMG terpolymer can not only effectively improve the heat resistance of the material, but also further improve the heat stability of the material. Observing Comparative Examples 1-4, it is found that adding PBT can improve the chemical resistance of the material, but its mechanical properties decrease significantly with the increase in the addition amount of PBT, and for the material that improves the chemical resistance of the material by adding PE, not only the mechanical properties decrease, but also after adding more than 1 part of PE, the material surface peels off and shows delamination incompatibility. In Comparative Examples 5-9, after changing different variables, there are always some defects in the mechanical properties, chemical resistance, heat resistance and thermal stability of the ABS / PC alloy material, and it cannot meet the stringent use requirements.

[0082] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art in the technical field, without departing from the method of the present invention, several improvements and supplements can be made, and these improvements and supplements should also be regarded as the protection scope of the present invention.

Claims

1. A high chemical-resistant, high heat-stable, and high impact-resistant ABS / PC composite material, characterized in that, The composite material comprises raw material components in the following parts by weight: 15 - 30 parts of ABS resin; 30 - 60 parts of SAN resin; 20 - 40 parts of PC resin; 3 - 8 parts of chemical-resistant masterbatch; 2 - 6 parts of high impact resistance masterbatch; 0.5 - 5 parts of SMG copolymer; 0.1 - 1 part of lubricant; 0.1 - 1 part of antioxidant; The chemical-resistant masterbatch is polybutylene terephthalate grafted styrene-acrylonitrile copolymer PBT-g-SAN, wherein the PBT content is 50 - 90 wt%, the intrinsic viscosity of PBT is 0.6 - 1.2; the SAN content is 10 - 50 wt%, and the acrylonitrile content in the SAN is more than 30 wt%; The high impact resistance masterbatch is a mixture of one or two masterbatches of POE-g-SAN and PCTG-g-SAN; In the POE-g-SAN, the POE proportion is 40 - 80 wt%, the SAN proportion is 20 - 60 wt%, and the acrylonitrile content in the SAN is 25 - 35 wt%; In the PCTG-g-SAN, the PCTG content is 50 - 70 wt%, the SAN content is 30 - 50 wt%, and the acrylonitrile content in the SAN is more than 30 wt%.

2. The high chemical-resistant, high heat-stable, and high impact-resistant ABS / PC composite material according to claim 1, characterized in that, The ABS resin is emulsion ABS, wherein the butadiene content is 40 - 60 wt%, and the acrylonitrile content is 15 - 30 wt%.

3. The high chemical-resistant, high heat-stable, and high impact-resistant ABS / PC composite material according to claim 1, characterized in that, The acrylonitrile content in the SAN resin is more than 25 wt%, and the weight average molecular weight is between 80,000 - 150,000; the weight average molecular weight of the PC resin is between 18,000 - 40,000.

4. The high chemical-resistant, high heat-stable, and high impact-resistant ABS / PC composite material according to claim 1, characterized in that, The SMG copolymer is a terpolymer of styrene-methyl methacrylate-glycidyl methacrylate; wherein the methyl methacrylate monomer content is 10 - 85 wt%, the styrene monomer content is 14.5 - 70 wt%, and the glycidyl methacrylate content is 0.5 - 10 wt%.

5. The high chemical-resistant, high heat-stable, and high impact-resistant ABS / PC composite material according to claim 1, characterized in that, The antioxidant is a composite of hindered phenol antioxidants and phosphite antioxidants.

6. The high chemical-resistant, high heat-stable, and high impact-resistant ABS / PC composite material according to claim 1, characterized in that, The lubricant is one or several of fatty acid soaps, silicones, and low molecular weight waxes.

7. A preparation method of the high chemical-resistant, high heat-stable, and high impact-resistant ABS / PC composite material according to any one of claims 1-6, characterized in that, The preparation method comprises the following steps: S1. Pre-mix 15 - 30 parts of ABS resin, 30 - 60 parts of SAN resin, 20 - 40 parts of PC resin, 3 - 8 parts of chemical-resistant masterbatch, 2 - 6 parts of high impact resistance masterbatch, 0.5 - 5 parts of SMG copolymer, 0.1 - 1 part of antioxidant, and 0.1 - 1 part of lubricant; S2. Add the pre-mixture into a twin-screw extruder for melt extrusion to obtain the high chemical-resistant, high heat-stable, and high impact resistance ABS / PC composite material.

8. The preparation method according to claim 7, characterized in that, In step S2, the working temperature of the twin-screw extruder is 180 - 250 °C, and the screw speed is 300 - 600 rpm.

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