A polyphenylene ether composition, its preparation method and application

Abstract

This invention discloses a polyphenylene ether composition, its preparation method, and its applications. The polyphenylene ether composition comprises the following components: 9-26 parts PPE resin, 19-41 parts PA resin, 5-10 parts phosphorus-containing flame retardant A, 2-6 parts phosphorus-containing flame retardant B, 5-15 parts compatibilizer, and 10-40 parts glass fiber; the zero-shear viscosity of the polyphenylene ether composition is 10000-100000 Pa·s; the average retention length of the glass fiber is 0.2-0.35 mm; phosphorus-containing flame retardant A is selected from one or more of hypophosphite flame retardants, red phosphorus, and polyphosphate flame retardants; phosphorus-containing flame retardant B is selected from one or more of phosphate ester flame retardants and phosphazene flame retardants. The polyphenylene ether composition exhibits good ablation resistance.

Description

Technical Field

[0001] This invention belongs to the technical field of engineering plastics, and more specifically, relates to a polyphenylene ether composition, its preparation method, and its application. Background Technology

[0002] Polyphenylene oxide (PPE) is an engineering plastic with excellent comprehensive properties, including high strength, high rigidity, high heat resistance, and low smoke density. However, PPE also has some drawbacks, such as poor processability and poor solvent resistance, which limit its application in demanding environments. By blending PPE with polyamide (PA) to prepare alloys, the complementary properties of the two materials can be effectively achieved, leading to its widespread use in electronics, automotive, and other fields.

[0003] According to GB / T 38031-2020 "Safety Requirements for Power Batteries for Electric Vehicles", the flame retardant and ablation resistance properties of the materials used in the battery cover of new energy vehicles are very high. To meet the demand for replacing steel with plastic in battery cover materials, ablation-resistant PPE-PA compositions show great promise for application.

[0004] Patent CN116253982A discloses a flame-retardant, weather-resistant, and heat-resistant polyphenylene ether-nylon plastic alloy, comprising the following components: polyphenylene ether, nylon, flame retardant, compatibilizer, antioxidant, and light stabilizer. The antioxidant includes two or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis(2,4-dicumylphenyl)pentaerythritol diphosphite, and pentaerythritol-based dodecathiopropyl ester. While the aforementioned polyphenylene ether-nylon plastic alloy achieves a V-0 flame retardancy rating, its melt strength is low and cannot withstand prolonged high-temperature ablation. Therefore, providing a polyphenylene ether composition with excellent ablation resistance is a pressing technical problem that needs to be solved. Summary of the Invention

[0005] In view of the above-mentioned existing technical problems, the primary objective of the present invention is to provide a polyphenylene ether composition that has good ablation resistance.

[0006] A second objective of this invention is to provide a method for preparing a polyphenylene ether composition.

[0007] A third objective of this invention is to provide an application of a polyphenylene ether composition in the fields of electronics, electrical appliances, or automobiles.

[0008] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0009] A polyphenylene ether composition, by weight, comprises the following components: 9-26 parts PPE resin, 19-41 parts PA resin, 5-10 parts phosphorus-containing flame retardant A, 2-6 parts phosphorus-containing flame retardant B, 5-15 parts compatibilizer, and 10-40 parts glass fiber; the zero-shear viscosity of the polyphenylene ether composition is 10,000-100,000 Pa·s; the average retention length of the glass fiber is 0.2-0.35 mm; the phosphorus-containing flame retardant A is selected from one or more of hypophosphite flame retardants, red phosphorus, and polyphosphate flame retardants; the phosphorus-containing flame retardant B is selected from one or more of phosphate ester flame retardants and phosphazene flame retardants.

[0010] During the high-temperature ablation process, the surface of the polyphenylene ether composition is burned into carbon, while the matrix is ​​heated and melted, causing deformation. When the carbon layer is insufficient to support the flow of the melt under gravity, the material will perforate, leading to ablation failure.

[0011] The inventors discovered through research that the zero-shear viscosity of the composition and the average retention length of the glass fibers jointly affect the melt strength.

[0012] When the zero-shear viscosity of the prepared polyphenylene ether composition is within the above-mentioned range, the polyphenylene ether composition can maintain a certain melt strength, which is beneficial for ensuring the formation of a stable carbon layer in the melt during high-temperature ablation, avoiding collapse and perforation. Simultaneously, the above-mentioned zero-shear viscosity range can meet the flowability requirements of the polyphenylene ether composition during molding and processing, ensuring uniform dispersion of the flame retardant in the resin matrix. It can also reduce the shearing effect of the resin on the glass fibers during blending and extrusion, increasing the average retention length of the glass fibers. The specific average retention length of the glass fibers can form a continuous and stable three-dimensional glass fiber network in the polyphenylene ether-polyamide system, improving the melt strength of the system. If the average retention length of the glass fibers is too long, it indicates insufficient shear force, incomplete plasticization of the material, and a decrease in ablation resistance; if the average retention length of the glass fibers is too short, it cannot play an effective reinforcing role in the melt, leading to the failure of flame retardant ability during ablation.

[0013] Furthermore, the inventors discovered through research that the average retention length of the glass fiber and a specific combination of phosphorus-containing flame retardants jointly affect the thickness of the carbon layer.

[0014] Glass fibers with a specific average retention length not only enhance the melt strength of the polyphenylene ether-polyamide system but also effectively disperse and conduct heat, reducing thermal degradation and ensuring the formation of a stable carbon layer, thereby improving the material's ablation resistance. A specific combination of phosphorus-containing flame retardants A and B is used. Phosphorus-containing flame retardant A decomposes at high temperatures to generate free radicals, which can capture free radicals generated during combustion, thus interrupting the chain reaction of combustion and promoting rapid charring of the polymer to form a carbon layer. The synergistic effect of phosphorus-containing flame retardant B further improves flame retardant efficiency, while the decomposed substances form a non-volatile protective film on top of the existing carbon layer, thereby enhancing the carbon layer strength, improving oxygen and heat insulation effects, and achieving excellent ablation resistance.

[0015] This invention provides a polyphenylene ether composition. By controlling the zero-shear viscosity of the polyphenylene ether composition, the average retention length of the glass fiber, and specific phosphorus-containing flame retardants A and B, and by combining them with a compatibilizer in the system, the prepared polyphenylene ether composition exhibits good ablation resistance.

[0016] Specifically, the PPE resin accounts for no less than 7.4% of the mass percentage of the polyphenylene ether composition. More preferably, the PPE resin accounts for no less than 11.6% of the mass percentage of the polyphenylene ether composition.

[0017] Specifically, the PA resin accounts for no less than 16.3% of the mass percentage of the polyphenylene ether composition. More preferably, the PA resin accounts for no less than 19.6% of the mass percentage of the polyphenylene ether composition.

[0018] Specifically, the PPE resin can be 12 parts, 15 parts, 18 parts, 21 parts, 23 parts, 25 parts, or any range of the above values; the PA resin can be 21 parts, 23 parts, 25 parts, 27 parts, 29 parts, 31 parts, 33 parts, 35 parts, 37 parts, 40 parts, or any range of the above values; the glass fiber can be 13 parts, 15 parts, 18 parts, 20 parts, 23 parts, 25 parts, 28 parts, 30 parts, 33 parts, 35 parts, 38 parts, 40 parts, or any range of the above values.

[0019] Specifically, the zero-shear viscosity of the polyphenylene ether composition is 12000–81000 Pa·s; and the average retention length of the glass fiber is 0.230–0.312 mm.

[0020] Specifically, the zero-shear viscosity of the polyphenylene ether composition can be 20000 Pa·s, 30000 Pa·s, 40000 Pa·s, 50000 Pa·s, 60000 Pa·s, 70000 Pa·s, 80000 Pa·s, 90000 Pa·s, or any range formed by the above values, such as 45000~71000 Pa·s, 40000~80000 Pa·s, etc., and the present invention is not limited thereto. The test method for the zero-shear viscosity of the polyphenylene ether composition is as follows: the test is performed using a rotational rheometer, and the specific method can be found in JY / T0590-2020 "General Rules for Measurement Methods of Rotational Rheometer".

[0021] Specifically, the average retention length of the glass fiber in this invention can be 0.22 mm, 0.24 mm, 0.26 mm, 0.28 mm, 0.30 mm, 0.32 mm, 0.34 mm, etc., or any range formed by the above values, such as 0.24–0.28 mm, 0.26–0.32 mm, etc., and this invention is not limited thereto. The test method for the average retention length of the glass fiber is: optical microscope-image analyzer method. More specifically, the test method can be performed with reference to the method disclosed in patent CN 109164106 A. Those skilled in the art can adjust the average retention length of the glass fiber using conventional techniques in the art; for example, resins of different viscosities can be used, as resins of different viscosities will affect the shear strength during processing, thereby affecting the average retention length of the glass fiber; for example, it can be added from different feed ports of the screw extruder, thereby adjusting the average retention length of the glass fiber.

[0022] Specifically, the intrinsic viscosity of the PA resin is 1.5–3.0 dL / g. The intrinsic viscosity of the PA resin is tested using an Ubbelohde viscometer with sulfuric acid as the solvent.

[0023] Specifically, the intrinsic viscosity of the PPE resin is 0.4–0.45 dL / g. The intrinsic viscosity of the PPE resin is tested using an Ubbelohde viscometer with chloroform as the solvent.

[0024] Preferably, the phosphorus-containing flame retardant A is selected from one or more of diethylaluminum hypophosphite, diethylzinc hypophosphite, phenylaluminum hypophosphite, red phosphorus, and ammonium polyphosphate.

[0025] Preferably, the phosphate ester flame retardant is selected from one or more of triphenyl phosphate, selenophosphate, tributyl phosphate, trioctyl phosphate, toluene diphenyl phosphate, and isopropylated triphenyl phosphate; and / or

[0026] The phosphazene flame retardant is selected from one or more of hexaphenoxycyclotriphosphazene, hexachlorocyclotriphosphazene and their derivatives.

[0027] Preferably, the compatibilizer is one or more of PPE graft, SEBS graft, and POE graft; the graft portion of the PPE graft, SEBS graft, and POE graft is selected from one or more of maleic anhydride, fumaric anhydride, citric acid, and unsaturated dicarboxylic acid.

[0028] Preferably, the grafting rate of the PPE graft, SEBS graft, and POE graft is 0.6% to 3.5%. More preferably, the grafting rate is 0.6% to 1.5%. Under these preferred conditions, the polyphenylene ether composition exhibits superior melt strength and mechanical properties. More specifically, the grafting rate in this invention can be 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.7%, 1.9%, etc., or any range formed by the above values, such as 0.6% to 1.3%, 0.9% to 1.7%, etc., and this invention is not limited thereto. More specifically, the grafting rate is tested using infrared spectroscopy.

[0029] Preferably, the PA resin is selected from one or more of PA6 resin, PA46 resin, PA66 resin, PA610 resin, PA612 resin, PA66 / 6T resin, and PA6I / 6T resin. More preferably, the PA resin is PA66 resin and / or PA66 / 6T resin.

[0030] Preferably, the glass fiber has a diameter range of 8–15 μm and a length range of 2–5 mm.

[0031] Preferably, the polyphenylene ether composition further includes one or more of a lubricant, mineral powder, and colorant. The lubricant includes, but is not limited to, polyethylene wax, zinc stearate, lithium stearate, etc. The mineral powder includes, but is not limited to, talc, calcium carbonate, kaolin, mica powder, barium sulfate, etc. The colorant includes, but is not limited to, carbon black, titanium dioxide, zinc sulfide, titanium yellow, iron oxide red, etc.

[0032] Furthermore, the present invention claims protection for a method for preparing a polyphenylene ether composition, wherein PPE resin, PA resin, compatibilizer, phosphorus-containing flame retardant A, and phosphorus-containing flame retardant B are mixed and extruded, and glass fiber is added and extruded from a side feed port to obtain the polyphenylene ether composition.

[0033] Preferably, a twin-screw extruder is used for extrusion, wherein the length-to-diameter ratio of the twin-screw extruder is 40 to 56:1.

[0034] Preferably, the screw speed of the twin-screw extruder is 300 to 1000 rpm.

[0035] Preferably, the extrusion temperature is 250–280°C.

[0036] Furthermore, this invention claims protection for the application of a polyphenylene ether composition in the fields of electronics, electrical appliances, or automobiles. Specifically, the polyphenylene ether composition is suitable for power battery brackets, covers and housings, IGBT modules, high-voltage connectors, etc., especially in applications requiring high resistance to burning.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] This invention provides a polyphenylene ether composition. By controlling the zero-shear viscosity of the polyphenylene ether composition, the average retention length of the glass fiber, and specific phosphorus-containing flame retardants A and B, and by combining them with a compatibilizer in the system, the prepared polyphenylene ether composition exhibits good ablation resistance. Detailed Implementation

[0039] The present invention will be further described below with reference to the specification and specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.

[0040] The raw materials for the examples and comparative examples are as follows:

[0041] PPE resin 1, intrinsic viscosity 0.4 dL / g, PPE LXN040, Nantong Xingchen Synthetic Materials Co., Ltd.

[0042] PPE resin 2, intrinsic viscosity 0.43 dL / g, XYRON S201A, Asahi Kasei Corporation, Japan.

[0043] PPE resin 3, intrinsic viscosity 0.45 dL / g, PPE ZM045, Dalian Zhongmu Chemical Co., Ltd.

[0044] PPE resin 4, intrinsic viscosity 0.35 dL / g, PPE LXN035, Nantong Xingchen Synthetic Materials Co., Ltd.

[0045] PPE resin 5, intrinsic viscosity 0.5 dL / g, PPE LXN050, Nantong Xingchen Synthetic Materials Co., Ltd.

[0046] PA resin 1, PA6, intrinsic viscosity 2.4 dL / g, HY-2500A, Jiangsu Haiyang Chemical Fiber Co., Ltd.

[0047] PA resin 2, PA66, intrinsic viscosity 2.4 dL / g, PA66 U3600 NC01 SS, Invista Nylon Chemicals (China) Co., Ltd.

[0048] Phosphorus-containing flame retardant A, aluminum diethylphosphite, EXOLIT OP 1230, Clariant Chemicals Ltd.

[0049] Phosphorus-containing flame retardant B1, hexaphenoxycyclotriphosphazene, HPCTP, Hongda Dante Chemical Co., Ltd.

[0050] Phosphorus-containing flame retardant B2, triphenyl phosphate, WSFR-TPP, manufactured by Zhejiang Wansheng Technology Co., Ltd.

[0051] Flame retardant 1, magnesium hydroxide, Aitemag 12FD, Jiangsu Aitemag Flame Retardant Materials Co., Ltd.

[0052] Flame retardant 2, brominated polystyrene, BPS HM-20, Weifang Shuangfeng Chemical Co., Ltd.

[0053] Fiberglass, ECS10-03-568H, China Jushi Co., Ltd.

[0054] Compatibilizer 1 is PPE grafted with maleic anhydride, with a grafting rate of 1.5%. Compatibilizer 1 is prepared by blending 3% (by mass) of maleic anhydride with PPE resin 1 and extruding; the length-to-diameter ratio of the twin-screw extruder is 56:1; the screw speed of the twin-screw extruder is 600 rpm; and the extrusion temperature is 280℃.

[0055] Compatibilizer 2 is PPE grafted with maleic anhydride, with a grafting rate of 0.6%. The preparation method of compatibilizer 2 is as follows: 1.5% by mass of maleic anhydride is co-extruded with PPE resin 1.

[0056] Compatibilizer 3 is PPE grafted with maleic anhydride, with a grafting rate of 2.0%. The preparation method of compatibilizer 3 is as follows: referring to the preparation method of compatibilizer 1, 5% by mass of maleic anhydride is blended with PPE resin 1 and extruded.

[0057] Compatibilizer 4, POE graft, POE-g-MAH, grafting rate 3.5%, FB521A, Jia Yi Rong Polymer (Shanghai) Co., Ltd.

[0058] Unless otherwise specified, all components used in the parallel embodiments and comparative examples are the same commercially available products.

[0059] Example 1

[0060] The weight proportions of the raw materials used in Example 1 are shown in Table 1.

[0061] A method for preparing a polyphenylene ether composition, comprising the following steps:

[0062] PPE resin, PA resin, compatibilizer, phosphorus-containing flame retardant A, and phosphorus-containing flame retardant B are added to a high-speed mixer and mixed evenly to obtain a homogeneous material. The homogeneous material is fed into a twin-screw extruder (length-to-diameter ratio of 56:1, speed of 600 rpm) through the main feed port. Glass fiber is fed into the extruder through the side feed port and extruded (at 280°C). Granulation is then performed to obtain a polyphenylene ether composition.

[0063] Examples 2 to 11

[0064] The weight proportions of the raw materials used in the following embodiments are shown in Table 1.

[0065] The specific preparation steps for the following embodiments are the same as those for Embodiment 1.

[0066] Comparative Examples 1 to 8

[0067] The weight proportions of raw materials used in each of the following comparative examples are shown in Table 2.

[0068] Adding glass fibers from the main feed port will cause the glass fibers to break more. Therefore, in order to obtain a shorter average retained length of glass fibers, the difference between Comparative Example 6 and Example 1 is that the glass fibers are added to the extruder from the main feed port and then extruded.

[0069] The specific preparation steps for the other comparative examples are the same as those in Example 1.

[0070] Table 1

[0071]

[0072] Table 2 shows the formulation components for each comparative example:

[0073] Table 2

[0074]

[0075]

[0076] The polyphenylene ether compositions prepared in the above embodiments and comparative examples were tested using the following test methods.

[0077] Zero-shear viscosity: The zero-shear viscosity of the extruded polyphenylene ether composition was tested using a rotational rheometer at 300°C and a shear rate of 0.1 rad / s.

[0078] Notched impact strength: Injection-molded specimens of polyphenylene oxide composition, tested according to ISO 180:2019.

[0079] High-temperature flexural modulus: Injection-molded specimens of polyphenylene ether composition were tested according to ISO 178:2019 at a test temperature of 105℃.

[0080] Average retention length of glass fibers: The average retention length of glass fibers in the polyphenylene ether composition obtained by extrusion was tested according to the method disclosed in patent CN 109164106A.

[0081] Ablation resistance: The polyphenylene oxide composition was injection molded into a 2*150*150mm square plate, placed horizontally, and subjected to a 1000℃ flame ablation for 10 minutes. Observe whether dents or burn-through appear. "Pass" means no dents or burn-through appear; "Fail" means dents and / or burn-through appear.

[0082] Melt strength: The online melt strength of the extruded polyphenylene ether composition was tested using a Hacker torque rheometer.

[0083] Tables 3 and 4 show the performance test results for each embodiment and comparative example, respectively.

[0084] Table 3

[0085]

[0086] Table 4

[0087]

[0088] As shown by the example data, the present invention provides a polyphenylene ether composition. When the average retention length of the glass fiber is 0.2–0.35 mm and the zero-shear viscosity of the polyphenylene ether composition is 10,000–100,000 Pa·s, the polyphenylene ether composition exhibits excellent melt strength and ablation resistance. When subjected to flame ablation at 1000°C for 10 minutes under horizontal placement, no indentation or burn-through occurs; and the melt strength is ≥32 cN. More preferably, the melt strength is ≥49 cN.

[0089] As can be seen from Examples 1, 5 and 6, when the grafting rate of the grafted material in the compatibilizer is within the preferred range, the polyphenylene ether composition has superior melt strength and mechanical properties.

[0090] As can be seen from Example 1, Comparative Example 1 and Comparative Example 2, when the zero-shear viscosity of the polyphenylene ether composition is in the range of 10,000 to 100,000 Pa·s, no indentation or burn-through will occur in the burn resistance test.

[0091] As can be seen from Examples 1, 3, 4, 7 and 8, when a specific flame retardant is not used in the polyphenylene ether composition system, even if it has acceptable melt strength, its char layer strength is still insufficient, and the polyphenylene ether composition will show dents and burn-through, and the ablation resistance effect is unqualified.

[0092] As shown in Example 1 and Comparative Example 6, the polyphenylene ether composition exhibits excellent burn resistance when the average retained length of the glass fibers is in the range of 0.2–0.35 mm. However, when the average retained length of the glass fibers is below this range, the polyphenylene ether composition will show dents and burn-through.

[0093] The foregoing examples are merely illustrative, used to explain some features of the method described in this invention. The appended claims are intended to claim the broadest possible scope, and the embodiments presented herein are demonstrated by the applicant's actual experimental results. Therefore, the applicant intends that the appended claims are not limited by the selection of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within them, and variations within these ranges should also be interpreted as being covered by the appended claims where possible.

Claims

1. A polyphenylene ether composition, characterized in that, The following components are included by weight parts: PPE resin 9-26 parts, PA resin 19-41 parts, phosphorus-containing flame retardant A 5-10 parts, phosphorus-containing flame retardant B 2-6 parts, compatibilizer 5-15 parts, glass fiber 10-40 parts; The zero shear viscosity of the polyphenyl ether composition is 10000-100000 Pa·s; The average retention length of the glass fiber is 0.2-0.35 mm; The phosphorus-containing flame retardant A is selected from one or more of aluminum diethyl hypophosphite, zinc diethyl hypophosphite, and aluminum phenyl hypophosphite; and the phosphorus-containing flame retardant B is selected from one or more of phosphate ester flame retardants and phosphazene flame retardants.

2. The polyphenylene ether composition according to Claim 1, wherein The zero shear viscosity of the polyphenyl ether composition is 12000-81000 Pa·s; and the average retention length of the glass fiber is 0.230-0.312 mm.

3. The polyphenylene ether composition according to Claim 1, wherein The phosphate ester flame retardant is selected from one or more of triphenyl phosphate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, cresyl diphenyl phosphate, and isopropylated triphenyl phosphate; and / or The phosphazene flame retardant is selected from one or more of hexaphenoxy cyclotriphosphazene, hexachlorocyclotriphosphazene, and derivatives thereof.

4. The polyphenylene ether composition according to Claim 1, wherein The compatibilizer is one or more of PPE grafts, SEBS grafts, and POE grafts; and the grafting portion of the PPE grafts, SEBS grafts, and POE grafts is selected from one or more of maleic anhydride, fumaric anhydride, citric acid, and unsaturated dicarboxylic acid.

5. The polyphenylene ether composition according to Claim 4, wherein The grafting rate of the PPE grafts, SEBS grafts, and POE grafts is 0.6-3.5%.

6. The polyphenylene ether composition according to Claim 1, wherein The PA resin is selected from one or more of PA6 resin, PA46 resin, PA66 resin, PA610 resin, PA612 resin, PA66 / 6T resin, and PA6I / 6T resin.

7. The polyphenylene ether composition according to Claim 1, wherein The polyphenyl ether composition includes one or more of lubricants, mineral powder, and colorants.

8. A process for the preparation of the polyphenylene ether composition according to any one of claims 1 to 7, characterized in that, The PPE resin, PA resin, compatibilizer, phosphorus-containing flame retardant A, and phosphorus-containing flame retardant B are mixed and extruded, and the glass fiber is added from a side feeding port for extrusion to obtain the polyphenyl ether composition.

9. Use of the polyphenyl ether composition according to any one of claims 1-7 in the field of electronics, electrical appliances, or automobiles.

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