A weather-resistant low-temperature PC / ASA composite material and its preparation method and application

Abstract

The present invention provides a weather-resistant low-temperature PC / ASA composite material, a preparation method thereof and an application thereof. The PC / ASA composite material comprises the following components in parts by weight: 50-60 parts of PC resin, 10-30 parts of ASA resin, 5-15 parts of improver, 1-3 parts of antioxidant, 2-10 parts of compatibilizer, 5-10 parts of flame retardant and 1-3 parts of color powder. The preparation method comprises the following steps: mixing the above materials in a blender according to parts by weight, putting the mixed materials into a twin-screw extruder for extrusion granulation, cooling, pelletizing and drying to obtain a weather-resistant low-temperature PC / ASA composite material. The present invention helps to improve the low-temperature impact strength, mechanical properties and antioxidant properties of the PC / ASA composite material, thereby extending the service life of the material.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a weather-resistant and low-temperature PC / ASA composite material and a preparation method and application thereof. Background Art

[0002] PC is polycarbonate, an amorphous, highly transparent thermoplastic engineering plastic with good electrical insulation, elongation, toughness and impact resistance, and is widely used in the manufacture of optical discs, automotive parts, bulletproof glass, eyeglass lenses and other products. However, its disadvantages are that it may soften or decompose at high temperatures, is sensitive to organic solvents, is prone to stress cracking, and is difficult to process.

[0003] ASA is a copolymer of acrylonitrile-acrylate-styrene, a ternary polymer formed by copolymerization of acrylonitrile, styrene and acrylic rubber, and has the advantages of strong UV resistance, waterproofness and chemical resistance. Compared with ABS resin, ASA resin does not contain carbon-carbon double bonds, which makes ASA resin have about 10 times better weather resistance than ABS, but due to the higher glass transition temperature of ASA resin, the low-temperature impact strength of ASA resin is much lower than that of ABS resin.

[0004] PC / ASA composite material combines the advantages of PC and ASA, and is widely used for its excellent comprehensive performance. However, PC / ASA composite material still has problems such as poor low-temperature impact strength, poor mechanical properties and easy aging, which limits the further expansion of the use of this material. Melting fluorocarbon resins such as polyvinylidene fluoride resins have excellent weather resistance, corrosion resistance and other characteristics, and are widely used. However, they have problems such as poor solubility in organic solvents and difficult processing. When using melting fluorocarbon resins such as polyvinylidene fluoride resins to prepare PC / ASA composite materials, there are problems such as poor improvement in low-temperature impact strength and mechanical properties. The prior art reports the problem of improving the low-temperature impact strength of materials by using silicone toughening agents, but during use, there are still disadvantages such as poor compatibility of silicone toughening agents with other polymer materials and high process requirements, which makes the effect of improving the material not obvious.

[0005] In view of the problems existing in the prior art, how to provide a PC / ASA composite material with high low-temperature impact strength, good mechanical properties and good antioxidant properties is a problem to be solved urgently by the present invention. Summary of the invention

[0006] The object of the present invention is to provide a weather-resistant and low-temperature PC / ASA composite material to solve the problems raised in the above background technology.

[0007] A further object of the present invention is to provide the application of the above PC / ASA composite material in household appliances, automobile parts and building materials.

[0008] To achieve the above object, the present invention provides a weather-resistant and low-temperature PC / ASA composite material, characterized in that it comprises the following components in parts by weight: 50-60 parts of PC resin, 10-30 parts of ASA resin, 5-15 parts of improver, 1-3 parts of antioxidant, 2-10 parts of compatibilizer, 5-10 parts of flame retardant, and 1-3 parts of color powder;

[0009] The improving agent is a modified fluorocarbon resin;

[0010] The antioxidants include hydroxylamine antioxidants and phosphite antioxidants.

[0011] As a further improvement, the modified fluorocarbon resin is obtained by reacting epoxy resin and FEVE resin.

[0012] As a further improvement, the synthesis of the modified fluorocarbon resin comprises the following steps: stirring and dispersing the epoxy resin and the FEVE resin in an organic solvent, adding an inorganic filler and a curing agent to react, and after the reaction is completed, post-processing is performed to obtain the modified fluorocarbon resin.

[0013] The inorganic filler is nano titanium dioxide; the curing agent is isocyanate prepolymer.

[0014] As a further improvement, the hydroxylamine antioxidant is at least one of N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, and dioctylamine; the phosphite antioxidant is at least one of tris(2,4-di-tert-butyl)phenyl phosphite, distearyl pentaerythritol diphosphite, and tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenyl diphosphite.

[0015] In order to have better anti-aging performance and extend the service life, preferably, the hydroxylamine antioxidant is N,N-dibenzylhydroxylamine, and the phosphite antioxidant is tris(2,4-di-tert-butyl)phenyl phosphite.

[0016] As a further improvement, the weight ratio of the hydroxylamine antioxidant to the phosphite antioxidant is 0.5-2.

[0017] As a further improvement, the flame retardant is at least one of brominated triazine, decabromodiphenylethane, triphenyl phosphate, tris(2,4-dibromophenyl)phosphate, and potassium perfluorobutyl sulfonate.

[0018] In order to have a better flame retardant effect, preferably, the flame retardant is tris(2,4-dibromophenyl)phosphate.

[0019] As a further improvement, the compatibilizer is at least one of styrene-acrylonitrile grafted maleic anhydride, styrene grafted maleic anhydride, and ethylene-methyl acrylate copolymer.

[0020] The present invention provides a weather-resistant and low-temperature PC / ASA composite material, characterized in that the preparation of the PC / ASA composite material comprises the following steps:

[0021] (1) PC resin, ASA resin, improver, antioxidant, compatibilizer, flame retardant and color powder are placed in a high-speed stirrer and mixed according to weight;

[0022] (2) feeding the mixed material into a twin-screw extruder for extrusion granulation, the processing temperature is 200-250° C., and the screw speed is 500-600 rpm;

[0023] (3) The extruded material is cooled, pelletized, and dried to obtain a weather-resistant and low-temperature PC / ASA composite material.

[0024] The invention provides an application of a weather-resistant and low-temperature PC / ASA composite material in household appliances, automobile parts and building materials.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] The PC / ASA composite material provided by the present invention has excellent tensile strength, flexural strength, low-temperature impact strength and melt index, indicating that the material has good mechanical properties and good weather resistance and low-temperature impact performance, and is easy to process and shape. The PC / ASA composite material also has a long oxidation induction period, indicating that the material has excellent anti-aging performance and can extend the service life of the material. DETAILED DESCRIPTION

[0027] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0028] In the following embodiments, except for the modified fluorocarbon resin, the other compound monomers and related reagents used can be purchased from the market, among which PC resin was purchased from Cangzhou Dahua Group Co., Ltd. with the item number CH8155, ASA resin was purchased from Suzhou Yunmao New Materials Co., Ltd. with the model number PW-957, FEVE resin was purchased from Suzhou Chuangyuan Chemical Co., Ltd. with the model number JF-3X, epoxy resin was purchased from Yueyang Baling Huaxing Petrochemical Co., Ltd. with the model number E-51, nano titanium dioxide was purchased from Jiangsu Fuzhan Pharmaceutical Co., Ltd. with the model number TBF, and isocyanate prepolymer was purchased from Dongguan Normante New Materials Co., Ltd. Materials Co., Ltd., model N3300, styrene-acrylonitrile grafted maleic anhydride was purchased from Dongguan Zhangmutou Hengtai Plastic Raw Materials Business Department, model AS-01, styrene grafted maleic anhydride was purchased from Dongguan Sujia Polymer Raw Materials Co., Ltd., model 0489, ethylene-methyl acrylate copolymer was purchased from Arkema Group, model AX8900, polyvinylidene fluoride resin was purchased from Arkema Group, model 2851-00, silicone toughener was purchased from Mitsubishi Chemical Group Corporation, model S-2030, and color powder was purchased from Hunan Jufa Pigment Co., Ltd., model JF-B2852.

[0029] The preparation method of modified fluorocarbon resin comprises the following steps:

[0030] 5g of epoxy resin and 50g of FEVE resin were added to a mixed solvent of 10mL of butyl acetate and 10mL of xylene and stirred and dispersed at a stirring speed of 800rpm for 30min. Then, 10g of inorganic filler nano-titanium dioxide and 10g of curing agent isocyanate prepolymer were added to react for 60min at a stirring speed of 600rpm. After the reaction was completed, the mixture was filtered through an 80-mesh filter to obtain a modified fluorocarbon resin.

[0031] The preparation methods of Examples 1-3 and Comparative Examples 1-4 comprise the following steps:

[0032] (1) PC resin, ASA resin, improver, antioxidant, compatibilizer, flame retardant and color powder were mixed in a high-speed stirrer according to weight proportions, with a stirring speed of 300 rpm and a stirring time of 40 min;

[0033] (2) feeding the mixed material into a twin-screw extruder for extrusion granulation at a processing temperature of 230° C. and a screw speed of 600 rpm;

[0034] (3) The extruded material was cooled in a 20° C. water tank, pelletized at a pelletizing speed of 200 rpm, and finally dried in a 90° C. forced air drying oven for 3 hours to obtain a weather-resistant low-temperature PC / ASA composite material.

[0035] The components and contents used in Examples 1-3 and Comparative Examples 1-4 are shown in Table 1 below:

[0036] Table 1

[0037]

[0038] The weather-resistant low-temperature PC / ASA composite material obtained in Examples 1-3 and Comparative Examples 1-4 was tested for tensile strength, flexural strength, low-temperature impact strength, oxidation induction period and melt index. The test method is as follows:

[0039] Tensile strength: tested according to ISO 527 standard, test speed 50mm / min;

[0040] Bending strength: tested according to ISO 178 standard, test speed 2mm / min;

[0041] Low temperature impact strength: tested according to ISO 179-1:2010(E) standard, the test temperature is -30℃;

[0042] Oxidation induction period: tested according to GB / T 19466.6-2009 standard, the test temperature is 180℃;

[0043] Melt index: tested in accordance with ISO 1133-1:2011(E) standard, test conditions are 220℃×10Kg.

[0044] The measured results are shown in Table 2:

[0045] Table 2

[0046]

[0047] It can be seen from Example 2 and Comparative Examples 1-2 in Table 2 that compared with the PC / ASA composite material prepared by using a polyvinylidene fluoride resin or a silicone toughening agent and other improving agents, the PC / ASA composite material prepared by using a modified fluorocarbon resin as an improving agent has better tensile strength, flexural strength, and low-temperature impact strength, and can also extend the oxidation induction period of the prepared PC / ASA composite material to a certain extent.

[0048] It can be seen from Example 2 and Comparative Examples 3-4 that, compared with the PC / ASA composite material prepared by using hydroxylamine antioxidants alone or hindered phenol antioxidants such as 2,6-di-tert-butyl-4-methylphenol in combination with hydroxylamine antioxidants, the PC / ASA composite material prepared by using hydroxylamine antioxidants and phosphite antioxidants has a longer oxidation induction period, indicating stronger antioxidant ability, and the tensile strength, flexural strength and low-temperature impact strength of the prepared PC / ASA composite material are all improved.

[0049] It can be seen from the test results of Examples 1-3 that the PC / ASA composite material prepared by the preparation method provided by the present invention has better tensile strength, flexural strength, low-temperature impact strength, oxidation induction period and melt index.

[0050] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A weather-resistant and low-temperature PC / ASA composite material, characterized in that: Contains the following components in parts by weight: 50-60 parts of PC resin, 10-30 parts of ASA resin, 5-15 parts of improver, 1-3 parts of antioxidant, 2-10 parts of compatibilizer, 5-10 parts of flame retardant, 1-3 parts of color powder; The improving agent is a modified fluorocarbon resin; The antioxidants include hydroxylamine antioxidants and phosphite antioxidants; The synthesis of the modified fluorocarbon resin comprises the following steps: stirring and dispersing the epoxy resin and the FEVE resin in an organic solvent, adding an inorganic filler and a curing agent to react, and after the reaction is completed, post-processing to obtain the modified fluorocarbon resin; The weight ratio of the hydroxylamine antioxidant to the phosphite antioxidant is 0.5-2.

2. The weather-resistant low-temperature PC / ASA composite material according to claim 1, characterized in that: The hydroxylamine antioxidant is at least one of N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, and dioctylamine; the phosphite antioxidant is at least one of tris(2,4-di-tert-butyl)phenyl phosphite, distearyl pentaerythritol diphosphite, and tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenyl diphosphite.

3. The weather-resistant low-temperature PC / ASA composite material according to claim 1, characterized in that: The flame retardant is at least one of bromotriazine, decabromodiphenylethane, triphenyl phosphate, tris(2,4-dibromophenyl)phosphate and potassium perfluorobutyl sulfonate.

4. The weather-resistant and low-temperature PC / ASA composite material according to claim 1, characterized in that: The compatibilizer is at least one of styrene-acrylonitrile grafted maleic anhydride, styrene grafted maleic anhydride, and ethylene-methyl acrylate copolymer.

5. The weather-resistant and low-temperature PC / ASA composite material according to claim 1, characterized in that: The preparation of the PC / ASA composite material comprises the following steps: (1) Mix PC resin, ASA resin, improver, antioxidant, compatibilizer, flame retardant and color powder in a high-speed stirrer according to weight; (2) The mixed material is fed into a twin-screw extruder for extrusion granulation at a processing temperature of 200-250°C and a screw speed of 500-600 rpm; (3) The extruded material is cooled, pelletized, and dried to obtain a weather-resistant and low-temperature PC / ASA composite material.

6. Application of the weather-resistant and low-temperature PC / ASA composite material according to claim 1 in household appliances, auto parts, and building materials.

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