Glass fiber-reinforced flame-retardant polyphenyl ether composition, and preparation method therefor and use thereof

Abstract

Disclosed in the present invention is a glass fiber-reinforced flame-retardant polyphenyl ether composition, which comprises the following components in parts by weight: 40-70 parts of a polyphenyl ether; 10-20 parts of HIPS; 0.1-0.6 parts of an epoxy resin; 10-30 parts of glass fibers; 0.2-0.8 parts of a glass fiber surface modifier; and 8-15 parts of a flame retardant. In the present invention, by means of blending a polyphenyl ether having a specific molecular weight distribution with HIPS, the impact resistance is improved, and a high-temperature cooling liquid resistance retention rate exceeding 90% can also be achieved; furthermore, by means of the modified glass fibers and a specific content of the epoxy resin, not only can the impact resistance of the glass fiber-reinforced polyphenyl ether composition be significantly improved, but the "candlewick" effect of the glass fibers during the combustion process can also be improved, such that the glass fiber-reinforced flame-retardant polyphenyl ether composition of the present invention has a flame-retardant level of V-0. Moreover, the glass fiber-reinforced flame-retardant polyphenyl ether composition of the present invention also has the advantages of cooling-liquid resistance and good melt flowability.

Description

A glass fiber reinforced flame retardant polyphenylene ether composition and its preparation method and application Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a glass fiber reinforced flame retardant polyphenylene ether composition, a preparation method 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 for 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, its electrification continues to improve, and the temperature resistance requirements for materials continue to decrease. The normal working stability of liquid cooling plates are all below 100°C. However, based on safety considerations, the requirements for the high-temperature performance retention rate of materials under coolant are constantly increasing. Currently, there is a requirement to immerse the material in coolant for 2000 hours at 90°C, 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 requires V-0 above 1.6mm and cantilever beam notch impact strength ≥10KJ / m 2 , flexural strength ≥ 120 MPa, and a melt flow rate ≥ 10 g / 10 min at 300°C and 5 kg (a melt flow rate below this value makes it difficult to process liquid cooling plates for new energy vehicles). Although glass fiber flame-retardant reinforced polyphenylene ether (PPE) offers the advantages of high rigidity, acid and alkali resistance, high temperature resistance, moisture and heat resistance, and dimensional stability, and can meet the conventional performance requirements of liquid cooling plates, the "candle wick" effect of glass fiber in glass fiber-reinforced PPE makes it difficult to achieve a V-0 flame retardancy rating. This is also the reason why V-1 flame retardancy is the predominant grade of glass fiber-reinforced PPE on the market. Therefore, it is difficult to obtain glass fiber-reinforced flame-retardant polyphenylene ether compositions that simultaneously achieve a V-0 rating above 1.6 mm, good reinforcement properties, and a high melt flow rate. Summary of the Invention

[0003] The purpose of the present invention is to overcome the above technical defects and provide a product with the advantages of coolant resistance, V-0 flame retardancy, 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, comprising the following components in parts by weight:

[0006] 40-70 parts of polyphenylene ether;

[0007] HIPS 10-20 copies;

[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 is as follows: the molecular weight of the polyphenylene ether accounting for 20-50% of the total weight of the polyphenylene ether is in the range of 25000-45000 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 9000-16000 g / mol.

[0014] The present invention does not particularly limit the parameters of HIPS. The melt index of HIPS is in accordance with ISO 1133-1:2011 standard, with test conditions of 200° C. and 5 kg, and the melt index range is 3-12 g / 10 min.

[0015] The present invention has no particular limitation on the parameters of the epoxy resin. Experiments have shown that the purpose of the present invention can be achieved when the epoxy resin has a viscosity of ≤1000 mPa.s as measured at 25°C according to GB / T 22314-2008 standard.

[0016] Preferably, the molecular weight distribution of the polyphenylene ether 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 25000-45000 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 9000-16000 g / mol.

[0017] Preferably, the sum of the weight of the polyphenylene ether having a molecular weight in the range of 25,000-45,000 g / mol and the weight of the polyphenylene ether having 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 polyphenylene ether in the technical solution of this application is: solvent chloroform, GPC test.

[0019] The repeating units of the polyphenylene ether are derived from a copolymer of 2,6-dimethylphenol units.

[0020] The polyphenylene ether of the present invention can be prepared by 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 under stable oxygen supply conditions, a toluene solution of 2,6-dimethylphenol is added dropwise, 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. The polymer is separated by precipitation with anhydrous ethanol, dissolved in toluene, re-precipitated with sewage ethanol, and 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 for 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 test 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 skilled person may choose to add 0.01-1 parts of an antioxidant and 0.01-1 parts of a lubricant according to actual needs. The antioxidant may be a phenolic antioxidant, a phosphite antioxidant, or a metal deactivator. Other modifiers, such as fillers and weathering agents, may also be added according to actual needs. The content of the polyphenylene ether in the composition of the present invention is not less than 30 wt%.

[0027] The preparation method of the glass fiber reinforced flame retardant polyphenylene ether composition of the present invention comprises the following steps: after uniformly mixing the components according to the proportion, the components are fed into a twin-screw extruder, glass fiber is fed sideways, and after extrusion and granulation, the glass fiber reinforced flame retardant polyphenylene ether composition is obtained; wherein the screw speed is 250-500 rpm; and the extrusion temperature is 230-290°C.

[0028] The application of the glass fiber reinforced flame retardant polyphenylene ether composition of the present invention is used for the liquid cooling plate of new energy vehicles, and has a flame retardant grade of V-0 with a thickness of 1.6 mm and an Izod beam notched impact strength of ≥10 KJ / m 2 , flexural strength ≥ 120MPa, melt flow rate of the material at 300℃ and 5KG ≥ 10g / 10min, and coolant resistance ≥ 92% (the tensile specimen is placed in a coolant-resistant solution of 50% ethylene glycol by mass ratio at 90℃ and immersed for 2000h. According to ISO 527-2:2012 standard, the tensile properties of the material are tested at a tensile rate of 10mm / min, and the tensile property retention rate before and after is compared).

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

[0030] The present invention improves impact resistance by blending HIPS with polyphenylene ether of a specific molecular weight distribution, achieving over 90% retention of high-temperature coolant resistance. Furthermore, by combining modified glass fiber with a specific epoxy resin content, the glass fiber-reinforced polyphenylene ether composition is significantly enhanced and the "wicking" effect of the glass fiber during combustion is mitigated, resulting in a V-0 flame retardancy rating for the glass fiber-reinforced flame-retardant polyphenylene ether composition. Furthermore, the glass fiber-reinforced flame-retardant polyphenylene ether composition exhibits coolant resistance and excellent melt fluidity. DETAILED DESCRIPTION

[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 are not intended to limit the present invention in any form. It should be noted that, for those skilled in the art, several variations and improvements can be made without departing from the scope of the present invention. These all fall within the scope of protection of the present invention.

[0032] The following polyphenylene ether was prepared in-house using the following method: Toluene as the solvent, a catalyst system consisting of copper chloride and diethylamine (at a molar ratio of amine to copper of 35:1) was added sequentially to a reactor. Under a stable oxygen supply, a toluene solution of 2,6-dimethylphenol (2,6-dimethylphenol:copper ion) was added dropwise. The molar ratio of 2,6-dimethylphenol to copper ion was 35:1. The reaction was allowed to proceed at 20°C for 10 minutes to 4 hours. Longer reaction times increase molecular weight, and the molecular weight of the material can be controlled by adjusting the reaction time. After the reaction period, acetic acid was added to terminate the experiment. The polymer was isolated by precipitation with anhydrous ethanol, dissolved in toluene, reprecipitated with wastewater ethanol, and dried in a vacuum oven to constant weight.

[0033] Polyphenylene ether A: reaction time 10 min, monomer 2,6-dimethylphenol, molecular weight distribution 6000-8000 g / mol, homemade;

[0034] Polyphenylene ether B: reaction time 20 min, monomer 2,6-dimethylphenol, molecular weight distribution 9000-11000 g / mol, homemade;

[0035] Polyphenylene ether C: reaction time 25 min, monomer 2,6-dimethylphenol, molecular weight mainly distributed in the range of 12000-14000 g / mol, homemade;

[0036] Polyphenylene ether D: reaction time 30 min, monomer 2,6-dimethylphenol, molecular weight mainly distributed in the range of 13000-16000 g / mol, homemade;

[0037] Polyphenylene ether E: reaction time 50 min, monomer 2,6-dimethylphenol, molecular weight mainly distributed in the range of 25000-28000 g / mol, homemade;

[0038] Polyphenylene ether F: reaction time 1.5 h, monomer 2,6-dimethylphenol, molecular weight mainly distributed in 41000-45000 g / mol, homemade;

[0039] Polyphenylene ether G: reaction time 2 h, monomer 2,6-dimethylphenol, molecular weight mainly distributed in 46000-50000 g / mol, homemade;

[0040] HIPS: PS MA5210, Astor;

[0041] Glass fiber 1: average diameter is about 10 μm, ECS309A-3-H, Chongqing National Day;

[0042] Glass fiber 2: average diameter about 13 μm, EMG13-70C, boulder;

[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] 1,3-Phenylene tetrakis (2,6-dimethylphenyl) phosphate: PX-200, Daihachi, Japan;

[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 with glass fiber side feeding, and after extrusion granulation, a 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 are prepared and the vertical burning grade of the material is tested.

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

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

[0057] (4) Retention rate of high-temperature coolant resistance: The tensile specimens were placed in a coolant-resistant liquid containing 50% ethylene glycol by mass in water at 90°C 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. The tensile property retention rates before and after the tests were compared to evaluate the performance.

[0058] (5) Melt flow rate test: Tested in accordance with 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 ether type 1 EEEEEEF Polyphenylene ether content 135201015202525 Polyphenylene ether type 2 CBCCCCD Polyphenylene ether content 235204035302525 HIPS 10201515151515 Glass fiber 110302020202020 Aminosilane coupling agent 0.20.80.40.40. 40.40.4 Toughener 1422222 Epoxy resin A 0.10.60.40.40.40.40.4 Tributyl phosphate 8151010101010 Antioxidant 0.30.30.30.30.30.30.3 Flame retardant grade V-0V-0V-0V-0V-0V-0V-0 Bending strength, MPa 124194161163165164168 Izod notched impact strength, kJ / m2 12.813.812.913.113.613.313.7Melt flow rate, g / 10min23.817.427.623.921.818.511.6Retention rate, %94959295969394

[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 ether E 25252525 Polyphenylene ether C 25252525 HIPS 15151515 Glass fiber 1202020 Glass fiber 220 Aminosilane coupling agent 0.4 0.4 0.4 0.4 Toughener 2222 Epoxy resin A 0.4 0.4 0.4 Epoxy resin B 0.4 Tributyl phosphate 1010 Phosphazene 10 PX-20010 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 Izod notched impact strength, kJ / m 2 10.413.012.713.5 Melt flow rate, g / 10min16.418.420.123.4 Retention rate, %92949792

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

[0065] It can be seen from Examples 6 / 10 / 11 that when phosphazene is the preferred flame retardant, the high-temperature coolant resistance is better.

[0066] Table 3: Weight parts 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 ether type 1 EEGEGEE Polyphenylene ether content 15452525254035 Polyphenylene ether type 2 CCCAACC Polyphenylene ether content 24552525254035 HIPS 15151515151010 Glass fiber 120202020201010 Aminosilane coupling agent 0.40.40.40.40.40.40 .2 Maleic anhydride 0.2 Toughener 2222211 Epoxy resin A 0.40.40.40.40.40.10.1 Tributyl phosphate 101010101088 Antioxidant 0.30.30.30.30.30.30.3 Flame retardant grade V-0V-0V-0V-0V-0V-1V-0 Bending strength, MPa 168171162159164103121 Izod notched impact strength, kJ / m 2 12.113.513.39.710.110.911.2 Melt flow rate, g / 10min28.98.76.719.77.438.424.2 Retention rate, %86898982848889

[0068] It can be seen from Comparative Example 1 that if the polyphenylene ether content in the range of 9000-16000 g / mol is too high, the high-temperature coolant resistance is poor.

[0069] It can be seen from Comparative Example 2 that if the polyphenylene ether content is too low within the range of 9000-16000 g / mol, although the high-temperature coolant resistance reaches 94%, the melt flow rate is extremely low.

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

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

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

[0073] Table 4: Weight parts 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 ether E353535 Polyphenylene ether C353535 HIPS1010 Glass fiber 1101010 Aminosilane coupling agent 0.20.20.2 Toughener 111 Epoxy resin A00.80.1 Tributyl phosphate 888 Antioxidant 0.30.30.3 Flame retardant grade V-1V-0V-0 Bending strength, MPa 123126131 Izod notched impact strength, kJ / m 2 11.79.18.7 Melt flow rate, g / 10min23.812.75.4 Retention rate, %879091

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

[0076] It can be seen from Comparative Example 9 that if the epoxy resin content is too high, the melt fluidity and coolant resistance will be reduced.

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

Claims

1. A glass fiber reinforced flame retardant polyphenylene ether composition, characterized in that: By weight, it includes the following components: 40-70 parts of polyphenylene ether; HIPS 10-20 copies; Glass fiber 10-30 parts; 1-4 parts of toughening agent; Glass fiber surface modifier 0.2-0.8 parts; Epoxy resin 0.1-0.6 parts; Flame retardant 8-15 parts; The molecular weight distribution of the polyphenylene ether is as follows: the molecular weight of the polyphenylene ether accounting for 20-50% of the total weight of the polyphenylene ether is in the range of 25000-45000 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 9000-16000 g / mol.

2. The glass fiber reinforced flame retardant polyphenylene ether composition according to claim 1, characterized in that: The molecular weight distribution of the polyphenylene ether is as follows: the molecular weight of the polyphenylene ether accounting for 30-40% of the total weight of the polyphenylene ether is in the range of 25000-45000 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 9000-16000 g / mol.

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

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

5. The glass fiber reinforced flame retardant polyphenylene ether composition according to claim 1, characterized in that: The glass fiber surface modifier is selected from at least one of silane coupling agents; the silane coupling agent is selected from at least one of aminosilane coupling agents and methoxysilane coupling agents.

6. The glass fiber reinforced flame retardant polyphenylene ether composition according to claim 1, characterized in that: The flame retardant is selected from at least one of tributyl phosphate, resorcinol bis(2,6-dimethylphenyl) phosphate and phosphazene; preferably, the flame retardant is selected from phosphazene.

7. The glass fiber reinforced flame retardant polyphenylene ether composition according to claim 1, characterized in that: 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.

8. The glass fiber reinforced flame retardant polyphenylene ether composition according to claim 1, characterized in that: By weight, it also includes 0.01-1 part of antioxidant and 0.01-1 part of lubricant.

9. The method for preparing the glass fiber reinforced flame retardant polyphenylene ether composition according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing the components uniformly according to the proportion, feeding the components into a twin-screw extruder, feeding the glass fiber side, extruding and granulating the components, and obtaining a glass fiber reinforced flame retardant polyphenylene ether composition; wherein the screw speed is 250-500 rpm; and the extrusion temperature is 230-290°C.

10. Use of the glass fiber reinforced flame retardant polyphenylene ether composition according to any one of claims 1 to 8, characterized in that: Used for liquid cooling plates of new energy vehicles, with a flame retardant grade of V-0 at a thickness of 1.6mm and an Izod beam notched impact strength of ≥10KJ / m 2 , flexural strength ≥120MPa, melt flow rate of the material at 300℃, 5KG ≥10g / 10min.