A polyphenylene ether composition and its preparation method and application
Through the combination technology of polyphenylene ether, polystyrene, zinc oxide and phosphorus-based antioxidants, the problem that polyphenylene ether materials are difficult to take into account high flame retardancy, high mechanical strength and thermal oxygen aging resistance under high temperature environments is solved, and the comprehensive performance of polyphenylene ether composite materials is improved under high temperature conditions.
Patent Information
- Application Number
- CN202411992303.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-31
- Publication Date
- 2025-04-08
AI Technical Summary
Polyphenylene ether materials are difficult to take into account high flame retardancy, high mechanical strength and thermal oxygen aging resistance in high temperature environments, which limits their application in photovoltaics and electronic appliances.
By combining polyphenylene ether, polystyrene, zinc oxide and phosphorus-based antioxidant, a polyphenylene ether composition is formed, and the thermal deterioration of the polyphenylene ether material is inhibited by the synergistic effect of the phosphorus-based antioxidant and zinc oxide.
The tensile strength and impact resistance of polyphenylene ether composite materials under high temperature conditions are significantly improved, ensuring that they still maintain good mechanical properties and flame retardant properties after long-term thermal oxygen aging.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of polymer materials, and in particular to a polyphenylene ether composition and a preparation method and application thereof. Background Art
[0002] Polyphenylene ether (PPE)-based resin compositions have been widely used as appearance materials, industrial products, and in the fields of office appliance accessories, automotive accessories, and building materials because of their heat resistance, electrical properties, dimensional stability, impact resistance, and low specific gravity, and because they do not use halogen compounds or antimony compounds that impose a heavy burden on the environment, and because they have the advantages of self-extinguishing properties.
[0003] In recent years, with the development of photovoltaic, electronic and electrical fields, in addition to short-term properties such as mechanical properties, there are higher requirements for the long-term performance of materials, especially the thermal oxygen aging resistance of materials, because many application scenarios in this field need to be in a high temperature environment for a long time. Under thermal oxygen conditions, insufficient thermal oxygen aging resistance of materials will lead to the deterioration of their mechanical properties (such as tensile and impact properties), thus affecting their later use.
[0004] However, pure PPE has poor melt fluidity, and polystyrene (PS) is often added to improve its processing fluidity; at the same time, PPE has poor flame retardancy, and halogen-free flame retardants are usually added to modify its flame retardancy, but the addition of modifying additives such as polystyrene and halogen-free flame retardants will affect the mechanical properties and heat-oxidation aging resistance of the resulting polyphenylene ether material, especially the commonly used phosphate flame retardants, which will significantly reduce the heat-oxidation aging resistance of the polyphenylene ether material. This makes it difficult for polyphenylene ether materials to simultaneously take into account high flame retardancy, high mechanical strength and heat-oxidation aging resistance, which limits their application in the fields of photovoltaics and electronic appliances.
[0005] Therefore, it is of great significance to design and develop a polyphenylene ether material that can take into account high flame retardancy, high mechanical strength and long-term thermal oxidative aging performance. Summary of the invention
[0006] In order to solve the above technical problems, the present invention provides a polyphenylene ether composition and a preparation method and application thereof. The polyphenylene ether composition can make the obtained polyphenylene ether composite material have high flame retardancy, high mechanical strength and heat-oxidative aging resistance.
[0007] To achieve this object, the present invention adopts the following technical solutions:
[0008] In a first aspect, the present invention provides a polyphenylene ether composition, wherein the raw materials for preparing the polyphenylene ether composition include the following components in parts by weight:
[0009]
[0010] In the polyphenylene ether composition of the present invention, by compounding polyphenylene ether, polystyrene, zinc oxide and phosphorus-based antioxidant, the obtained polyphenylene ether composite material can have high flame retardancy, high mechanical strength and long-term thermal oxidative aging performance. Furthermore, the phosphorus-based antioxidant, as a free radical inhibitor, can stabilize the hydroperoxide free radicals generated due to the thermal effect, and compounding it with zinc oxide can effectively inhibit the thermal degradation of the polyphenylene ether material. Therefore, the compounding of the two can exert a synergistic effect, and can significantly improve the tensile strength and impact resistance of the obtained polyphenylene ether composite material after long-term thermal aging under high temperature conditions.
[0011] In the present invention, the content of polyphenylene ether is 50-65 parts by weight, for example, it can be 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight, 60 parts by weight, 62 parts by weight or 65 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.
[0012] The content of polystyrene is 15-25 parts by weight, for example, it can be 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight or 25 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively enumerates the specific points included in the said range.
[0013] The content of zinc oxide is 3-7 parts by weight, for example, it can be 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight or 7 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.
[0014] The content of phosphorus-based antioxidant is 2-4 parts by weight, for example, it can be 2 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.4 parts by weight, 3.6 parts by weight, 3.8 parts by weight or 4 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.
[0015] Preferably, the mass ratio of the polyphenylene ether to polystyrene is (2.5-3.7):1, wherein (2.5-3.5) can be, for example, 2.5, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.5 or 3.7, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.
[0016] In the present invention, by limiting the mass ratio of polyphenylene ether to polystyrene, the matrix compatibility of the obtained polyphenylene ether composition can be higher and the thermal deformation ability can be stronger. When the mass ratio of the two is lower than 2.5:1, the polyphenylene ether content is too low, the deformation is serious, and its tensile strength is affected. At the same time, the tensile strength and flame retardancy of the obtained polyphenylene ether composite material are reduced after aging; when the mass ratio of the two is higher than 3.7:1, the polyphenylene ether content is too high, the compatibility is poor, and it is easy to deteriorate and become brittle, that is, its notch impact resistance is poor. At the same time, its tensile strength will also be reduced, and the obtained polyphenylene ether composite material has poor thermal oxygen aging resistance.
[0017] Preferably, the polyphenylene ether comprises 2,6-dimethyl-1,4-phenyl ether units and / or 2,3,6-trimethyl-1,4-phenyl ether units.
[0018] Preferably, the weight average molecular weight of the polyphenylene ether is 80000-200000 (for example, 80000, 90000, 100000, 120000, 140000, 160000, 180000 or 200000, etc.), and the intrinsic viscosity in chloroform at 25°C is 0.35-0.6dL / g (for example, 0.35dL / g, 0.38dL / g, 0.4dL / g, 0.45dL / g, 0.5dL / g, 0.55dL / g or 0.6dL / g, etc.).
[0019] Preferably, the polystyrene comprises high impact polystyrene.
[0020] Preferably, main components of the high impact polystyrene include polystyrene and polybutadiene.
[0021] Preferably, the weight average molecular weight of the high impact polystyrene is 30000-100000 (for example, 30000, 40000, 50000, 60000, 70000, 80000, 90000 or 100000, etc.), and the intrinsic viscosity in chloroform at 25°C is 0.6-3dL / g (0.6dL / g, 0.8dL / g, 1dL / g, 1.5dL / g, 2dL / g, 2.5dL / g or 3dL / g, etc.).
[0022] Preferably, based on the total mass of the raw materials for preparing the polyphenylene ether composition as 100%, the total content of zinc oxide and phosphorus-based antioxidant is 7-9%, for example, it can be 7%, 7.2%, 7.4%, 7.6%, 7.8%, 8%, 8.2%, 8.4%, 8.6%, 8.8% or 9%, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.
[0023] In the present invention, when the total content of zinc oxide and phosphorus-based antioxidant is 7-9% of the total mass of the raw materials, the two can play a synergistic role, thereby effectively improving the mechanical properties and heat-oxidation aging resistance of the obtained polyphenylene ether composite material. When the total content of the two is too high, the tensile strength and notched impact strength of the obtained polyphenylene ether composite material are significantly reduced, that is, the mechanical properties are not good, thus affecting its scope of use; when the total content of the two is too low, the tensile strength retention rate and notched impact strength retention rate of the obtained polyphenylene ether composite material after high-temperature aging are significantly reduced, that is, the heat-oxidation aging resistance of the obtained polyphenylene ether composite material is not good; further, when the total content of the two is 8% and the mass ratio is 5:3, the obtained polyphenylene ether composite material has the best comprehensive performance of mechanical properties and heat-oxidation aging resistance.
[0024] Preferably, the phosphorus-based antioxidant comprises a phosphite antioxidant and / or a hindered aryl phosphite antioxidant.
[0025] Preferably, the phosphite includes any one of monophosphite, pentaerythritol distearyl diphosphite (antioxidant 618), pentaerythritol dioctyl diphosphite or pentaerythritol diphenyl diphosphite, or a combination of at least two thereof.
[0026] Preferably, the hindered aromatic phosphite includes any one or a combination of at least two of tris(2,4-di-tert-butylphenyl)phosphite (antioxidant 168), tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene phosphite, pentaerythritol diphosphite bis(2,4-di-tert-butylphenyl) ester (antioxidant THP-24), pentaerythritol diphosphite bis(2,6-di-tert-butyl-4-methylphenyl) ester (PEP-36) or tris(nonylphenyl)phosphite (antioxidant TNP).
[0027] Preferably, the raw materials for preparing the polyphenylene ether composition further include a toughening agent.
[0028] Preferably, the toughening agent includes any one of SEBS, MBS, EBA, SBS or SEEPS, or a combination of at least two thereof.
[0029] Preferably, the content of the toughening agent is 10-18 parts by weight, for example, it can be 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight or 18 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.
[0030] In a second aspect, the present invention provides a method for preparing the polyphenylene ether composition as described in the first aspect, the preparation method comprising the following steps:
[0031] The raw materials including polyphenylene ether, polystyrene, zinc oxide and phosphorus-based antioxidant are mixed and melt co-extruded to obtain the polyphenylene ether composition.
[0032] Preferably, the mixing is performed under stirring.
[0033] Preferably, the stirring speed is 550-650rpm, for example, it can be 550rpm, 560rpm, 570rpm, 580rpm, 590rpm, 600rpm, 610rpm, 620rpm, 630rpm, 640rpm or 650rpm, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.
[0034] Preferably, the mixing time is 10-20 min, for example, it can be 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min or 20 min, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.
[0035] Preferably, the melt coextrusion is carried out in a twin-screw extruder.
[0036] Preferably, the rotational speed of the twin-screw extruder is 450-550r / min, for example, it can be 450r / min, 460r / min, 470r / min, 480r / min, 490r / min, 500r / min, 510r / min, 520r / min, 530r / min, 540r / min or 550r / min, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.
[0037] Preferably, the residence time of the twin-screw extruder is 2-4 min, for example, it can be 2 min, 2.2 min, 2.4 min, 2.6 min, 2.8 min, 3 min, 3.2 min, 3.4 min, 3.6 min, 3.8 min or 4 min, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range.
[0038] Preferably, the temperature of the twin-screw extruder includes:
[0039] The temperature of zone 1 is 195-205°C (for example, 196°C, 197°C, 198°C, 199°C, 200°C, 201°C, 202°C, 203°C or 204°C), the temperature of zone 2 is 245-255°C (for example, 246°C, 247°C, 248°C, 249°C, 250°C, 251°C, 252°C, 253°C or 254°C), and the temperature of zone 3 is 275-285°C (for example, 276°C, 277°C, 278°C , 279°C, 280°C, 281°C, 282°C, 283°C or 284°C, etc.), the temperature of zone four is 270-280°C (for example, it can be 271°C, 272°C, 273°C, 274°C, 275°C, 276°C, 277°C, 278°C or 279°C, etc.), the temperature of zone five is 270-280°C (for example, it can be 271°C, 272°C, 273°C, 274°C, 275°C, 276°C, 277°C, 278°C or 279°C, etc.), The temperature of zone 6 is 270-280°C (for example, it can be 271°C, 272°C, 273°C, 274°C, 275°C, 276°C, 277°C, 278°C or 279°C, etc.), the temperature of zone 7 is 265-275°C (for example, it can be 266°C, 267°C, 268°C, 269°C, 270°C, 271°C, 272°C, 273°C or 274°C, etc.), and the temperature of zone 8 is 265-275°C (for example, it can be 266°C, 267°C, 268°C, 269°C, 270°C, 271°C, 272°C, 273°C or 274°C, etc.). , 269℃, 270℃, 271℃, 272℃, 273℃ or 274℃, etc.), the temperature of zone nine is 265-275℃ (for example, it can be 266℃, 267℃, 268℃, 269℃, 270℃, 271℃, 272℃, 273℃ or 274℃, etc.), the temperature of zone ten is 265-275℃ (for example, it can be 266℃, 267℃, 268℃, 269℃, 270℃, 271℃, 272℃, 273℃ or 274℃, etc.).
[0040] In a third aspect, the present invention provides a polyphenylene ether composite material, wherein the polyphenylene ether composite material comprises the polyphenylene ether composition described in the first aspect.
[0041] Preferably, the polyphenylene ether composite material further comprises an auxiliary agent, carbon black and a composite dye.
[0042] Preferably, the auxiliary agent includes an anti-drip agent and a mold release agent.
[0043] Preferably, the composite dye comprises titanium dioxide.
[0044] Preferably, the preparation method of the polyphenylene ether composite material comprises the following steps:
[0045] The polyphenylene ether composition described in the first aspect is added to a high-speed mixer with an auxiliary agent, carbon black and a composite dye in a ratio of 98.2:1:0.5:0.3 and mixed evenly. The mixing time is 12-18 minutes (for example, it can be 12 minutes, 13 minutes, 14 minutes, 15 minutes, 16 minutes, 17 minutes or 18 minutes, etc.), and the mixed materials are added to a twin-screw extruder for melt co-extrusion. The screw speed, residence time and temperature settings of the extruder are the same as the relevant parameter settings of the melt co-extrusion process in the preparation method of the polyphenylene ether composition described in the second aspect, so as to obtain the polyphenylene ether composite material.
[0046] In a fourth aspect, the present invention provides an application of the polyphenylene ether composite material as described in the third aspect in photovoltaic energy storage, electronic appliances, automobiles, medical products, and aerospace.
[0047] Compared with the prior art, the present invention has at least the following beneficial effects:
[0048] (1) In the polyphenylene ether composition provided by the present invention, by compounding polyphenylene ether, polystyrene, zinc oxide and a phosphorus-based antioxidant, the obtained polyphenylene ether composite material can have high flame retardancy, high mechanical strength and long-term thermal oxidative aging performance.
[0049] (2) The phosphorus-based antioxidant in the present invention acts as a free radical inhibitor, which can stabilize the hydroperoxide free radicals generated due to the thermal effect. When it is compounded with zinc oxide, it can effectively inhibit the thermal degradation of the polyphenylene ether material. Therefore, the compounding of the two can exert a synergistic effect, thereby significantly improving the tensile strength and impact resistance of the obtained polyphenylene ether composite material after long-term thermal aging under high temperature conditions. DETAILED DESCRIPTION
[0050] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.
[0051] Some of the raw material information involved in the following examples and comparative examples are as follows:
[0052] Polyphenylene ether (PPE): purchased from Nantong Xingchen Company LXN040;
[0053] High impact polystyrene (HIPS): purchased from SABIC Innovative Plastics GEH HIPS1897;
[0054] Toughening agent SEBS: purchased from Kraton G1651;
[0055] Phosphorus-based antioxidant: phosphite, purchased from Shanghai Jizhi Biochemical Company (Phosphite A).
[0056] The reagents or raw materials not specially specified in the examples and comparative examples of the present invention are all commercially available.
[0057] Example 1
[0058] This embodiment provides a polyphenylene ether composition, and the raw materials for preparing the composition include the following components in parts by weight:
[0059]
[0060]
[0061] The preparation method of the polyphenylene ether composition is as follows:
[0062] According to the above weight proportions, polyphenylene ether, high impact polystyrene, toughening agent, zinc oxide and phosphorus-based antioxidant are added to a high-speed mixer and mixed for 15 minutes, and the mixed raw materials are added to a twin-screw extruder for melt co-extrusion, and the extruder temperature is: the temperature of zone 1 is 200°C, the temperature of zone 2 is 250°C, the temperature of zone 3 is 280°C, the temperature of zone 4 is 275°C, the temperature of zone 5 is 275°C, the temperature of zone 6 is 275°C, the temperature of zone 7 is 270°C, the temperature of zone 8 is 270°C, the temperature of zone 9 is 270°C, the temperature of zone 10 is 270°C, the extruder screw speed is 500r / min, and the residence time is 3min. After screw extrusion, the mixture is cooled, blown dry and pelletized to obtain the polyphenylene ether composition.
[0063] Example 2
[0064] This embodiment provides a polyphenylene ether composition, and the raw materials for preparing the composition include the following components in parts by weight:
[0065]
[0066] The preparation method of the polyphenylene ether composition is as follows:
[0067] According to the above weight proportions, polyphenylene ether, high impact polystyrene, toughening agent, zinc oxide and phosphorus-based antioxidant (phosphite, Shanghai Aladdin P-EPQ) are added to a high-speed mixer and mixed for 10 minutes. The mixed raw materials are added to a twin-screw extruder for melt co-extrusion. The extruder temperature is: the temperature of zone 1 is 195°C, the temperature of zone 2 is 245°C, the temperature of zone 3 is 275°C, the temperature of zone 4 is 270°C, the temperature of zone 5 is 270°C, the temperature of zone 6 is 270°C, the temperature of zone 7 is 265°C, the temperature of zone 8 is 265°C, the temperature of zone 9 is 265°C, the temperature of zone 10 is 265°C, the screw speed of the extruder is 450r / min, and the residence time is 4min. After screw extrusion, the mixture is cooled, blown dry, and pelletized to obtain the polyphenylene ether composition.
[0068] Example 3
[0069] This embodiment provides a polyphenylene ether composition, and the raw materials for preparing the composition include the following components in parts by weight:
[0070]
[0071] The preparation method of the polyphenylene ether composition is as follows:
[0072] According to the above weight proportions, polyphenylene ether, polystyrene (PS, Chimei, Taiwan, China) PG-383M), toughening agent, zinc oxide and phosphorus-based antioxidant are added to a high-speed mixer and mixed for 20 minutes. The mixed raw materials are added to a twin-screw extruder for melt co-extrusion. The extruder temperature is: the temperature of zone 1 is 205°C, the temperature of zone 2 is 255°C, the temperature of zone 3 is 285°C, the temperature of zone 4 is 280°C, the temperature of zone 5 is 280°C, the temperature of zone 6 is 280°C, the temperature of zone 7 is 275°C, the temperature of zone 8 is 275°C, the temperature of zone 9 is 275°C, the temperature of zone 10 is 275°C, the screw speed of the extruder is 550r / min, and the residence time is 2min. After screw extrusion, the polyphenylene ether composition is obtained by cooling, drying and pelletizing.
[0073] The preparation methods of Examples 4-11 and Comparative Examples 1-2 are the same as that of Example 1, and the weight proportions of the corresponding raw material components are shown in Table 1.
[0074] Table 1
[0075]
[0076]
[0077] Comparative Example 3
[0078] This comparative example provides a polyphenylene ether composition, which differs from Example 1 only in that zinc oxide is replaced by magnesium oxide, and other raw materials, contents and preparation methods are the same as those in Example 1.
[0079] Application Example 1
[0080] This application example provides a polyphenylene ether composite material, and the preparation method thereof comprises the following steps:
[0081] The polyphenylene ether composition (Example 1), auxiliary agents (PTFE and polyethylene wax in a mass ratio of 1:1, PTFE purchased from DuPont MP100 in the United States, polyethylene wax purchased from Honeywell AC), carbon black and composite dye (TiO2) were added to a high-speed mixer in a mass ratio of 98.2:1:0.5:0.3 and mixed evenly for 15 minutes. The mixed materials were added to a twin-screw extruder for melt co-extrusion. The settings of the extruder temperature, extruder screw speed and residence time were the same as the relevant parameter settings of the melt co-extrusion process in Example 1. After screw extrusion, cooling, drying and pelletizing were performed, and the extruder temperature and masterbatch parameters were the same to obtain the polyphenylene ether composite material.
[0082] Application Example 2-11
[0083] The polyphenylene ether composition (Example 1) in Application Example 1 was replaced by the polyphenylene ether compositions (Examples 2-11) respectively, and the other components, contents and preparation methods were the same as those in Application Example 1.
[0084] Comparative Application Examples 1-3
[0085] The polyphenylene ether composition (Example 1) in Application Example 1 was replaced by polyphenylene ether compositions (Comparative Examples 1-3) respectively, and other components, contents and preparation methods were the same as those in Application Example 1.
[0086] The polyphenylene ether compositions obtained in Application Examples 1-11 and Comparative Application Examples 1-3 were subjected to performance tests, and the test methods / standards are as follows:
[0087] (1) Notched impact strength test: Tested in accordance with ISO 179 standard;
[0088] (2) Tensile strength test: Tested in accordance with ISO 527-2 standard;
[0089] (3) Flame retardancy test: Tested according to UL94 standard;
[0090] (4) Thermal oxygen aging resistance test: After the material is aged in an oven at 160°C for 500 hours, the notched impact strength, tensile strength and flame retardancy of the material are tested, and the performance changes of the material before and after thermal oxygen aging are compared:
[0091] Notched impact strength retention rate = (notched impact strength after aging / notched impact strength before aging) × 100%;
[0092] Tensile strength retention rate = (tensile strength after aging / tensile strength before aging) × 100%.
[0093] The test results are shown in Table 2.
[0094] Table 2
[0095]
[0096] In Table 2, “-” indicates that level V cannot be achieved.
[0097] The test results show that:
[0098] (1) It can be seen from Application Examples 1 to 3 that the present invention, by compounding polyphenylene ether, polystyrene, zinc oxide and a phosphorus-based antioxidant, enables the obtained polyphenylene ether composite material to have good heat-oxidative aging resistance while maintaining good mechanical properties and flame retardant properties, that is, a polyphenylene ether composite material with excellent comprehensive performance is obtained.
[0099] (2) By comparing Application Example 1 with Application Examples 4-7, it can be seen that the mass ratio of polyphenylene ether to high-impact polystyrene in Application Example 4 is higher than 3.7:1, the polyphenylene ether content is too high, the compatibility is poor, and it is easy to deteriorate and become brittle, so that the notched impact strength of the obtained polyphenylene ether composite material before aging is significantly reduced, and at the same time, its tensile strength will also decrease, and its thermal oxygen aging resistance is not good; in Application Example 5, the mass ratio of polyphenylene ether to high-impact polystyrene is lower than 2.5:1, and the tensile strength of the obtained polyphenylene ether composite material before aging is reduced, and the tensile strength retention rate and flame retardancy after aging are reduced. It shows that the present invention can further improve the comprehensive properties (mechanical properties, flame retardant properties and thermal oxygen aging resistance) of the obtained polyphenylene ether composite material by limiting the mass ratio of polyphenylene ether to high-impact polystyrene.
[0100] (3) By comparing Application Example 1 with Application Examples 8-11, it can be seen that in Application Example 8, the phosphorus-based antioxidant remains unchanged, the content of zinc oxide is reduced, and when the total content of the two is 6% of the total mass of the raw material, the tensile strength retention rate and the notched impact strength retention rate of the polyphenylene ether composite material obtained after aging are significantly reduced, that is, the heat-oxidative aging resistance of the obtained polyphenylene ether composite material is not good; similarly, when the total content of the two is adjusted to 10% of the total mass of the raw material in Application Example 9, the tensile strength and notched impact strength of the polyphenylene ether composite material obtained before aging are significantly reduced, that is, the mechanical properties of the obtained polyphenylene ether composite material are not good, which further affects the scope of use of the obtained polyphenylene ether composite material. Therefore, the present invention can further improve the comprehensive performance of the obtained polyphenylene ether composite material by adjusting the proportion of the total content of zinc oxide and phosphorus-based antioxidant in the total mass of the raw material, especially when the total content of the two is 8% and the mass ratio of the two is 5:3, the comprehensive performance of the obtained polyphenylene ether composite material is the best, which maintains good flame retardant properties while also having good mechanical properties (tensile strength reaches 15.5MPa, notched impact strength reaches 66.7KJ / m 2 ) and excellent heat-oxidative aging resistance (tensile strength retention rate reaches 83.2%, notched impact strength retention rate reaches 76.9%).
[0101] (4) By comparing Application Example 1 with Comparative Application Examples 1-2, it can be seen that when only zinc oxide or phosphorus-based antioxidants are added, the comprehensive performance of the obtained polyphenylene ether composite materials is not good, indicating that the present invention can make the zinc oxide and phosphorus-based antioxidants play a synergistic role through the compounding of the two, so that the obtained polyphenylene ether composite materials have good mechanical properties and excellent heat-oxidative aging resistance while maintaining good flame retardant properties, that is, have good comprehensive performance, and can be better applied to photovoltaic energy storage, automobile, medical, aerospace and other technical fields.
[0102] (5) By comparing Application Example 1 with Comparative Application Example 3, it can be seen that the present invention can better synergize with the phosphorus-based antioxidant by selecting a specific heat stabilizer oxidizing property, thereby obtaining a technical effect of better resistance to heat and oxygen aging. When zinc oxide is not used, the above-mentioned good technical effect cannot be achieved.
[0103] In summary, the present invention compounds polyphenylene ether, polystyrene, zinc oxide and a phosphorus-based antioxidant to obtain a polyphenylene ether composite material having high flame retardancy, high mechanical strength and long-term thermal oxidative aging performance.
[0104] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.
Claims
1. A polyphenylene ether composition, characterized in that The raw materials for preparing the polyphenylene ether composition include the following components in parts by weight:
2. The polyphenylene ether composition according to claim 1, characterized in that The mass ratio of the polyphenylene ether to the polystyrene is (2.5-3.7):1; Preferably, the polyphenylene ether comprises 2,6-dimethyl-1,4-phenyl ether units and / or 2,3,6-trimethyl-1,4-phenyl ether units; Preferably, the weight average molecular weight of the polyphenylene ether is 80,000-200,000, and the intrinsic viscosity is 0.35-0.6 dL / g; Preferably, the polystyrene comprises high impact polystyrene; Preferably, the main components of the high impact polystyrene include polystyrene and polybutadiene; Preferably, the high impact polystyrene has a weight average molecular weight of 30,000-10,000 and an intrinsic viscosity of 0.6-3 dL / g.
3. The polyphenylene ether composition according to claim 1 or 2, characterized in that: Based on 100% of the total mass of the raw materials for preparing the polyphenylene ether composition, the total content of the zinc oxide and the phosphorus-based antioxidant is 7-9%.
4. The polyphenylene ether composition according to any one of claims 1 to 3, characterized in that The phosphorus-based antioxidant includes a phosphite antioxidant and / or a hindered aryl phosphite antioxidant; Preferably, the phosphite includes any one or a combination of at least two of monophosphite, pentaerythritol distearyl diphosphite, pentaerythritol dioctyl diphosphite or pentaerythritol diphenyl diphosphite; Preferably, the hindered aromatic phosphite includes any one of tris(2,4-di-tert-butylphenyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene phosphite, pentaerythritol diphosphite bis(2,4-di-tert-butylphenyl) ester, pentaerythritol diphosphite bis(2,6-di-tert-butyl-4-methylphenyl) ester or tris(nonylphenyl)phosphite or a combination of at least two thereof.
5. The polyphenylene ether composition according to any one of claims 1 to 4, characterized in that: The raw materials for preparing the polyphenylene ether composition also include a toughening agent; Preferably, the toughening agent includes any one or a combination of at least two of SEBS, MBS, EBA, SBS or SEEPS; Preferably, the content of the toughening agent is 10-18 parts by weight.
6. A method for preparing a polyphenylene ether composition according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: The raw materials including polyphenylene ether, polystyrene, zinc oxide and phosphorus-based antioxidant are mixed and melt co-extruded to obtain the polyphenylene ether composition.
7. The method for preparing the polyphenylene ether composition according to claim 6, characterized in that: The mixing is carried out under stirring; Preferably, the stirring speed is 550-650rpm; Preferably, the mixing time is 10-20 min.
8. The method for preparing the polyphenylene ether composition according to claim 6 or 7, characterized in that: The melt coextrusion is carried out in a twin-screw extruder; Preferably, the speed of the twin-screw extruder is 450-550r / min; Preferably, the residence time of the twin-screw extruder is 2-4 min; Preferably, the temperature of the twin-screw extruder includes: The temperature of zone one is 195-205℃, the temperature of zone two is 245-255℃, the temperature of zone three is 275-285℃, the temperature of zone four is 270-280℃, the temperature of zone five is 270-280℃, the temperature of zone six is 270-280℃, the temperature of zone seven is 265-275℃, the temperature of zone eight is 265-275℃, the temperature of zone nine is 265-275℃, and the temperature of zone ten is 265-275℃.
9. A polyphenylene ether composite material, characterized in that: The polyphenylene ether composite material comprises the polyphenylene ether composition according to any one of claims 1 to 5.
10. Use of the polyphenylene ether composite material according to claim 9 in photovoltaic energy storage, electronic appliances, automobiles, medical products, and aerospace.