A ppe composite material and preparation method and application thereof

Abstract

The application discloses a PPE composite material and a preparation method and application thereof, and belongs to the field of high polymer materials. The high-temperature yellowing resistance of the material is improved by adding a specific amount of an anti-yellowing agent into PPE resin and controlling the proportion of the antioxidant, benzoin and specific types of inorganic color powder in the anti-yellowing agent within a specific range. The three additives have low amounts and low costs, and are beneficial to maintaining excellent mechanical properties of the material, so that the obtained material is suitable for preparing electronic and electrical field products such as electronic industrial control housings, heat dissipation fans, photovoltaic energy storage upper covers and the like.

Description

Technical Field

[0001] This application relates to the field of polymer materials, specifically to a PPE composite material and its preparation method and application. Background Technology

[0002] Polyphenylene ether (PPO), chemically known as poly2,6-dimethyl-1,4-phenylene ether, was developed in the 1960s. It is also commonly abbreviated as PPO or PPE, and is considered one of the world's five major engineering plastics, along with PA (polyamide), PC (polycarbonate), PBT (polybutylene terephthalate), and POM (polyoxymethylene). PPE has a relatively low density and is a non-crystalline polymer material. It possesses excellent mechanical properties, high heat resistance, superior chemical resistance, extremely low water absorption, and excellent flame retardancy, making it widely used in new energy, electronics, automotive electronics, and office automation (OA) fields.

[0003] However, during high-temperature processing or use, PPE undergoes a Fries-like rearrangement reaction, altering its molecular structure and generating chromogenic substances such as quinones, leading to yellowing and affecting the product's color stability. Therefore, it is necessary to develop a technology to effectively address the yellowing problem of PPE at high temperatures. Summary of the Invention

[0004] Based on the deficiencies of the existing technology, the purpose of this application is to provide a PPE composite material, its preparation method and application, wherein the PPE composite material has excellent high-temperature yellowing resistance.

[0005] To achieve the above objectives, in a first aspect, this application provides a PPE composite material comprising the following components in parts by weight: 100 parts of PPE resin, Antioxidant 0.1~1.5 parts, Benzoin 0.1~1.5 parts, Inorganic pigment powder 0.5~2 parts; The inorganic pigment is at least one of tungstate and acetate.

[0006] During their research, the inventors discovered that adding appropriate amounts of antioxidants, benzoin, and specific inorganic colorants to PPE resin can effectively prevent yellowing at high temperatures. The antioxidants inhibit the oxidation behavior of PPE resin; benzoin, as a highly efficient reducing agent, quenches oxygen free radicals generated during high-temperature oxidation of PPE resin, preventing the production of coloring substances; and using at least one of tungstate and acetate as inorganic colorants, the color of the inorganic colorant exhibits a temperature response, neutralizing the color change of the matrix resin through its own color change, inhibiting changes in the reddish hue (a value) of the material. Furthermore, the cations of the inorganic colorant can complex with PPE resin, inhibiting the movement of PPE resin molecular chains towards oxygen free radicals, and also reducing the impact of oxidation reactions on product color to a certain extent. By adding antioxidants, benzoin, and specific types of inorganic pigments to PPE resin and controlling their amounts within the aforementioned suitable range, these three components can synergistically improve the material's high-temperature yellowing resistance, making the material less prone to yellowing at high temperatures. At the same time, the addition of these three components is relatively low, resulting in lower costs and also helping the material maintain excellent mechanical properties.

[0007] Preferably, the PPE resin content in the PPE composite material is 40% or more by mass, such as 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 87.6% or more, or any two of these ranges.

[0008] The antioxidant is present in an amount of 0.1 to 1.5 parts by weight, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, or 1.5 parts by weight, or any range formed by two or more of these amounts. Preferably, the antioxidant is present in an amount of 0.3 to 0.8 parts by weight, so as to improve the yellowing resistance of the composite material at a lower cost.

[0009] The benzoin is present in an amount of 0.1 to 1.5 parts by weight, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5 parts by weight, or any range formed by two or more of these amounts. Preferably, the benzoin is present in an amount of 0.3 to 1 part by weight, so as to improve the yellowing resistance of the composite material at a lower cost.

[0010] The inorganic pigment is present in an amount of 0.5 to 2 parts by weight, such as 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, or any range formed by two or more of these amounts. Preferably, the inorganic pigment is present in an amount of 1.2 to 1.5 parts by weight, so as to improve the yellowing resistance of the composite material at a lower cost.

[0011] Preferably, in the PPE composite material, the antioxidant content by mass percentage is between 0.1% and 1.3%, such as within the range formed by any two of the following: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, or more.

[0012] Preferably, in the PPE composite material, the mass percentage content of benzoin is between 0.1% and 1.3%, such as within the range formed by any two of the following: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3% or more.

[0013] Preferably, in the PPE composite material, the mass percentage content of the inorganic pigment is between 0.2% and 1.7%, such as within the range formed by any two of the following: 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%.

[0014] Preferably, the inorganic pigment includes at least one of sodium tungstate, potassium tungstate, magnesium tungstate, calcium tungstate, cobalt tungstate, sodium acetate, potassium acetate, magnesium acetate, and calcium acetate, so as to improve the high-temperature yellowing resistance of the PPE composite material.

[0015] More preferably, the inorganic pigment includes sodium tungstate to further improve the high-temperature yellowing resistance of the PPE composite material.

[0016] Preferably, the antioxidant includes at least one of symmetric hindered phenolic antioxidants, asymmetric hindered phenolic antioxidants, and phosphite antioxidants.

[0017] More preferably, the antioxidant includes at least one of N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide) (i.e., RIANOX 1098), 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane (REVONOX 608), 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (antioxidant GA-80), pentaerythritol tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (i.e., antioxidant 1010), and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (i.e., PEP-36).

[0018] Preferably, the viscosity of the PPE resin is below 0.43 dL / g to avoid excessive melt viscosity during processing, which would reduce the shear strength of the material during processing (such as the shear strength in the screw barrel), prevent the material from overheating and degrading, leading to performance degradation and excessive yellowing, and thus ensure the color stability of the composite material.

[0019] More preferably, the viscosity of the PPE resin is 0.35~0.4 dL / g, so that the melt viscosity is more suitable during processing. This not only reduces the overheating degradation caused by material shear plasticization, but also the PPE resin itself has good thermal stability, thus making the high-temperature yellowing resistance of the composite material better.

[0020] The viscosity of the PPE resin was tested as follows: it was measured using an Ubbelohde viscometer, with chloroform as the solvent, at a test temperature of 25°C, and the solution viscosity was 0.5 g / dL.

[0021] Preferably, the PPE composite material further comprises the following components in parts by weight: 0 to 30 parts of HIPS (high-impact polystyrene) resin. For example, HIPS is in the range of 0, 5, 10, 15, 20, 25, 30 parts by weight, or any combination thereof. In some embodiments, HIPS is 10 to 30 parts by weight. In one embodiment, HIPS is 5 to 15 parts by weight.

[0022] Preferably, the HIPS resin has a melt index of 3~10 g / 10 min at a temperature of 200°C and a load of 5 kg. The melt index of the HIPS resin is tested according to standard ISO 1133-1-2022.

[0023] Preferably, the PPE composite material further includes the following components in parts by weight: 0 to 18 parts of toughening agent. For example, the toughening agent is in the range of 0, 2, 5, 7, 10, 12, 15, 18 parts by weight, or any combination thereof. Preferably, the toughening agent is a thermoplastic elastomer, which includes at least one of ethylene-propylene-diene terpolymer (EPDM), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene rubber (SBR), styrene-ethylene / butene-styrene block copolymer (SEBS), and grafts of styrene-ethylene / butene-styrene block copolymer (grafts of SEBS).

[0024] Preferably, the PPE composite material further includes the following components in parts by weight: 0 to 12 parts of flame retardant. For example, the toughening agent is in the range of 0, 2, 5, 7, 10, 12 parts by weight, or any combination thereof. In one embodiment, the flame retardant is 0.01 to 12 parts by weight.

[0025] Preferably, the flame retardant includes at least one of halogen-free phosphorus-based flame retardants and phosphorus-nitrogen-based flame retardants.

[0026] Preferably, the flame retardant includes at least one of bisphenol A bis(diphenyl phosphate) (BDP) and melamine cyanurate (MCA).

[0027] Depending on the requirements, at least one of the following can be added to the PPE composite material: heat stabilizer, light stabilizer, lubricant, and ultraviolet absorber, but not limited thereto.

[0028] For example, the heat stabilizer includes at least one of the following types of heat stabilizers: calcium-zinc, barium-zinc, organotin, etc. The heat stabilizer may be selected in the range of 0 to 0.2 parts by weight, such as 0.01 parts by weight, 0.1 parts by weight, 0.2 parts by weight, or any range formed by two or more of the above.

[0029] For example, the light stabilizer includes at least one type of light stabilizer such as hindered phenols and hindered amines. The light stabilizer may be selected in the range of 0 to 0.2 parts by weight, such as 0.01 parts by weight, 0.1 parts by weight, 0.2 parts by weight, or any range formed by two or more of the above.

[0030] For example, the lubricant includes at least one of the types of lubricants such as esters, hydrocarbons, and amides. The lubricant may be selected in the range of 0 to 0.2 parts by weight, such as 0.01 parts by weight, 0.1 parts by weight, 0.2 parts by weight, or any range formed by two or more of the above.

[0031] For example, the ultraviolet absorber includes at least one of the following types of ultraviolet absorbers: benzotriazoles, hydroxybenzophenones, triazines, etc. The ultraviolet absorber may be selected in the range of 0 to 0.2 parts by weight, such as 0.01 parts by weight, 0.1 parts by weight, 0.2 parts by weight, or any range formed by two or more of the above.

[0032] Secondly, this application provides a method for preparing the PPE composite material, comprising the following steps: mixing and dispersing the component raw materials, melt extruding, granulating, and obtaining the PPE composite material.

[0033] In some embodiments, the melt extrusion is carried out in a screw extruder, such as a twin-screw extruder. Preferably, the process parameters of the screw extruder are set as follows: Zone 1: 260℃, Zone 2: 270℃, Zone 3: 280℃, Zone 4: 270℃, Zone 5: 270℃, Zone 6: 260℃, screw speed: 300~1000rpm, screw length-to-diameter ratio: (40~56):1.

[0034] Thirdly, this application provides applications of the PPE composite material in the field of electronics and electrical engineering, such as industrial control housings, cooling fan housings and blades, photovoltaic energy storage covers, etc.

[0035] Compared with the prior art, the beneficial effects of this application are as follows: This application adds a specific amount of anti-yellowing agent to PPE resin and controls the ratio of antioxidant, benzoin and specific types of inorganic pigments in the anti-yellowing agent within a specific range to synergistically improve the high-temperature yellowing resistance of the material. At the same time, the addition of these three substances is low, the cost is low, which helps the material maintain excellent mechanical properties and makes the resulting material suitable for use in electronic and electrical products. Detailed Implementation

[0036] To better illustrate the purpose, technical solutions, and advantages of this application, the following description, in conjunction with specific embodiments and comparative examples, aims to provide a detailed understanding of the content of this application, rather than limiting it. All other embodiments obtained by those skilled in the art without inventive effort are within the protection scope of this application. Unless otherwise specified, the experimental reagents and instruments involved in the implementation of this application are commonly used reagents and instruments. In this application, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0037] The raw materials used in the following embodiments and comparative examples are shown below. Unless otherwise specified, all raw materials are commercially available. In addition, the same raw materials were used in each parallel experiment: PPE resin 1: Purchased from Dalian Zhongmu Chemical Co., Ltd., grade PPE ZM035, viscosity is 0.35dL / g; PPE resin 2: purchased from Nantong Xingchen Synthetic Materials Co., Ltd., grade PPE LXN040, viscosity 0.40 dL / g; PPE resin 3: purchased from Asahi Kasei Corporation, Japan, grade XYRON S203A, viscosity 0.32 dL / g; PPE resin 4: Purchased from Asahi Kasei Corporation, Japan, grade XYRON S201A, viscosity 0.43 dL / g; Antioxidant 1: RIANOX 1098, commercially available; Antioxidant 2: REVONOX 608, commercially available; Antioxidant 3: Antioxidant 1010, commercially available; Antioxidant 4: PEP-36, commercially available; Benzoin: Commercially available; Inorganic pigment 1: Sodium tungstate, commercially available; Inorganic pigment 2: Magnesium acetate, commercially available; Inorganic pigment 3: Cobalt tungstate, commercially available; Inorganic pigment 4: Sodium acetate, commercially available; Inorganic pigment 5: Sodium sulfate, commercially available; HIPS resin: purchased from Yashide Chemical (Jiangsu) Co., Ltd., grade PS MA5201 (Jiangsu), with a melt index of 4.5 g / 10 min at a temperature of 200°C and a load of 5 kg. Toughening agent: SEBS, purchased from TSRC Corporation, SEBS 6151; Flame retardant: BDP, purchased from Zhejiang Wansheng Technology Co., Ltd., brand name: WSFR-BDP-N2.

[0038] The following examples and comparative examples all provide a PPE composite material, the specific composition of which is shown in Table 1 or Table 2. Their preparation methods include the following steps: The raw materials were mixed and dispersed, melt-extruded in a twin-screw extruder, and granulated to obtain a PPE composite material. The twin-screw extruder had an aspect ratio of 52:1, a rotation speed of 480 rpm, and the temperatures in each zone were as follows: Zone 1: 260℃, Zone 2: 270℃, Zone 3: 280℃, Zone 4: 270℃, Zone 5: 270℃, Zone 6: 260℃.

[0039] Table 1 Table 2 The PPE composite materials of the above examples and comparative examples were injection molded into color samples of 2mm*45mm*80mm at an injection temperature of 280℃, and the performance of the color samples was then tested as follows: Initial color: The Lab value of the color swatch is measured using a colorimeter, where L0 represents the initial brightness, a0 represents the initial redness, and b0 represents the initial blueness. Color after aging: The color swatches were aged at 120℃ and 170℃ for 48 hours. The color of the aging swatches was tested using a colorimeter. The brightness, redness, and blueness after aging were recorded as L, a, and b, respectively. The color change ΔE before and after aging was calculated using the following formula: ΔE=((L-L0) 2 +(a-a0) 2 +(b-b0) 2 ) 1 / 2 .

[0040] The test results are shown in Table 3.

[0041] Table 3 As can be seen from the above data, the PPE composite materials of each embodiment of this application have excellent high-temperature yellowing resistance, such as ΔE below 3.5 after aging at 120℃ for 48h and ΔE below 6.5 after aging at 170℃ for 48h.

[0042] A comparison of Examples 1-10 with Comparative Examples 1-4 shows that the absence of any one of benzoin or inorganic pigment, or any one of benzoin or antioxidant, significantly deteriorates the high-temperature yellowing resistance of the composite material. This indicates that antioxidants, benzoin, and inorganic pigment can synergistically improve the high-temperature yellowing resistance of the composite material. Moreover, when the antioxidant is 0.1-1.5 parts by weight, the benzoin is 0.1-1.5 parts by weight, and the inorganic pigment is 0.5-2 parts by weight, especially when the antioxidant is 0.3-0.8 parts by weight, the benzoin is 0.3-1 parts by weight, and the inorganic pigment is 1.2-1.5 parts by weight, the high-temperature yellowing resistance of the composite material is even better, and the cost is low.

[0043] A comparison of Examples 1, 14-16 and Comparative Example 5 shows that when other inorganic pigments, such as sulfates, are used, their color is not sensitive to temperature changes and cannot neutralize the color changes of the matrix resin through their own color changes. This results in poor yellowing resistance of the composite material at high temperatures. However, when at least one of tungstate or acetate is used as an inorganic pigment, the inorganic pigment will make a suitable temperature response according to temperature changes. It can neutralize the color changes of the matrix resin through its own color changes and suppress the change of the red phase (a value) of the material, thereby making the composite material have excellent high-temperature yellowing resistance.

[0044] As can be seen from the comparison of Examples 1 and 17-19, when the viscosity of PPE resin is below 0.43 dL / g, especially in the range of 0.35-0.4 dL / g, the high-temperature yellowing resistance of the composite material is better.

[0045] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application and are not intended to limit the scope of protection of this application. Although this application has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of this application without departing from the substance and scope of the technical solutions of this application.

Claims

1. A PPE composite material, characterized in that, Includes the following components by weight: 100 parts of PPE resin, Antioxidant 0.1~1.5 parts, Benzoin 0.1~1.5 parts, Inorganic pigment powder 0.5~2 parts; The inorganic pigment is at least one of sodium tungstate, potassium tungstate, magnesium tungstate, calcium tungstate, cobalt tungstate, sodium acetate, potassium acetate, magnesium acetate, and calcium acetate. The antioxidant includes at least one of symmetric hindered phenolic antioxidants, asymmetric hindered phenolic antioxidants, and phosphite antioxidants.

2. The PPE composite material as described in claim 1, characterized in that, Includes the following components by weight: 100 parts of PPE resin, Antioxidant 0.3~0.8 parts, Benzoin 0.3~1 part, Inorganic pigment 1.2~1.5 parts.

3. The PPE composite material as described in claim 1, characterized in that, The inorganic pigment includes sodium tungstate.

4. The PPE composite material as described in claim 1, characterized in that, The antioxidants include at least one of N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), pentaerythritol tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane, and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.

5. The PPE composite material as described in claim 1, characterized in that, The intrinsic viscosity of the PPE resin is below 0.43 dL / g.

6. The PPE composite material as described in claim 5, characterized in that, The intrinsic viscosity of the PPE resin is 0.35 ~ 0.4 dL / g.

7. The PPE composite material as described in claim 1, characterized in that, It also includes the following components by weight: 10-30 parts of HIPS resin.

8. The PPE composite material as described in claim 7, characterized in that, The HIPS resin has a melt index of 3~10 g / 10 min at a temperature of 200°C and a load of 5 kg.

9. The PPE composite material as described in claim 1, characterized in that, It also includes the following components by weight: 5 to 18 parts toughening agent.

10. The PPE composite material as described in claim 9, characterized in that, The toughening agent is a thermoplastic elastomer, which includes at least one of ethylene-propylene-diene terpolymer, styrene-butadiene-styrene block copolymer, styrene-butadiene rubber, styrene-ethylene / butene-styrene block copolymer, and grafts of styrene-ethylene / butene-styrene block copolymer.

11. The PPE composite material as described in claim 1, characterized in that, It includes the following components by weight: 0.01 to 12 parts of flame retardant.

12. The PPE composite material as described in claim 11, characterized in that, The flame retardant includes at least one of halogen-free phosphorus-based flame retardants and phosphorus-nitrogen-based flame retardants.

13. A method for preparing the PPE composite material according to any one of claims 1 to 12, comprising the following steps: The raw materials are mixed and dispersed, melt-extruded, and granulated to obtain PPE composite material.

14. The application of the PPE composite material as described in any one of claims 1 to 12 in the field of electronics and electrical engineering.

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