A polyphenylene ether resin composition, a method for preparing the same, and an application thereof

Abstract

The application belongs to the field of polyphenyl ether resin compositions, and specifically discloses a polyphenyl ether resin composition, a preparation method and application thereof.The polyphenyl ether resin composition comprises the following components in parts by weight: 18-51 parts of polyphenyl ether resin and / or maleic anhydride grafted polyphenyl 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 greater than or equal to 210 DEG C.The application can improve the ablation resistance while maintaining good product appearance by simultaneously adding the crystalline polyamide and the amorphous polyamide.

Description

Technical Field

[0001] The present invention belongs to the field of polyphenylene ether resin compositions, and in particular 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 GB 38031 "Safety Requirements for Power Batteries for Electric Vehicles" for external fire and thermal runaway tests.

[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 of the polyphenylene ether composition involved in the above-mentioned prior art, the present invention will provide a polyphenylene ether resin composition and its preparation method and application.

[0006] To achieve the above objectives, the following technical solutions are specifically included:

[0007] A polyphenylene ether resin composition comprises 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 phosphorus-containing flame retardant, and 8-42 parts of glass fiber; the melting point of the crystalline polyamide is ≥210°C.

[0008] The present invention 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.

[0009] As a preferred embodiment of the present invention, 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.

[0010] The total mass percentage of the polyphenylene ether resin and / or the maleic anhydride grafted polyphenylene ether resin in the polyphenylene ether resin composition is not less than 20%.

[0011] As a preferred embodiment of the present invention, there is no special requirement for the intrinsic viscosity of the polyamide resin. For example, the intrinsic viscosity of the polyphenylene ether resin can be ≤42 cm 3 / g, you can choose 96% concentrated sulfuric acid as the solvent for testing according to ISO 307 2019 standard.

[0012] As a preferred embodiment of the present invention, the melting point of the crystalline polyamide is 211-300° C. The melting point of the crystalline polyamide can be tested using the DSC method, and the heating rate is preferably 5-10° C. / min.

[0013] As a preferred embodiment of the present invention, the melting point of the crystalline polyamide is 220-270° C.; the type of the amorphous polyamide is not limited.

[0014] 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-mentioned 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 said range.

[0015] As a preferred embodiment of the present invention, the crystalline polyamide resin includes at least one of PA66, PA56, and PA612.

[0016] As a preferred embodiment of the present invention, the amorphous polyamide resin includes at least one of PA3426 and PA1239.

[0017] As a preferred embodiment of the present invention, the mass ratio of the crystalline polyamide and the amorphous polyamide is crystalline polyamide: amorphous polyamide = (2.5-7):1. More preferably, the mass ratio of the crystalline polyamide and the amorphous polyamide is crystalline polyamide: amorphous polyamide = (2.8-5):1.

[0018] As a preferred embodiment of the present invention, the crystallinity of the crystalline polyamide is greater than 20%, more preferably 30-90%, and even more preferably 50-85%.

[0019] Under the above mass ratio of crystalline polyamide to amorphous polyamide, the polyphenylene ether resin composition has better ablation resistance.

[0020] As a preferred embodiment of the present invention, the mass percentage of terephthalic acid in the crystalline polyamide is less than 5%, more preferably less than 3%, more preferably less than 1%, and most preferably 0.

[0021] As a preferred embodiment of the present invention, the relative viscosity of the crystalline polyamide is 1-3, preferably, 2.4-2.7. The relative viscosity is tested in accordance with GB / T 1632-1993.

[0022] As a preferred embodiment of the present invention, the relative viscosity of the amorphous polyamide is 1-3, preferably, 2.4-2.7. The relative viscosity is tested in accordance with GB / T 1632-1993.

[0023] As a preferred embodiment of the present invention, 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).

[0024] As a further preferred embodiment of the present invention, the mass ratio of the polyphenylene ether resin to the maleic anhydride grafted polyphenylene ether resin is 1:(0.3-1.7), and more preferably 1:(0.8-1.2).

[0025] 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. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0026] As a preferred embodiment of the present invention, the grafting rate of the maleic anhydride grafted polyphenylene ether resin is 0.5-2%. 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).

[0027] 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.

[0028] As a preferred embodiment of the present invention, 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.

[0029] As a further preferred embodiment of the present invention, 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.

[0030] As a preferred embodiment of the present invention, the phosphorus-containing flame retardant includes at least one of diethyl aluminum hypophosphite, red phosphorus, phosphate flame retardants, and phosphazene flame retardants.

[0031] As a further preferred embodiment of the present invention, the present invention comprises at least one of diethyl aluminum hypophosphite, red phosphorus, and an organic phosphorus flame retardant.

[0032] As a preferred embodiment of the present invention, the organophosphorus flame retardant includes at least one of flame retardant BDP, flame retardant RDP, flame retardant TPP, and phosphazene.

[0033] As a preferred embodiment of the present invention, 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.

[0034] 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.

[0035] As a preferred embodiment of the present invention, the length of the glass fiber is within 10 mm.

[0036] A method for preparing a polyphenylene ether resin composition comprises 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.

[0037] As a preferred embodiment of the present invention, the extrusion temperature is 220-300°C.

[0038] The polyphenylene ether resin composition of the present invention is used in a battery cover. The polyphenylene ether resin composition can meet the requirements of the corresponding components of the battery pack for ablation resistance and appearance performance. For example, when used in a battery cover, a product with a length greater than 1 m has no appearance problems and meets the requirements for its ablation resistance performance.

[0039] 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

[0040] To better illustrate the objectives, technical solutions, and advantages of the present invention, the present invention will be further described below with reference to specific examples. The experimental methods used in the examples and / or comparative examples are conventional methods unless otherwise specified; the materials and reagents used are commercially available unless otherwise specified.

[0041] Raw material brand information:

[0042] (1) PPE resin:

[0043] PPE-1, trade name PPE LXN040, maleic anhydride grafting rate is 0, intrinsic viscosity is 41cm 3 / g;

[0044] PPE-2, trade name FB820, MAH grafted polyphenylene ether resin, maleic anhydride grafting rate of 1.5%, viscosity 40cm 3 / g.

[0045] (2) PA resin A:

[0046] PA-A-1: PA66, trade name PA66 U3600, melting point 263°C, INVISTA Nylon Chemical (China) Co., Ltd.

[0047] PA-A-2: PA612, trade name D PA612, melting point 218°C, Arkema;

[0048] PA-A-3: PA56 E-2260, melting point 269°C, Cathay (Wusu) Biomaterials Co., Ltd.

[0049] PA-A-4: PA1010 G150, melting point 204°C, Shandong Guangyin Materials Co., Ltd.

[0050] The above melting point was tested using a DSC method with a heating rate of 10°C / min.

[0051] (3) PA resin B:

[0052] PA-B-1: Selar PA3426, DuPont;

[0053] PA-B-2: PA1239, Pingdingshan Beiande Plastics Co., Ltd.

[0054] (4) Phosphorus flame retardant:

[0055] Flame retardant: red phosphorus, FR9950KF, Tongcheng Xinde New Materials Co., Ltd.

[0056] (5) Glass fiber: ECS10-03-584 short cut length 3mm, boulder.

[0057] Performance testing:

[0058] Vertical burning performance: vertical burning performance is tested according to UL94 2018 standard;

[0059] Ablation resistance: Linear ablation rate (mm / s): The linear ablation rate of the sample was tested in accordance with the national military standard GJB 323A-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.

[0060] Injection molding appearance evaluation: Observe the appearance through the heat retention injection molding color plate. The appearance grade standards are as follows:

[0061] A: Excellent appearance, no external defects;

[0062] B: slightly whitish;

[0063] C: Large area of ​​whitening.

[0064] Examples 1-12 and Comparative Examples 1-7

[0065] Examples 1-12 and Comparative Examples 1-7 were prepared according to the formula in Table 1 and the following steps:

[0066] 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.

[0067] Table 1

[0068]

[0069] Table 2

[0070] Raw materials / weight parts Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 PPE-1 40 40 40 40 40 40 40 PA-A-1 - 38 - 63 10 30 30 PA-A-4 30 - - - - - - PA-B-1 8 - 38 8 8 3 20 fiberglass 20 20 20 20 20 20 20 Flame Retardant-A 4 4 4 4 4 4 4 Vertical burning V-2 V-0 V-0 V-1 V-0 V-0 V-0 Linear ablation rate mm / s 6.6 1.8 9.8 4.1 6.4 1.5 5.9 Appearance A C B C B B A

[0071] It can be seen from the above Examples 1-12 that the flame retardant grade of the polyphenylene ether resin composition of the present invention is V-0, which meets the ablation resistance of a 100×100 mm sample.

[0072] 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.

[0073] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polyphenylene ether resin composition, characterized in that The composition comprises 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 phosphorus-containing flame retardant, and 8-42 parts of glass fiber; the melting point of the crystalline polyamide is ≥210°C, and the mass percentage of terephthalic acid in the crystalline polyamide is less than 5%.

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 Include 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, 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.

5. The polyphenylene ether resin composition according to claim 1, wherein The phosphorus-containing flame retardant includes at least one of diethyl aluminum hypophosphite, red phosphorus, phosphate flame retardants, and phosphazene flame retardants.

6. 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: 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.

7. The polyphenylene ether resin composition according to claim 1, wherein The crystalline polyamide resin includes at least one of PA66, PA56, and PA612; the amorphous polyamide resin includes at least one of PA3426 and PA1239.

8. A method for preparing the polyphenylene ether resin composition according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: extruding and granulating 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.

9. Use of the polyphenylene ether resin composition according to any one of claims 1 to 7 in a battery top cover.

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