A kind of ablation-resistant polyphenylene ether composition and preparation method thereof

Abstract

The present invention relates to an ablation-resistant polyphenylene ether composition and a preparation method thereof, comprising a PPE resin, a maleic anhydride grafted PPE resin, a polyamide resin, a phosphorus-containing flame retardant and glass fiber. The present invention can significantly improve the ablation resistance of the polyphenylene ether by introducing a special polyamide resin and an appropriate amount of flame retardant, and at the same time has excellent mechanical properties and has good market application prospects.

Description

Technical Field

[0001] The invention belongs to the field of modified plastics, and particularly relates to an ablation-resistant polyphenylene ether composition and a preparation method thereof. Background Art

[0002] Polyphenylene ether compositions have the advantages of excellent flame retardancy, high rigidity, and light density, and therefore have been widely used in power battery packs. However, conventional polyphenylene ether compositions have poor ablation resistance and cannot meet the requirements of external fire and thermal runaway tests in GB 38031 "Safety Requirements for Power Batteries for Electric Vehicles". This limits their application. For example, the upper cover of the power battery pack still uses thermosetting materials such as SMC to meet the ablation resistance requirements. However, materials such as SMC have a high specific gravity, low production efficiency, and are not recyclable, with a high overall cost. Therefore, the industry hopes to develop solutions for ablation-resistant polyphenylene ether compositions to improve production efficiency and reduce overall costs. Summary of the invention

[0003] The technical problem to be solved by the present invention is to provide an ablation-resistant polyphenylene ether composition and a preparation method thereof, wherein the composition can significantly improve the ablation resistance of polyphenylene ether and has excellent mechanical properties and good market application prospects.

[0004] The present invention provides an ablation-resistant polyphenylene ether composition, comprising the following components in parts by weight:

[0005]

[0006] The polyamide resin contains terephthalic acid, and the total mass content of the terephthalic acid in the polyamide resin is 10-30%.

[0007] In the present invention, the total mass content ratio of terephthalic acid in the polyamide resin can be determined by pyrolysis gas chromatography-mass spectrometry using a terephthalic acid standard sample to establish a quantitative ratio.

[0008] Preferably, the phosphorus content of the phosphorus-containing flame retardant is 10%-100%. In the present invention, the phosphorus content of the phosphorus-containing flame retardant can be tested by ion chromatography.

[0009] Preferably, 0.25±0.0002 g of PPE resin is dissolved in 50 mL of concentrated sulfuric acid (96%), and the concentrated sulfuric acid flow time t0 and the sample solution flow time t are measured and recorded in a 25°C constant temperature water bath. The melt viscosity range is 30-55 cm 3 / g; softening point is above 200°C. Specifically, the melt viscosity of the PPE resin can be 30cm 3 / g, 35cm 3 / g, 40cm 3 / g, 45cm 3 / g, 50cm 3 / g, 55cm 3 / g, etc.; the softening point of the PPE resin can be: 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, etc., all of which can realize the present invention.

[0010] Preferably, the polyamide resin is at least one of PA10T, PA5T56, PA66, PA6, and PA6T66, wherein at least one of the resins contains terephthalic acid monomer.

[0011] Preferably, the total proportion of terephthalic acid in the polyamide resin is 15-25%. If the proportion of terephthalic acid in the polyamide resin is too low, the ablation requirements cannot be met; if the proportion of terephthalic acid is too high, the material production and processing performance will deteriorate and it cannot be processed at normal processing temperature.

[0012] Preferably, the phosphorus-containing flame retardant is at least one of flame retardant BDP, flame retardant RDP, TPP, phenoxy polyphosphazene, red phosphorus, and diethyl aluminum hypophosphite.

[0013] Preferably, the phosphorus content of the phosphorus-containing flame retardant is 10%-50%. If the phosphorus-containing flame retardant is added in too low a proportion, it cannot play a flame retardant role; if the phosphorus-containing flame retardant is added in too high a proportion, it will have an adverse effect on the impact strength.

[0014] Preferably, the present invention further comprises at least one of a toughening agent, a mineral powder, a lubricant, and a colorant.

[0015] The toughening agent is not particularly limited, including but not limited to ethylene-octene copolymer (POE), SEBS, etc. From the perspective of improving toughness, maleic anhydride grafted POE or maleic anhydride grafted SEBS is preferred, and the grafting rate is more preferably 0.5-2%. The amount of the toughening agent added is within 10%.

[0016] The mineral powder is calcium carbonate, talc, mica, kaolin, magnesium hydroxide, boehmite, etc. The addition amount of the mineral powder is within 40%.

[0017] The lubricant is polyethylene wax, zinc stearate, lithium stearate, etc. The added amount of the lubricant is within 3%.

[0018] The colorant is carbon black, titanium dioxide, zinc sulfide, iron red, titanium yellow, etc. The added amount of the colorant is within 3%.

[0019] Preferably, the following components are included by weight:

[0020]

[0021] The present invention also provides a method for preparing an ablation-resistant polyphenylene ether composition, comprising the following steps:

[0022] The components are added into a mixer and mixed evenly to obtain an evenly mixed material; the evenly mixed material is extruded and granulated through a twin-screw extruder to obtain an ablation-resistant polyphenylene ether composition.

[0023] The present invention also provides an application of the ablation-resistant polyphenylene ether composition in a power battery pack.

[0024] The mechanism of the present invention is as follows:

[0025] Conventional thermoplastic materials will melt and drip quickly at high temperatures in ablation tests. When glass fibers are added, the melt strength of the material is greatly improved, and the time for dripping at high temperatures can be extended, but it is still not enough to withstand high temperatures. However, if the material can be carbonized quickly during the ablation process and form a dense carbon layer, further ablation can be prevented. Therefore, on the one hand, the melt viscosity of the material should be increased, and on the other hand, the carbonization rate should be increased.

[0026] Conventional polyphenylene ether has high melt viscosity and carbonization rate, but its softening point temperature is too low. As the temperature rises, the melt viscosity will drop rapidly, so the material will still melt. The present invention increases the softening temperature of the polyphenylene ether composition by adding a polyamide resin containing a specific content of terephthalic acid to the polyphenylene ether composition, and at the same time greatly increases the melt viscosity and carbonization rate of the polyphenylene ether composition, thereby ensuring that the composition has balanced performance; on this basis, an appropriate amount of phosphorus-containing flame retardant is added to further significantly increase the carbonization rate of the polyphenylene ether and the flame retardant performance of the composition, so that it has excellent ablation resistance and excellent mechanical properties.

[0027] Beneficial Effects

[0028] The invention can significantly improve the ablation resistance of polyphenylene ether by introducing a special polyamide resin and an appropriate amount of flame retardant, and at the same time has excellent mechanical properties and good market application prospects. DETAILED DESCRIPTION

[0029] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0030] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0031] The raw materials used in the following examples and comparative examples are as follows:

[0032] PPE resin 1#: intrinsic viscosity is 41.5 cm 3 / g, softening point is 200℃, Nantong Xingchen Synthetic Materials Co., Ltd., trade name is PPE LXN040.

[0033] PPE resin 2#: melt viscosity is 46.5cm 3 / g, softening point is 200℃, Handan Fengfeng Xinbao New Material Technology Co., Ltd., trade name is PPO XB045.

[0034] Maleic anhydride grafted PPE 1# (denoted as MPPE), trade name FB820, Jiayirong Co., Ltd.

[0035] Maleic anhydride grafted PPE 2#, trade name GPM5601, Ningbo Nengzhiguang New Material Technology Co., Ltd.

[0036] PA resin 1#: PA5T56 copolymer, trade name ECOPENT 2260, the proportion of terephthalic acid is 25%.

[0037] PA resin 2#: PA10T, trade name Vicnyl 700-01NC001, the proportion of terephthalic acid is 50%.

[0038] PA resin 3#: PA6, trade name PA M2400, the proportion of terephthalic acid is 0.

[0039] Phosphorus-containing flame retardant 1#: BDP, trade name CR-741, phosphorus content is 8.9%.

[0040] Phosphorus-containing flame retardant 2#, phenoxy polyphosphazene, trade name HPCTP, phosphorus content is 13.45%.

[0041] Phosphorus-containing flame retardant 3#: red phosphorus masterbatch, trade name FR9950KF, phosphorus content is 50%.

[0042] Glass fiber: Brand: ECS13-03-540H, Jushi Co., Ltd.

[0043] The compositions of the embodiments and comparative examples of the present invention are prepared by the following process:

[0044] The components are added into a mixer and mixed evenly to obtain a uniformly mixed material; the uniformly mixed material is extruded and granulated through a twin-screw extruder to obtain an ablation-resistant polyphenylene ether composition. The screw temperature is 280°C.

[0045] The embodiments and comparative examples were subjected to the following test methods or test standards:

[0046] Vicat softening point: The Vicat softening point of the polyphenylene ether composition was tested with reference to ISO-75-2-2013.

[0047] Fire test results: The material was processed into a plate with a thickness of 200×200×3mm, and an external fire test was performed in accordance with GB / T 38031-2020. After the test, the plate was observed for burn-through, molten droplets, etc. If the plate structure remains basically good without burn-through, molten droplets, etc., it is considered to have passed the fire test.

[0048] Vertical flammability: Refer to UL94 2018 and test the vertical flammability of a 1.5 mm thick test piece. In the test, the flammability that reaches UL94 V-0 is marked as OK, and the flammability that does not reach UL94 V-0 is marked as NG.

[0049] Viscosity: Referring to standard ISO 3219-1:2021, the viscosity of the polyphenylene ether composition was tested at 280° C. and 0.2 rad / s.

[0050] Notched impact strength: tested in accordance with standard ISO 180-2019.

[0051] Formulas and test results of embodiments and comparative examples (parts by weight)

[0052]

[0053]

[0054]

[0055] From the results of Examples 1-9, it can be seen that the present invention can significantly improve the ablation resistance of polyphenylene ether by introducing a special polyamide resin and a special flame retardant, and at the same time has excellent mechanical properties. The polyphenylene ether composition of the present invention has a Vicat softening point of 220-250°C, a viscosity of 1600-2900 mPa*s, and a notched impact strength of 8.5-13 KJ / m 2 .

[0056] Compared with Examples 1 and 8, when too much PPE resin (Comparative Example 1) or polyamide resin (Comparative Example 2) is added, the results of the fire test are not ideal. It can be seen from Example 3, Comparative Example 3 and Comparative Example 7 that if the proportion of terephthalic acid in the polyamide resin is too high, the ablation requirements cannot be met; if the proportion of terephthalic acid is too low, the material production and processing performance will deteriorate and it cannot be processed at normal processing temperatures. It can be seen from Example 3 and Comparative Example 4 that when the phosphorus content of the phosphorus-containing flame retardant is less than 10%, the ablation resistance is not significantly improved. It can be seen from Example 8, Comparative Example 5 and Comparative Example 6 that the addition ratio of the phosphorus-containing flame retardant is too low and it cannot play a role in ablation resistance; if the addition ratio is too high, it will have an adverse effect on the impact strength. It can be seen from Example 8, Comparative Example 8 and Comparative Example 9 that if the addition ratio of glass fiber is too low, the viscosity of the material cannot be increased, and thus the fire test cannot be guaranteed. If the addition ratio is too high, the impact strength of the material will be adversely affected.

Claims

1. An ablation-resistant polyphenylene ether composition, characterized in that: In parts by weight, it comprises the following components: The polyamide resin contains terephthalic acid, and the total mass content of terephthalic acid in the polyamide resin is 15-25%; the melt viscosity of the PPE resin is in the range of 30-55cm 3 / g; the softening point is above 180°C; the phosphorus content of the phosphorus-containing flame retardant is 10%-50%.

2. The polyphenylene ether composition according to claim 1, characterized in that: The phosphorus-containing flame retardant is at least one of flame retardant BDP, flame retardant RDP, TPP, phenoxy polyphosphazene, red phosphorus, and diethyl aluminum hypophosphite.

3. The polyphenylene ether composition according to claim 1, characterized in that: It also includes at least one of a toughening agent, mineral powder, a lubricant, and a colorant.

4. A method for preparing the ablation-resistant polyphenylene ether composition according to any one of claims 1 to 3, comprising the following steps: The components are added into a mixer and mixed evenly to obtain an evenly mixed material; the evenly mixed material is extruded and granulated through a twin-screw extruder to obtain an ablation-resistant polyphenylene ether composition.

5. Use of the ablation-resistant polyphenylene ether composition according to any one of claims 1 to 3 in a power battery pack.

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