A glass fiber-reinforced flame-retardant polyphenylene ether composition, its preparation method and application

Abstract

The present invention discloses a glass fiber reinforced flame retardant polyphenylene ether composition, which comprises the following components by weight: 40 - 70 parts of polyphenylene ether; 10 - 20 parts of HIPS; 0.1 - 0.6 parts of epoxy resin; 10 - 30 parts of glass fiber; 0.2 - 0.8 parts of glass fiber surface modifier; 8 - 15 parts of flame retardant. By blending polyphenylene ether with a specific molecular weight distribution with HIPS, the impact resistance is improved, and a high-temperature coolant resistance retention rate of over 90% can also be obtained; further, through the modified glass fiber and a specific content of epoxy resin, not only can the impact resistance of the glass fiber reinforced polyphenylene ether composition be significantly improved, but also the "wick" effect of the glass fiber during combustion can be improved, so that the glass fiber reinforced flame retardant polyphenylene ether composition of the present invention has a V-0 flame retardant rating. At the same time, the glass fiber reinforced flame retardant polyphenylene ether composition of the present invention also has the advantages of coolant resistance and good melt fluidity.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly to a glass fiber reinforced flame retardant polyphenylene ether composition, a preparation method thereof, and an application thereof. Background Art

[0002] As a key component of new energy vehicles, the liquid cooling plate of new energy vehicles can effectively dissipate heat from the battery in the new energy battery pack, and can ensure the stable operation of the battery. And with the development of new energy vehicles, their electrification is continuously improved, and the temperature resistance requirements for materials are continuously reduced. The normal working stability of the liquid cooling plate is below 100°C. However, based on safety considerations, the requirements for the high-temperature performance retention rate of materials in the coolant are continuously increasing. Currently, it is required that the material be immersed in the coolant at 90°C for 2000 h, and the performance retention rate of the material is required to be ≥90%. In addition, based on the functional requirements of the liquid cooling plate of new energy vehicles, it has certain requirements for flame retardancy, toughness, and fluidity. It is required to have V-0 above 1.6 mm, the notched Izod impact strength ≥10 KJ / m 2 , the flexural strength ≥120 MPa, and the melt flow rate of the material at 300°C and 5 KG ≥10 g / 10 min (if the melt flow rate is lower than this value, it is difficult to process the liquid cooling plate of new energy vehicles). Although glass fiber flame retardant reinforced polyphenylene ether (PPE) has the advantages of high rigidity, acid and alkali resistance, high temperature resistance, heat and humidity resistance, and dimensional stability, it can meet the conventional performance requirements of the liquid cooling plate. However, due to the "wick" effect of glass fiber in glass fiber reinforced PPE, it is difficult for the material to reach the V-0 flame retardant grade, which is also the reason why the glass fiber reinforced PPE products on the market are mainly V-1 flame retardant grade products. Therefore, it is difficult to obtain a glass fiber reinforced flame retardant polyphenylene ether composition that simultaneously has V-0 above 1.6 mm, good reinforcement performance, and high melt flow rate in this field. Summary of the Invention

[0003] The purpose of the present invention is to overcome the above technical defects and provide a composition with the advantages of resistance to coolant, V-0 flame retardancy, good impact resistance, and good fluidity.

[0004] The present invention is achieved through the following technical solutions:

[0005] A glass fiber reinforced flame retardant polyphenylene ether composition, by weight, comprises the following components:

[0006] 40-70 parts of polyphenylene ether;

[0007] 10-20 parts of HIPS;

[0008] 10-30 parts of glass fiber;

[0009] 1-4 parts of toughening agent;

[0010] 0.2 - 0.8 parts of glass fiber surface modifier;

[0011] 0.1 - 0.6 parts of epoxy resin;

[0012] 8 - 15 parts of flame retardant;

[0013] The molecular weight distribution of the polyphenylene ether described is: the molecular weight of the polyphenylene ether accounting for 20 - 50% of the total weight of the polyphenylene ether is in the range of 25,000 - 45,000 g / mol, and the molecular weight of the polyphenylene ether accounting for 50 - 80% of the total weight of the polyphenylene ether is in the range of 9,000 - 16,000 g / mol.

[0014] The present invention has no particular limitation on the parameters of HIPS. The melt index of HIPS, according to the ISO 1133 - 1:2011 standard, under the test conditions of 200 °C and 5 KG, has a melt index range of 3 - 12 g / 10 min.

[0015] The present invention has no particular limitation on the parameters of the epoxy resin. It has been confirmed through experiments that when the viscosity of the epoxy resin tested at 25 °C using the GB / T 22314 - 2008 standard is ≤1000 mPa·s, the object of the present invention can be achieved.

[0016] Preferably, the molecular weight distribution of the polyphenylene ether described is: the molecular weight of the polyphenylene ether accounting for 30 - 40% of the total weight of the polyphenylene ether is in the range of 25,000 - 45,000 g / mol, and the molecular weight of the polyphenylene ether accounting for 60 - 70% of the total weight of the polyphenylene ether is in the range of 9,000 - 16,000 g / mol.

[0017] Preferably, the sum of the weights of the polyphenylene ether with a molecular weight in the range of 25,000 - 45,000 g / mol and the polyphenylene ether with a molecular weight in the range of 9,000 - 16,000 g / mol accounts for more than 95% of the total weight of the polyphenylene ether.

[0018] The test method for the molecular weight distribution of the polyphenylene ether in the technical solution of this application is: using chloroform as the solvent and GPC test.

[0019] The repeating unit of the polyphenylene ether described is derived from a 2,6 - dimethylphenol unit copolymer.

[0020] The polyphenylene ether of the present invention can be a homemade method or a commercially available product. The homemade method is as follows: a catalytic system consisting of toluene, copper chloride, and diethylamine is sequentially added to a reactor, and a toluene solution of 2,6-dimethylphenol is added dropwise under stable oxygen supply conditions, and the reaction is carried out at 20°C for a period of time. The longer the reaction time, the greater the molecular weight, and the molecular weight of the material is controlled according to the reaction time. After a period of reaction, acetic acid is added to terminate the experiment, and the polymer is separated by precipitation with anhydrous ethanol, dissolved in toluene, and re-precipitated with sewage ethanol, and then dried in a vacuum oven to constant weight. In the above method, the amine / copper molar ratio is preferably 30-40:1, and the molar ratio of the amount of 2,6-dimethylphenol to copper ions is preferably 30-40:1.

[0021] The testing method of the number average molecular weight of polyphenylene ether is as follows: tetrahydrofuran is used as a solvent and the polyphenylene ether is prepared by gel chromatography.

[0022] The average diameter range of the glass fiber that can realize the present invention is 8-14 microns. Preferably, the average diameter range of the glass fiber measured by the secondary element is 8-12 microns.

[0023] The glass fiber surface modifier is selected from silane coupling agents; the silane coupling agent is selected from at least one of aminosilane coupling agents and methoxysilane coupling agents.

[0024] The flame retardant is selected from at least one of tributyl phosphate, resorcinol bis(2,6-dimethylphenyl) phosphate and phosphazene. In order to further improve the coolant resistance, the flame retardant is preferably selected from phosphazene.

[0025] The toughening agent is selected from at least one of ethylene-propylene rubber, nitrile rubber, butadiene rubber, ethylene-vinyl acetate copolymer, polyolefin elastomer, styrene-butadiene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer and styrene-ethylene / propylene-styrene block copolymer.

[0026] The technician can choose whether to add 0.01-1 part of antioxidant and 0.01-1 part of lubricant according to actual needs. The antioxidant can be a phenolic antioxidant, a phosphite antioxidant or a metal passivator. It is also possible to choose whether to add other modifiers, such as fillers, weathering agents, etc. according to actual needs. In the composition of the present invention, the content of polyphenylene ether is not less than 30wt%.

[0027] The preparation method of the glass fiber reinforced flame retardant polyphenylene ether composition of the present invention comprises the following steps: according to the ratio, each component is evenly mixed, and then enters into a twin-screw extruder, glass fiber is side-fed, and after extrusion granulation, the glass fiber reinforced flame retardant polyphenylene ether composition is obtained; wherein, the screw speed is 250-500rpm; and the extrusion temperature is 230-290℃.

[0028] Application of the glass fiber reinforced flame retardant polyphenylene ether composition of the present invention, used for the liquid cooling plate of new energy vehicles, with a flame retardant grade of V-0 for a thickness of 1.6 mm, and a notched Izod impact strength ≥ 10 KJ / m 2 , a flexural strength ≥ 120 MPa, a melt flow rate of the material at 300 °C and 5 KG ≥ 10 g / 10 min, and a coolant resistance performance ≥ 92% (placing a tensile specimen in a coolant of 50% aqueous solution of ethylene glycol at 90 °C and soaking for 2000 h, testing the tensile properties of the material according to the ISO 527-2:2012 standard with a tensile rate of 10 mm / min, and passing the retention rate of the tensile properties before and after comparison).

[0029] The present invention has the following beneficial effects:

[0030] By blending polyphenylene ether with a specific molecular weight distribution with HIPS, the impact resistance of the present invention is improved, and a high-temperature coolant resistance performance retention rate of more than 90% can also be obtained; further, through the modified glass fiber and a specific content of epoxy resin, not only can the glass fiber reinforced polyphenylene ether composition be significantly improved, but also the "wick" effect of the glass fiber during combustion can be improved, so that the glass fiber reinforced flame retardant polyphenylene ether composition of the present invention has a flame retardant level of V-0. At the same time, the glass fiber reinforced flame retardant polyphenylene ether composition of the present invention also has the advantages of good coolant resistance and good melt fluidity. Embodiment

[0031] The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made. These all belong to the protection scope of the present invention.

[0032] The following polyphenylene ether is prepared by the following method: In a reactor, toluene is added as a solvent, and a catalytic system composed of copper chloride and diethylamine (amine / copper molar ratio is 35:1) is added. Under a stable oxygen supply condition, a toluene solution of 2,6-dimethylphenol is added dropwise, and the molar ratio of the amount of 2,6-dimethylphenol to copper ions is 35:1. React at 20 °C for 10 min - 4 h. The longer the reaction time, the larger the molecular weight, and the molecular weight of the material is controlled according to the reaction time. After reacting for a period of time, acetic acid is added to terminate the experiment. After separating the polymer by precipitation with anhydrous ethanol, dissolving it with toluene, and then reprecipitating it with sewage ethanol, it is dried to a constant weight in a vacuum oven.

[0033] Polyphenylene ether A: The reaction time is 10 min, the monomer is 2,6-dimethylphenol, and the molecular weight distribution is 6000 - 8000 g / mol, self-made;

[0034] Polyphenylene Oxide B: Reaction time is 20 min, monomer is 2,6-dimethylphenol, molecular weight is distributed in the range of 9000 - 11000 g / mol, self-made;

[0035] Polyphenylene Oxide C: Reaction time is 25 min, monomer is 2,6-dimethylphenol, molecular weight is mainly distributed in the range of 12000 - 14000 g / mol, self-made;

[0036] Polyphenylene Oxide D: Reaction time is 30 min, monomer is 2,6-dimethylphenol, molecular weight is mainly distributed in the range of 13000 - 16000 g / mol, self-made;

[0037] Polyphenylene Oxide E: Reaction time is 50 min, monomer is 2,6-dimethylphenol, molecular weight is mainly distributed in the range of 25000 - 28000 g / mol, self-made;

[0038] Polyphenylene Oxide F: Reaction time is 1.5 h, monomer is 2,6-dimethylphenol, molecular weight is mainly distributed in the range of 41000 - 45000 g / mol, self-made;

[0039] Polyphenylene Oxide G: Reaction time is 2 h, monomer is 2,6-dimethylphenol, molecular weight is mainly distributed in the range of 46000 - 50000 g / mol, self-made;

[0040] HIPS: PS MA5210, Yashide;

[0041] Glass Fiber 1: Average diameter is about 10 μm, ECS309A - 3 - H, Chongqing Guoqing;

[0042] Glass Fiber 2: Average diameter is about 13 μm, EMG13 - 70C, Jushi;

[0043] Epoxy Resin A: 2021P, Daicel;

[0044] Epoxy Resin B: Epikote 828, Hexion;

[0045] Toughening Agent: SEBS 6151, Formosa Plastics;

[0046] Maleic Anhydride: Commercially available;

[0047] Aminosilane Coupling Agent: KH 550, Commercially available;

[0048] Triphenyl Phosphate: WSFR - TPP, Wansheng;

[0049] Tetrakis(2,6 - dimethylphenyl) - 1,3 - phenylenediphosphate: PX - 200, Dainippon Ink and Chemicals, Inc.;

[0050] Phosphazene: HPCTP, Commercially available;

[0051] Antioxidant: Antioxidant 1010 and antioxidant 168 are compounded in a weight ratio of 1:2.

[0052] The preparation method of the glass fiber reinforced flame retardant polyphenylene ether composition of the embodiment and the comparative example is as follows: after uniformly mixing the components according to the ratio, the components are fed into a twin-screw extruder, and the glass fiber is fed sideways. After extrusion granulation, the glass fiber reinforced flame retardant polyphenylene ether composition is obtained; wherein the screw speed is 250-500rpm; and the extrusion temperature is 230-290°C.

[0053] Various tests:

[0054] (1) Flame retardant grade: According to UL94-2022 standard, 1.6 mm standard specimens were prepared and the vertical burning grade of the material was tested.

[0055] (2) Flexural strength: Test the flexural strength of the material in accordance with ISO 178-2019.

[0056] (3) Izod notched impact strength: tested in accordance with ISO 180-2019, type A notch.

[0057] (4) High-temperature coolant resistance retention rate: The tensile specimens were placed in a coolant-resistant solution of 50% by mass ethylene glycol water at 90°C and immersed for 2000 h. The tensile properties of the material were tested at a tensile rate of 10 mm / min in accordance with ISO 527-2:2012 standard. The tensile property retention rate before and after was compared for evaluation.

[0058] (5) Melt flow rate test: Tested in accordance with standard ISO 1133-1:2011, test conditions: 300°C, 5kg.

[0059] Table 1: Weight parts and test results of glass fiber reinforced flame retardant polyphenylene ether compositions of Examples 1-7

[0060] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Polyphenylene Oxide Type 1 E E E E E E F Polyphenylene Oxide Content 1 35 20 10 15 20 25 25 Polyphenylene Oxide Type 2 C B C C C C D Polyphenylene Oxide Content 2 35 20 40 35 30 25 25 HIPS 10 20 15 15 15 15 15 Glass Fiber 1 10 30 20 20 20 20 20 Aminosilane Coupling Agent 0.2 0.8 0.4 0.4 0.4 0.4 0.4 Toughening Agent 1 4 2 2 2 2 2 Epoxy Resin A 0.1 0.6 0.4 0.4 0.4 0.4 0.4 Tributyl Phosphate 8 15 10 10 10 10 10 Antioxidant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Flame Retardant Grade V-0 V-0 V-0 V-0 V-0 V-0 V-0 Flexural Strength, MPa 124 194 161 163 165 164 168 <![CDATA[Izod impact strength of cantilever beam, kJ / m 2 > 12.8 13.8 12.9 13.1 13.6 13.3 13.7 Melt Flow Rate, g / 10min 23.8 17.4 27.6 23.9 21.8 18.5 11.6 Retention Rate, % 94 95 92 95 96 93 94

[0061] It can be seen from Examples 3-7 that the preferred polyphenylene ether molecular weight distribution range has better high-temperature coolant resistance, and better overall mechanical properties and melt flow rate.

[0062] Table 2: Weight parts and test results of glass fiber reinforced flame retardant polyphenylene ether compositions of Examples 8-11

[0063] Example 8 Example 9 Example 10 Example 11 Polyphenylene Oxide E 25 25 25 25 Polyphenylene Oxide C 25 25 25 25 HIPS 15 15 15 15 Glass Fiber 1 20 20 20 Glass Fiber 2 20 Aminosilane Coupling Agent 0.4 0.4 0.4 0.4 Toughening Agent 2 2 2 2 Epoxy Resin A 0.4 0.4 0.4 Epoxy Resin B 0.4 Tributyl Phosphate 10 10 Phosphonitrile 10 PX - 200 10 Antioxidant 0.3 0.3 0.3 0.3 Flame Retardant Grade V-0 V-0 V-0 V-0 Flexural Strength, MPa 156 164 157 160 <![CDATA[Izod impact strength of cantilever beam, kJ / m 2 > 10.4 13.0 12.7 13.5 Melt Flow Rate, g / 10min 16.4 18.4 20.1 23.4 Retention Rate, % 92 94 97 92

[0064] It can be seen from Examples 6 / 8 that the embodiments of glass fibers with preferred diameters have better mechanical properties, better melt flow rates, and better high-temperature coolant resistance.

[0065] As can be seen from Examples 6 / 10 / 11, when the flame retardant is preferably phosphonitrile, the high-temperature resistant coolant performance is better.

[0066] Table 3: Parts by weight and test results of glass fiber-reinforced flame-retardant polyphenylene ether compositions of Comparative Examples 1-7

[0067] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Polyphenylene Oxide Type 1 E E G E G E E Polyphenylene Oxide Content 1 5 45 25 25 25 40 35 Polyphenylene Oxide Type 2 C C C A A C C Polyphenylene Oxide Content 2 45 5 25 25 25 40 35 HIPS 15 15 15 15 15 10 10 Glass Fiber 1 20 20 20 20 20 10 10 Aminosilane Coupling Agent 0.4 0.4 0.4 0.4 0.4 0.2 Maleic Anhydride 0.2 Toughening Agent 2 2 2 2 2 1 1 Epoxy Resin A 0.4 0.4 0.4 0.4 0.4 0.1 0.1 Tributyl Phosphate 10 10 10 10 10 8 8 Antioxidant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Flame Retardant Grade V-0 V-0 V-0 V-0 V-0 V-1 V-0 Flexural Strength, MPa 168 171 162 159 164 103 121 <![CDATA[Izod impact strength of cantilever beam, kJ / m 2 > 12.1 13.5 13.3 9.7 10.1 10.9 11.2 Melt Flow Rate, g / 10min 28.9 8.7 6.7 19.7 7.4 38.4 24.2 Retention Rate, % 86 89 89 82 84 88 89

[0068] As can be seen from Comparative Example 1, when the content of polyphenylene ether in the range of 9000-16000 g / mol is too high, the high-temperature resistant coolant performance is poor.

[0069] As can be seen from Comparative Example 2, when the content of polyphenylene ether in the range of 9000-16000 g / mol is too low, although the high-temperature resistant coolant performance reaches 94%, the melt flow rate is extremely low.

[0070] As can be seen from Comparative Examples 3-5, when the molecular weight of polyphenylene ether is not within the scope of the present invention, the advantages of high melt flow rate and good high-temperature resistant coolant performance cannot be achieved simultaneously.

[0071] As can be seen from Comparative Example 6, when the total content of polyphenylene ether is too high, the impact resistance and high-temperature resistant coolant performance are poor.

[0072] As can be seen from Comparative Example 7, when using maleic anhydride, a commonly used glass fiber modifier in the art, for modification, the coolant retention rate is low.

[0073] Table 4: Parts by weight and test results of glass fiber-reinforced flame-retardant polyphenylene ether compositions of Comparative Examples 8-10

[0074] Comparative Example 8 Comparative Example 9 Comparative Example 10 Polyphenylene Oxide E 35 35 35 Polyphenylene Oxide C 35 35 35 HIPS 10 10 Glass Fiber 1 10 10 10 Aminosilane Coupling Agent 0.2 0.2 0.2 Toughening Agent 1 1 1 Epoxy Resin A 0 0.8 0.1 Tributyl Phosphate 8 8 8 Antioxidant 0.3 0.3 0.3 Flame Retardant Grade V-1 V-0 V-0 Flexural Strength, MPa 123 126 131 <![CDATA[Izod impact strength of cantilever beam, kJ / m 2 > 11.7 9.1 8.7 Melt Flow Rate, g / 10min 23.8 12.7 5.4 Retention Rate, % 87 90 91

[0075] As can be seen from Comparative Example 8, if the epoxy resin is not added, the flame retardant grade and coolant resistance performance will be reduced.

[0076] As can be seen from Comparative Example 9, if the epoxy resin addition content is too high, the melt fluidity and coolant resistance performance will decrease.

[0077] As can be seen from Comparative Example 10, when HIPS is not contained, both the Izod notched impact strength and the melt flow rate are low.

Claims

1. A glass fiber reinforced flame retardant polyphenylene ether composition, characterized in that, By weight, it comprises the following components: 40 - 70 parts of polyphenylene ether; 10 - 20 parts of HIPS; 10 - 30 parts of glass fiber; 1 - 4 parts of toughening agent; 0.2 - 0.8 part of glass fiber surface modifier; 0.1 - 0.6 part of epoxy resin; 8 - 15 parts of flame retardant; The molecular weight distribution of the polyphenylene ether is as follows: the molecular weight of 20 - 50% of the total weight of the polyphenylene ether is in the range of 25,000 - 45,000 g / mol, and the molecular weight of 50 - 80% of the total weight of the polyphenylene ether is in the range of 9,000 - 16,000 g / mol; The glass fiber surface modifier is selected from at least one of silane coupling agents.

2. The glass fiber reinforced flame retardant polyphenylene ether composition according to claim 1, wherein The molecular weight distribution of the polyphenylene ether is as follows: the molecular weight of 30 - 40% of the total weight of the polyphenylene ether is in the range of 25,000 - 45,000 g / mol, and the molecular weight of 60 - 70% of the total weight of the polyphenylene ether is in the range of 9,000 - 16,000 g / mol.

3. The glass fiber reinforced flame retardant polyphenylene ether composition according to claim 1, characterized in that, The repeating unit of the polyphenylene ether is derived from a copolymer of 2,6 - dimethylphenol units.

4. The glass fiber-reinforced flame-retardant polyphenylene ether composition according to claim 1, wherein The average diameter range of the glass fiber is 8 - 12 microns.

5. The glass fiber-reinforced flame-retardant polyphenylene ether composition according to claim 1, wherein The silane coupling agent is selected from at least one of amino silane coupling agents and methoxy silane coupling agents.

6. The glass fiber-reinforced flame-retardant polyphenylene ether composition according to claim 1, wherein The flame retardant is selected from at least one of tributyl phosphate, resorcinol bis(2,6 - dimethylphenyl) phosphate, and phosphonitrile.

7. The glass fiber reinforced flame retardant polyphenylene ether composition according to claim 6, characterized in that, The flame retardant is selected from phosphonitrile.

8. The glass fiber reinforced flame retardant polyphenylene ether composition according to claim 1, wherein, The toughening agent is selected from at least one of ethylene - propylene rubber, nitrile rubber, cis - 1,4 - polybutadiene rubber, ethylene - vinyl acetate copolymer, polyolefin elastomer, styrene - butadiene - styrene block copolymer, styrene - ethylene / butene - styrene block copolymer, and styrene - ethylene / propylene - styrene block copolymer.

9. The glass fiber-reinforced flame-retardant polyphenylene ether composition according to claim 1, wherein By weight, it further comprises 0.01 - 1 part of antioxidant and 0.01 - 1 part of lubricant.

10. The preparation method of the glass fiber reinforced flame retardant polyphenylene ether composition according to any one of claims 1-9, characterized in that, It includes the following steps: according to the ratio, mix each component evenly, then enter a twin - screw extruder, feed the glass fiber from the side, and after extrusion granulation, a glass fiber - reinforced flame - retardant polyphenylene ether composition is obtained; wherein, the screw speed is 250 - 500 rpm; the extrusion temperature is 230 - 290 °C.

11. Use of the glass fiber-reinforced flame-retardant polyphenylene ether composition according to any one of claims 1-9, characterized in that, For the liquid cooling plate of new energy vehicles, it has a flame retardant grade of V-0 with a thickness of 1.6 mm and a notched Izod impact strength of ≥10 KJ / m 2 , a flexural strength of ≥120 MPa, and a melt flow rate of ≥10 g / 10 min for the material at 300 °C and 5 kg.