Polyphenylene ether resin composition, preparation method therefor, and use thereof

Abstract

The present application discloses a polyphenylene ether resin composition, a preparation method therefor, and a use thereof. The polyphenylene ether resin composition of the present application comprises the following components in parts by weight: 18-51 parts of polyphenylene ether resin and / or maleic anhydride grafted polyphenyl ether resin, 18-42 parts of a crystalline polyamide, 4-11 parts of an amorphous polyamide, 1-13 parts of a phosphorus-containing flame retardant, and 8-42 parts of glass fiber, the melting point of the crystalline polyamide being ≥210°C. By means of adding crystalline polyamide and amorphous polyamide, the present application can improve ablation resistance while ensuring good product appearance performance.

Description

A polyphenylene ether resin composition and its preparation method and application Technical Field

[0001] The present invention relates to the field of polyphenylene ether resin compositions, and specifically relates to a polyphenylene ether resin composition, a preparation method thereof, and an application thereof. Background Art

[0002] At present, in order to meet the requirements of ablation resistance, the cover plates on power batteries are mainly produced using thermosetting plastics. However, thermosetting plastics have a high specific gravity, low production efficiency, are not recyclable, and have a high overall cost. Polyphenylene ether (PPE) compositions have the advantages of excellent flame retardancy, high rigidity, light density, very high melt viscosity and carbonization rate, and can be used on the cover plates of power batteries. However, because the softening point of polyphenylene ether is too low, the polyphenylene ether group material will still melt, and the ablation resistance is poor, and it still cannot meet the requirements of the external fire and thermal runaway tests in GB38031 "Safety Requirements for Power Batteries for Electric Vehicles".

[0003] In the prior art, glass fiber is often added to polyphenylene ether materials. However, after adding glass fiber, although the melt strength of the material is greatly improved and the time for molten droplets to occur at high temperatures can be extended, it is still insufficient to withstand high temperatures and the ablation resistance does not meet the requirements. Patent document CN115594970A discloses the introduction of terephthalic acid polyamide with an aromatic structure into the polyphenylene ether structure to increase the melting point of the polyphenylene ether and thus improve the ablation resistance. However, because aromatization is required on the polyamide molecule, the preparation method conditions and process are relatively harsh, resulting in a sharp increase in production costs. In addition, the presence of glass fiber in the system also exacerbates the material's appearance problems such as floating fibers, resulting in obvious appearance problems such as floating fibers during injection molding of the entire system. The size of the general power battery cover is over 1m, or even over 2m, and the shear strength during injection molding is strong. When using conventional polyphenylene ether composition materials for preparation, the crystallization rate is fast and it is easy to degrade, further exacerbating appearance quality problems such as water splashes, air marks, and floating fibers.

[0004] Therefore, the industry hopes to further develop solutions for polyphenylene ether compositions to improve the product's ablation resistance and injection molding appearance while reducing overall costs. Summary of the Invention

[0005] In response to the problems of poor ablation resistance and appearance performance of polyphenylene ether compositions, this application will provide a polyphenylene ether resin composition, a preparation method and application thereof.

[0006] The specific technical solutions include the following:

[0007] A polyphenylene ether resin composition comprises the following components in parts by weight:

[0008] 18-51 parts of polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin, 18-42 parts of crystalline polyamide, 4-11 parts of amorphous polyamide, 1-13 parts of phosphorus-containing flame retardant, and 8-42 parts of glass fiber; the melting point of the crystalline polyamide is ≥210°C.

[0009] In some embodiments, the crystalline polyamide has a melting point of 220-270°C.

[0010] In some embodiments, at least one of the following is included:

[0011] The mass ratio of the crystalline polyamide to the amorphous polyamide is crystalline polyamide:amorphous polyamide=(2.5-7):1;

[0012] The polyphenylene ether resin composition comprises polyphenylene ether resin and maleic anhydride grafted polyphenylene ether resin, and the mass ratio of the polyphenylene ether resin to the maleic anhydride grafted polyphenylene ether resin is 1:(0.3-2).

[0013] In some embodiments, the mass percentage of terephthalic acid in the crystalline polyamide is less than 5%.

[0014] In some embodiments, the ratio of the total mass of the polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin to the total mass of the crystalline polyamide and the amorphous polyamide is (0.7-1.5):1.

[0015] In some embodiments, the phosphorus-containing flame retardant includes at least one of diethyl aluminum hypophosphite, red phosphorus, phosphate flame retardants, and phosphazene flame retardants.

[0016] In some embodiments, the polyphenylene ether resin composition further comprises at least one of the following components in parts by weight: 0.01-5 parts of a toughening agent, 0.01-5 parts of a lubricant, 0.01-5 parts of a colorant, and 0.01-5 parts of a filler.

[0017] In some embodiments, the crystalline polyamide resin includes at least one of PA66 (polyhexamethylene adipamide), PA56 (polypentamethylene adipamide), and PA612 (polyhexamethylene dodecane diamide); the amorphous polyamide resin includes at least one of PA6I / 6T and PA12 (polylaurolactam).

[0018] The present application also provides a method for preparing the polyphenylene ether resin composition, comprising the following steps: extruding and granulating polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin, crystalline polyamide, amorphous polyamide, a phosphorus-containing flame retardant and glass fiber to obtain the polyphenylene ether resin composition.

[0019] The present application also provides an application of the polyphenylene ether resin composition in a battery top cover.

[0020] Compared with the prior art, the present invention has the following beneficial effects: by simultaneously adding crystalline PA resin and amorphous PA resin, the present invention improves the ablation resistance while maintaining good product appearance and impact strength. DETAILED DESCRIPTION

[0021] The present application provides a polyphenylene ether resin composition, comprising the following components in parts by weight: 18-51 parts of polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin, 18-42 parts of crystalline polyamide, 4-11 parts of amorphous polyamide, 1-13 parts of a phosphorus-containing flame retardant, and 8-42 parts of glass fiber; the melting point of the crystalline polyamide is ≥210°C.

[0022] The present application improves the ablation resistance while maintaining good product appearance by adding a specific content of crystalline polyamide with a specific melting point and a specific content of amorphous polyamide, and compounding a specific content of glass fiber.

[0023] In some embodiments, the polyphenylene ether resin composition comprises the following components in parts by weight: 35-45 parts of polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin, 25-35 parts of crystalline polyamide, 5-10 parts of amorphous polyamide, 2-6 parts of phosphorus-containing flame retardant, and 15-25 parts of glass fiber.

[0024] In some embodiments, in the polyphenylene ether resin composition, the total mass percentage of the polyphenylene ether resin and / or the maleic anhydride grafted polyphenylene ether resin is no less than 20%.

[0025] In some embodiments, there is no special requirement for the intrinsic viscosity of the polyphenylene ether resin. In some embodiments, the intrinsic viscosity of the polyphenylene ether resin can be ≤42 cm 3 In some embodiments, 96% concentrated sulfuric acid can be selected as the solvent for testing according to ISO 307-2019 standard.

[0026] In some embodiments, the melting point of the crystalline polyamide is 211-300° C. In some embodiments, the melting point of the crystalline polyamide can be tested using a DSC method. In some embodiments, the heating rate is preferably 5-10° C. / min.

[0027] In some embodiments, the melting point of the crystalline polyamide is 220-270° C. There is no limitation on the type of the amorphous polyamide.

[0028] The melting point of crystalline polyamide can be 215, 220, 225, 230, 235, 240, 245, 250, 265, 270, 275, 280, 295, 300°C and above, as well as specific point values ​​between the above point values ​​and ranges consisting of any two of the above point values. Due to limited space and for the sake of simplicity, this application no longer exhaustively lists the specific point values ​​included in the said range.

[0029] In some embodiments, the crystalline polyamide resin includes at least one of PA66, PA56, and PA612.

[0030] In some embodiments, the amorphous polyamide resin includes at least one of PA6I / 6T and PA12.

[0031] In some embodiments, the amorphous polyamide resin includes at least one of PA3426 and PA1239.

[0032] In some embodiments, the mass ratio of the crystalline polyamide to the amorphous polyamide is crystalline polyamide:amorphous polyamide = (2.5-7): 1. In some embodiments, the mass ratio of the crystalline polyamide to the amorphous polyamide is crystalline polyamide:amorphous polyamide = (2.8-5):1.

[0033] In some embodiments, the crystallinity of the crystalline polyamide is greater than 20%. In some embodiments, the crystallinity of the crystalline polyamide is 30-90%. In some embodiments, the crystallinity of the crystalline polyamide is 50-85%.

[0034] Under the above mass ratio of crystalline polyamide to amorphous polyamide, the polyphenylene ether resin composition has better ablation resistance.

[0035] In some embodiments, the crystalline polyamide has a terephthalic acid content of less than 5% by weight. In some embodiments, the crystalline polyamide has a terephthalic acid content of less than 3% by weight. In some embodiments, the crystalline polyamide has a terephthalic acid content of less than 1% by weight. In some embodiments, the crystalline polyamide has a terephthalic acid content of 0% by weight.

[0036] In some embodiments, the relative viscosity of the crystalline polyamide is 1 to 3. In some embodiments, the relative viscosity of the crystalline polyamide is 2.4 to 2.7. In some embodiments, the relative viscosity is tested in accordance with GB / T1632-1993.

[0037] In some embodiments, the relative viscosity of the amorphous polyamide is 1 to 3. In some embodiments, the relative viscosity of the amorphous polyamide is 2.4 to 2.7. In some embodiments, the relative viscosity is measured in accordance with GB / T1632-1993.

[0038] In some embodiments, the polyphenylene ether resin composition includes polyphenylene ether resin and maleic anhydride grafted polyphenylene ether resin, and the mass ratio of the polyphenylene ether resin to the maleic anhydride grafted polyphenylene ether resin is 1:(0.3-2).

[0039] In some embodiments, the mass ratio of the polyphenylene ether resin to the maleic anhydride grafted polyphenylene ether resin is 1:(0.3-1.7). In some embodiments, the mass ratio is 1:(0.8-1.2).

[0040] The mass ratio of the polyphenylene ether resin and the maleic anhydride grafted polyphenylene ether resin can be (1:0.3), (1:0.4), (1:0.5), (1:0.6), (1:0.7), (1:0.8), (1:0.9), (1:1), (1:1.1), (1:1.2), (1:1.3), (1:1.4), (1:1.5), (1:1.6), (1:1.7), (1:1.8), (1:1.9), (1:2), etc., as well as specific point values ​​between the above point values ​​and ranges consisting of any two of the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values ​​included in the range.

[0041] In some embodiments, the grafting rate of the maleic anhydride grafted polyphenylene ether resin is 0.5-2%. In some embodiments, the grafting rate of the maleic anhydride grafted polyphenylene ether resin can be measured by conventional grafting rate testing methods in the art, such as acid-base titration (chemical titration).

[0042] In some embodiments, when a portion of MAH-modified polyphenylene ether resin is added to the polyphenylene ether resin, the ablation resistance of the polyphenylene ether resin composition is better.

[0043] In some embodiments, the ratio of the total mass of the polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin to the total mass of the crystalline polyamide and the amorphous polyamide is (0.7-1.5):1.

[0044] In some embodiments, the ratio of the total mass of the polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin to the total mass of the crystalline polyamide and the amorphous polyamide is (0.9-1.3):1.

[0045] In some embodiments, the phosphorus-containing flame retardant includes at least one of diethyl aluminum hypophosphite, red phosphorus, phosphate flame retardants, and phosphazene flame retardants.

[0046] In some embodiments, the phosphorus-containing flame retardant includes at least one of diethyl aluminum hypophosphite, red phosphorus, and an organic phosphorus flame retardant.

[0047] In some embodiments, the organophosphorus flame retardant includes at least one of flame retardant BDP, flame retardant RDP, flame retardant TPP, and phosphazene.

[0048] In some embodiments, the polyphenylene ether resin composition further comprises at least one of the following components in parts by weight: 0.01-5 parts of a toughening agent, 0.01-5 parts of a lubricant, 0.01-5 parts of a colorant, and 0.01-5 parts of a filler.

[0049] The toughening agent is not particularly limited and includes, but is not limited to, ethylene-octene copolymer (POE) and SEBS. The filler includes, but is not limited to, calcium carbonate, talc, mica, kaolin, magnesium hydroxide, and boehmite. The lubricant includes, but is not limited to, polyethylene wax, zinc stearate, and lithium stearate. The colorant includes, but is not limited to, carbon black, titanium dioxide, zinc sulfide, iron oxide red, and titanium yellow.

[0050] In some embodiments, the length of the glass fiber is less than 10 mm.

[0051] The present application also provides a method for preparing the polyphenylene ether resin composition, comprising the following steps: extruding and granulating polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin, crystalline polyamide, amorphous polyamide, a phosphorus-containing flame retardant and glass fiber to obtain the polyphenylene ether resin composition.

[0052] In some embodiments, polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin, crystalline polyamide, amorphous polyamide and phosphorus-containing flame retardant are added from the main feed port of a twin-screw extruder, and glass fiber is added from the side feed port for extrusion granulation.

[0053] In some embodiments, the extrusion temperature is 220-300°C.

[0054] The application of the polyphenylene ether resin composition described in this application in the battery cover plate can meet the requirements of the corresponding components of the battery pack for ablation resistance and appearance performance. For example, when used in the battery cover, products with a length greater than 1m have no appearance problems and meet the requirements of its ablation resistance performance.

[0055] To better illustrate the purpose, technical solutions, and advantages of this application, the present application will be further described below through specific examples. Unless otherwise specified, the experimental methods used in the examples and / or comparative examples are conventional methods; the materials and reagents used are all commercially available unless otherwise specified.

[0056] Raw material brand information:

[0057] (1) PPE resin:

[0058] PPE-1, trade name PPELXN040, maleic anhydride grafting rate 0, intrinsic viscosity 41cm 3 / g;

[0059] PPE-2, trade name FB820, MAH-grafted polyphenylene ether resin, maleic anhydride grafting rate of 1.5%, intrinsic viscosity 40cm 3 / g.

[0060] (2) PA resin A:

[0061] PA-A-1: PA66, trade name PA66U3600, melting point 263°C, INVISTA Nylon Chemical (China) Co., Ltd.

[0062] PA-A-2: PA612, trade name D PA612, melting point 218°C, Arkema;

[0063] PA-A-3: PA56E-2260, melting point 269°C, Cathay (Wusu) Biomaterials Co., Ltd.

[0064] PA-A-4: PA1010G150, melting point 204°C, Shandong Guangyin Materials Co., Ltd.

[0065] The above melting point was tested using a DSC method with a heating rate of 10°C / min.

[0066] (3) PA resin B:

[0067] PA-B-1: Selar PA3426, DuPont;

[0068] PA-B-2: PA1239, Pingdingshan Beiande Plastics Co., Ltd.

[0069] (4) Phosphorus flame retardant:

[0070] Flame retardant: red phosphorus, FR9950KF, Tongcheng Xinde New Materials Co., Ltd.

[0071] (5) Glass fiber: ECS10-03-584 short cut length 3mm, boulder.

[0072] Performance testing:

[0073] Vertical burning performance: vertical burning performance is tested according to UL942018 standard;

[0074] Ablation resistance: Linear ablation rate (mm / s): The linear ablation rate of the sample was tested in accordance with the national military standard GJB323A-1996 using an oxyacetylene ablation tester. The experimental conditions were an oxygen pressure of 0.4 MPa, an acetylene pressure of 0.095 MPa, a nozzle diameter of 2.0 mm, and a heat flux of 4186 KW / m 2 , ablation time 8s, sample size is 30mm in diameter and 10mm in thickness. The smaller the linear ablation rate, the better the ablation resistance.

[0075] Injection molding appearance evaluation: Observe the appearance through the heat retention injection molding color plate. The appearance grade standards are as follows:

[0076] A: Excellent appearance, no external defects;

[0077] B: slightly whitish;

[0078] C: Large area of ​​whitening.

[0079] Examples 1-12 and Comparative Examples 1-7

[0080] Examples 1-12 and Comparative Examples 1-7 were prepared according to the formula in Table 1 and the following steps:

[0081] Polyphenylene ether resin, crystalline polyamide, amorphous polyamide and phosphorus-containing flame retardant are added from the main feeding port of a twin-screw extruder, and short-cut glass fibers are added from the side feeding port for extrusion granulation at an extrusion temperature of 300°C.

[0082] Table 1

[0083] Table 2

[0084] It can be seen from the above Examples 1-12 that the flame retardant grade of the polyphenylene ether resin composition of the present application is V-0, which meets the ablation resistance performance of a 100×100 mm sample.

[0085] Comparing Examples 1-3 with Comparative Examples 1-3, simply adding crystalline polyamide resin or amorphous polyamide resin results in poor appearance and ablation resistance, respectively. Furthermore, when the melting point of the crystalline polyamide resin is less than 210°C, the polyphenylene ether resin composition exhibits poor flame retardancy and ablation resistance. Only by combining these two components can both achieve excellent appearance and ablation resistance. As shown in Example 1 and Comparative Example 4, due to the low melt viscosity of crystalline PA at high temperatures, excessive crystalline PA content can reduce the overall material's melt viscosity at high temperatures, thereby diminishing the ablation resistance of the polyphenylene ether resin composition.

[0086] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and are not intended to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A polyphenylene ether resin composition, characterized in that, Comprising the following components in parts by weight: Polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin 18 - 51 parts, crystalline polyamide 18 - 42 parts, amorphous polyamide 4 - 11 parts, phosphorus-containing flame retardant 1 - 13 parts, glass fiber 8 - 42 parts; the melting point of the crystalline polyamide ≥ 210 °C.

2. The polyphenylene ether resin composition according to claim 1, wherein The melting point of the crystalline polyamide is 220 - 270 °C.

3. The polyphenylene ether resin composition according to claim 1, wherein Comprising at least one of the following: The mass ratio of the crystalline polyamide to the amorphous polyamide is crystalline polyamide:amorphous polyamide = (2.5 - 7):1; The polyphenylene ether resin composition comprises polyphenylene ether resin and maleic anhydride grafted polyphenylene ether resin, and the mass ratio of the polyphenylene ether resin to the maleic anhydride grafted polyphenylene ether resin is 1:(0.3 - 2).

4. The polyphenylene ether resin composition according to claim 1, characterized in that, The mass percentage content of terephthalic acid in the crystalline polyamide is less than 5%.

5. The polyphenylene ether resin composition according to claim 1, wherein The ratio of the total mass of the polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin to the total mass of the crystalline polyamide and the amorphous polyamide is (0.7 - 1.5):

1.

6. The polyphenylene ether resin composition according to claim 1, wherein The phosphorus-containing flame retardant comprises at least one of aluminum diethylphosphinate, red phosphorus, phosphate flame retardants, and phosphazene flame retardants.

7. The polyphenylene ether resin composition according to claim 1, wherein The polyphenylene ether resin composition further comprises at least one of the following components in parts by weight: toughening agent 0.01 - 5 parts, lubricant 0.01 - 5 parts, colorant 0.01 - 5 parts, filler 0.01 - 5 parts.

8. The polyphenylene ether resin composition according to claim 1, wherein The crystalline polyamide resin comprises at least one of PA66, PA56, PA612; the amorphous polyamide resin comprises at least one of PA6I / 6T, PA12.

9. A method for preparing the polyphenylene ether resin composition according to any one of claims 1 to 8, characterized in that, Comprising the following steps: extruding and pelletizing the polyphenylene ether resin and / or maleic anhydride grafted polyphenylene ether resin, crystalline polyamide, amorphous polyamide, phosphorus-containing flame retardant, and glass fiber to obtain the polyphenylene ether resin composition.

10. Use of the polyphenylene ether resin composition according to any one of claims 1 to 8 in a battery upper cover plate.

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