Solvent-resistant PC / ABS composite material, preparation method and application thereof

Abstract

The application provides a solvent-resistant PC / ABS composite material and a preparation method and application thereof, and the preparation raw material of the solvent-resistant PC / ABS composite material comprises the following components in parts by weight: modified PC 40-95 parts; modified ABS 10-40 parts; toughening agent 2-10 parts; antioxidant 0.1-0.5 parts; compatibilizer 0.5-3 parts; and lubricant 0.1-1 part. The modified PC and the modified ABS are used as main raw materials, and then the toughening agent, the antioxidant, the compatibilizer and other auxiliary agents are added, so that the prepared PC / ABS composite material has good solvent resistance and environmental stress cracking resistance.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, and relates to a solvent-resistant PC / ABS composite material, its preparation method, and its application. Background Technology

[0002] Polycarbonate (PC resin, bisphenol A type PC) is a highly linear thermoplastic polymer material composed of alternating carbonate groups and benzene ring groups forming the molecular backbone. The presence of aromatic groups on the macromolecular backbone endows the molecular chain segments with strong overall rigidity, while the flexible carbonate groups impart good toughness to the chain segments. Therefore, PC materials possess high rigidity, high heat resistance, high impact resistance, and excellent mechanical properties. However, PC has high melt viscosity, is prone to stress cracking, and has poor solvent resistance, which limits its application range to some extent. To address these shortcomings of PC, it can be modified using acrylonitrile-butadiene-styrene graft copolymer (ABS).

[0003] PC / ABS composite material is a composite material made by blending polycarbonate (PC) and acrylonitrile-butadiene-styrene copolymer (ABS). It combines the excellent properties of both materials, with the moldability, flowability and chemical resistance of ABS, and the mechanical properties, high impact strength and high heat distortion temperature of PC.

[0004] To avoid environmental pollution caused by spraying or electroplating, PC / ABS composite materials are currently mostly used in paint-free applications. However, PC / ABS composite materials used in paint-free applications need to have strong solvent resistance. For example, when paint-free PC / ABS composite materials are used as materials for car steering wheels, users may have sunscreen, hand cream, etc. left on their hands. When PC / ABS composite materials are in contact with sunscreen, hand cream, etc. for a long time, their performance will be reduced due to insufficient solvent resistance.

[0005] Therefore, there is a desire in this field to develop a solvent-resistant PC / ABS composite material. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a solvent-resistant PC / ABS composite material, its preparation method, and its applications.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a solvent-resistant PC / ABS composite material, wherein the raw materials for preparing the solvent-resistant PC / ABS composite material include the following components in parts by weight:

[0009]

[0010] This invention uses modified PC and modified ABS as the main raw materials, and then adds toughening agents, antioxidants, compatibilizers and other additives to prepare PC / ABS composite materials with good solvent resistance and environmental stress cracking resistance. This expands the application space of PC / ABS composite materials and enables the application of PC / ABS composite materials in the field of paint-free coating, reducing costs and achieving environmental protection and low carbon emissions.

[0011] In this invention, the amount of modified PC used in the preparation of the solvent-resistant PC / ABS composite material can be 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, etc., by weight.

[0012] In this invention, the amount of modified ABS used in the preparation of the solvent-resistant PC / ABS composite material can be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, etc., by weight.

[0013] In this invention, the raw materials for preparing the solvent-resistant PC / ABS composite material can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc., by weight.

[0014] In this invention, the amount of antioxidant used in the preparation of the solvent-resistant PC / ABS composite material can be 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, etc., by weight.

[0015] In this invention, the amount of compatibilizer used in the preparation of the solvent-resistant PC / ABS composite material can be 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, etc., by weight.

[0016] In this invention, the amount of lubricant used in the preparation of the solvent-resistant PC / ABS composite material can be 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, etc., according to the weight of the raw materials.

[0017] Preferably, the raw materials for preparing the modified PC include the following components in parts by weight:

[0018]

[0019] Preferably, the amount of PC used in the preparation of the modified PC can be 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, etc., by weight.

[0020] Preferably, the amount of polyester used in the preparation of the modified PC can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc., by weight.

[0021] Preferably, the amount of coupling agent used in the preparation of the modified PC can be 0.5 parts, 1 part, 1.5 parts, 2 parts, etc., based on the weight of the raw materials.

[0022] Preferably, the amount of catalyst used in the preparation of the modified PC can be 0.001 parts, 0.002 parts, 0.003 parts, etc., by weight.

[0023] Preferably, the amount of compatibilizer used in the preparation of the modified PC can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, etc., based on the weight of the raw materials.

[0024] Preferably, the polyester comprises polybutylene terephthalate (PBT).

[0025] Preferably, the coupling agent comprises allyl glycidyl ether (AGE).

[0026] Preferably, the catalyst comprises sodium stearate.

[0027] Preferably, the compatibilizer includes polyethylene glycol (PEG). It should be noted that the compatibilizer referred to here is the compatibilizer used in the preparation of modified PC.

[0028] This invention uses allyl epoxy resin AGE as a coupling agent to prepare a blend of polycarbonate (PC) and polybutylene terephthalate (PBT) to improve the chemical resistance of PC. Specifically, the epoxy resin AGE undergoes an addition reaction with the acid end groups of PBT, and then the modified PBT undergoes a desired substitution reaction with PC.

[0029] Preferably, the modified PC is prepared by the following method:

[0030] The coupling agent, polyester, catalyst and compatibilizer are mixed in the prescribed amounts, extruded and granulated, and then the granulated product is mixed with PC and extruded and granulated again to obtain the modified PC.

[0031] Preferably, both extrusion granulation processes are performed in a twin-screw extruder.

[0032] Preferably, the PC raw material is dried in a forced-air oven at 110-130°C (e.g., 110°C, 120°C, 130°C, etc.) before extrusion.

[0033] Preferably, the raw materials for preparing the modified ABS include the following components by weight:

[0034] 80-98 parts of ABS;

[0035] Stearic acid alcohol auxiliaries 0.2-2 parts;

[0036] 0.5-6 parts TPU.

[0037] Preferably, the amount of ABS used in the preparation of the modified ABS can be 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, etc., by weight.

[0038] Preferably, the amount of stearic acid alcohol additives used in the preparation of the modified ABS can be 0.2 parts, 0.3 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, etc., based on the weight of the raw materials.

[0039] Preferably, the amount of TPU used in the preparation of the modified ABS can be 0.5 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, etc., by weight.

[0040] Preferably, the stearic acid alcohol adjuvant includes any one or a combination of at least two of ethyl octadecyl acetate (ES), ethylene glycol distearate (EGDS), glyceryl tristearate (GTS), or pentaerythritol stearate (PETS).

[0041] This invention utilizes TPU and stearic acid alcohol-based additives to modify ABS, thereby improving the reagent resistance and environmental stress cracking resistance of ABS.

[0042] Preferably, the modified ABS is prepared by the following method:

[0043] The modified ABS is obtained by mixing the formulated amounts of ABS, stearic acid alcohol additives and TPU, and then extruding and granulating the mixture.

[0044] Preferably, the extrusion granulation is carried out in a twin-screw extruder.

[0045] Preferably, the ABS raw material is dried in a forced-air oven at 70-90°C (e.g., 70°C, 80°C, 90°C, etc.) before extrusion.

[0046] Preferably, the toughening agent comprises any one or a combination of at least two of the following: olefin block copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic-silicone rubber toughening agent, ethylene-methyl acrylate, ethylene-butyl acrylate, or ethylene-acrylate-glycidyl methacrylate terpolymer.

[0047] Preferably, the antioxidant comprises tris(2,4-di-tert-butylphenyl) phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris(2,4-di-tert-butyl) phosphite, hindered phenol (3 The following are all of the following: octadecyl 5-dibutyl-4-hydroxyphenylpropionate, 1,3,5-tris(3,5-di-tert-butyl,4-hydroxybenzyl)triazine, 2,4,6-(1H,3H,5H)trione, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] or pentaerythritol distearate diphosphite.

[0048] Preferably, the compatibilizer comprises an anhydride-modified α-olefin copolymer, wherein the anhydride comprises any one or a combination of at least two of maleic anhydride, phthalic anhydride, fumaric anhydride or itaconic anhydride.

[0049] Preferably, the α-olefin in the anhydride-modified α-olefin copolymer includes any one or a combination of at least two of ethylene, α-propylene, α-butene, α-isobutene, α-butene, α-hexene, or α-octene.

[0050] It should be noted that the compatibilizer mentioned here refers to the compatibilizer directly used in the preparation of solvent-resistant PC / ABS composite materials.

[0051] Preferably, the lubricant comprises any one or a combination of at least two of the following: silane polymer, fatty acid salt, calcium stearate, zinc stearate, stearamide, methyl bis-stearamide, ethylene bis-oleamide, N,N-ethylene bis-stearamide, glyceryl monostearate, pentaerythritol stearate, or lignite waxes.

[0052] In a second aspect, the present invention provides a method for preparing a solvent-resistant PC / ABS composite material as described in the first aspect, the method comprising the following steps:

[0053] The modified PC, modified ABS, toughening agent, antioxidant, compatibilizer, and lubricant are mixed in the specified amounts and then extruded and granulated to obtain the solvent-resistant PC / ABS composite material.

[0054] Preferably, the extrusion granulation is carried out in a twin-screw extruder.

[0055] Thirdly, the present invention provides an application of the solvent-resistant PC / ABS composite material as described in the first aspect in automotive interior parts. Applying this PC / ABS composite material to automotive interior parts can avoid environmental pollution caused by painting.

[0056] Compared with the prior art, the present invention has at least the following beneficial effects:

[0057] This invention uses modified PC and modified ABS as the main raw materials, and then adds toughening agents, antioxidants, compatibilizers and other additives to prepare PC / ABS composite materials with good solvent resistance and environmental stress cracking resistance. Detailed Implementation

[0058] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0059] Preparation Examples 1-5

[0060] In Preparation Examples 1-5 of this invention, a modified PC is provided, which are respectively designated as modified PC-1, modified PC-2, modified PC-3, modified PC-4, and modified PC-5. The specific raw materials and their amounts (parts by weight) are shown in Table 1.

[0061] Table 1

[0062]

[0063] The preparation method includes the following steps:

[0064] The coupling agent, polyester, catalyst and compatibilizer are mixed in the prescribed amount, and then extruded and granulated in a twin-screw extruder. The granulated product is then mixed with PC and extruded and granulated again in a twin-screw extruder to obtain the modified PC.

[0065] The PC raw material is dried in a 120°C forced-air oven before extrusion.

[0066] Preparation Examples 6-12

[0067] In Preparation Examples 6-12 of this invention, a modified ABS is provided, which are respectively designated as modified ABS-1, modified ABS-2, modified ABS-3, modified ABS-4, modified ABS-5, modified ABS-6, and modified ABS-7. The specific raw materials and their amounts (parts by weight) are shown in Table 2.

[0068] Table 2

[0069]

[0070] In Table 2, the ABS brand is LG Acid and Alkali Resistant ABS from South Korea, and the TPU brand is Desmopan 345X from Covestro of Germany.

[0071] The preparation method includes the following steps:

[0072] The modified ABS is obtained by mixing the formulated amounts of ABS, stearic acid alcohol additives and TPU, and extruding and granulating the mixture in a twin-screw extruder.

[0073] The ABS raw material is dried in an 80°C forced-air oven before extrusion.

[0074] Examples 1-11 and Comparative Examples 1-7

[0075] The present invention provides a PC / ABS composite material in Examples 1-11 and Comparative Examples 1-7, respectively. The specific raw materials and their amounts (parts by weight) are shown in Tables 3 and 4.

[0076] Table 3

[0077]

[0078] Table 4

[0079]

[0080]

[0081] In Tables 3 and 4, the grade of PC is Sabic PC105; the grade of ABS is LG Acid and Alkali Resistant ABS from South Korea; the compatibilizer is maleic anhydride-grafted polypropylene with a grafting rate of 1.2%, manufactured by Ziheng Plastics; the antioxidant is hindered phenolic antioxidant, Antioxidant 1010 manufactured by DOUBLE BONDCHEMICAL IND. Ltd.; the lubricant is YY-GT100 silicone powder from Guangzhou Youyou Chemical Technology Co., Ltd.; and the toughening agent is INFUSE from Dow Chemical. TM OBC.

[0082] The preparation method includes the following steps:

[0083] The modified PC (or PC), modified ABS (or ABS), toughening agent, antioxidant, compatibilizer, and lubricant are mixed in the specified amounts and extruded and granulated in a twin-screw extruder to obtain the PC / ABS composite material.

[0084] The performance of the PC / ABS composite materials provided in the examples and comparative examples was tested using the following methods:

[0085] (1) Tensile elongation at break before experiment: Tensile elongation at break was tested on the PC / ABS composite materials provided in the examples and comparative examples in accordance with ISO 527.

[0086] (2) Elongation at break after experiment: Sunscreen (brand name: ) was applied to the PC / ABS composite materials provided in the examples and comparative examples. After placing the Ultraguard Sunscreen Lotion (SPF 70+) for 5 days, perform a tensile elongation at break test according to ISO 527.

[0087] The performance test results are shown in Table 5.

[0088] Table 5

[0089]

[0090]

[0091] As can be seen from Table 5, the PC / ABS composite material provided in the embodiments of the present invention has a high tensile elongation at break before and after applying sunscreen (tensile elongation at break before experiment: 110%-120%; tensile elongation at break after experiment: 58%-75%), and the retention rate of elongation at break after experiment is high (50.86%-62.5%).

[0092] Compared to the examples, the PC / ABS composite material provided in the comparative example had lower tensile elongation at break both before and after applying sunscreen. In particular, the tensile elongation at break was significantly reduced after applying sunscreen, and the retention rate of elongation at break after the experiment was significantly lower.

[0093] The applicant declares that this invention illustrates the solvent-resistant PC / ABS composite material, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of this invention.

Claims

1. A solvent-resistant PC / ABS composite material, characterized in that, The raw materials for preparing the solvent-resistant PC / ABS composite material include the following components by weight: Modified PC 40-95 parts; Modified ABS 10-40 parts; Toughening agent 2-10 parts; Antioxidant 0.1-0.5 parts; Compatibilizer 0.5-3 parts; Lubricant 0.1-1 part; The raw materials for preparing the modified PC, by weight, include the following components: PC 85-95 copies; 5-15 parts polyester; 0.5-2 parts of coupling agent; Catalyst 0.001-0.003 parts; 1-2 parts compatibilizer; The polyester includes polybutylene terephthalate; The modified PC was prepared by the following method: The coupling agent, polyester, catalyst and compatibilizer are mixed in the prescribed amounts, extruded and granulated, and then the granulated product is mixed with PC and extruded and granulated again to obtain the modified PC. The raw materials for preparing the modified ABS, by weight, include the following components: 80-98 parts of ABS; Stearic acid alcohol auxiliaries 0.2-2 parts; 0.5-6 parts TPU; The stearic acid alcohol adjuvants include any one or a combination of at least two of ethyl octadecanoate, ethylene glycol distearate, glyceryl tristearate, or pentaerythritol stearate.

2. The solvent-resistant PC / ABS composite material according to claim 1, characterized in that, The coupling agent includes allyl glycidyl ether.

3. The solvent-resistant PC / ABS composite material according to claim 1, characterized in that, The catalyst includes sodium stearate.

4. The solvent-resistant PC / ABS composite material according to claim 1, characterized in that, The compatibilizer in the raw materials for preparing the modified PC includes polyethylene glycol.

5. The solvent-resistant PC / ABS composite material according to claim 1, characterized in that, Both extrusion granulation processes were carried out in a twin-screw extruder.

6. The solvent-resistant PC / ABS composite material according to claim 1, characterized in that, The PC raw material also includes a drying step before extrusion granulation.

7. The solvent-resistant PC / ABS composite material according to claim 1, characterized in that, The modified ABS was prepared by the following method: The modified ABS is obtained by mixing the formulated amounts of ABS, stearic acid alcohol additives and TPU, and then extruding and granulating the mixture.

8. The solvent-resistant PC / ABS composite material according to claim 7, wherein the extrusion granulation is carried out in a twin-screw extruder.

9. The solvent-resistant PC / ABS composite material according to claim 7, wherein the ABS raw material further includes a drying step before extrusion granulation.

10. The solvent-resistant PC / ABS composite material according to claim 1, characterized in that, The toughening agent includes any one or a combination of at least two of the following: olefin block copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic-silicone rubber toughening agent, ethylene-methyl acrylate, ethylene-butyl acrylate, or ethylene-acrylate-glycidyl methacrylate terpolymer.

11. The solvent-resistant PC / ABS composite material according to claim 1, characterized in that, The antioxidants include tris(2,4-di-tert-butylphenyl) phosphite, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and... N,N' -Bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol ester, tris(2,4-di-tert-butyl)phosphite, hindered phenol (3,5-di-butyl-4-hydroxyphenylpropionate octadecyl) ester, 1,3,5-tris(3,5-di-tert-butyl,4-hydroxybenzyl)triazine, 2,4,6-(1H,3H,5H)trione, N,N' 1-Bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] or pentaerythritol distearate diphosphite, or any combination of at least two of these.

12. The solvent-resistant PC / ABS composite material according to claim 1, characterized in that, The compatibilizer in the raw materials for preparing the solvent-resistant PC / ABS composite material includes anhydride-modified α-olefin copolymers, wherein the anhydride includes any one or a combination of at least two of maleic anhydride, phthalic anhydride, fumaric anhydride or itaconic anhydride.

13. The solvent-resistant PC / ABS composite material according to claim 1, characterized in that, The lubricant includes silane polymers, fatty acid salts, calcium stearate, zinc stearate, stearamide, methyl bis-stearamide, and ethylene bis-oleamide. N, N- Any one or a combination of at least two of ethylene bis-stearamide, glyceryl monostearate, pentaerythritol stearate, or lignite waxes.

14. A method for preparing a solvent-resistant PC / ABS composite material as described in any one of claims 1-13, characterized in that, The preparation method includes the following steps: The modified PC, modified ABS, toughening agent, antioxidant, compatibilizer, and lubricant are mixed in the specified amounts and then extruded and granulated to obtain the solvent-resistant PC / ABS composite material.

15. The preparation method according to claim 14, characterized in that, The extrusion granulation is carried out in a twin-screw extruder.

16. The application of a solvent-resistant PC / ABS composite material as described in any one of claims 1-13 in automotive interior parts.

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