PPE composite material and preparation method and application thereof

Abstract

The invention discloses a PPE composite material as well as a preparation method and application thereof, and belongs to the field of high polymer materials. The anti-yellowing agent of a specific amount is added into the PPE resin, the proportion of the antioxidant, benzoin and the inorganic toner of a specific type in the anti-yellowing agent is controlled to be within a specific range, so that the high-temperature anti-yellowing performance of the material is synergistically improved, meanwhile, the addition amount of the antioxidant, benzoin and the inorganic toner is low, the cost is low, the excellent mechanical performance of the material can be kept, and the service life of the material is prolonged. The obtained material is suitable for preparing electronic and electrical field products such as good-appearance electronic industrial control shells, cooling fans and photovoltaic energy storage upper covers.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high polymer materials, in particular to a PPE composite material and a preparation method and application thereof. BACKGROUND

[0002] Polyphenylene oxide, the chemical name of which is poly 2, 6-dimethyl-1, 4-phenyl ether, was developed in the 1960s, and is also known as PPO (Polyphenylene Oxide) or PPE (Polypheyleneether). It is one of the five major engineering plastics in the world, together with PA (polyamide), PC (polycarbonate), PBT (polybutylene terephthalate) and POM (polyoxymethylene). PPE has a relatively small relative density and belongs to a non-crystalline polymer material. It has good mechanical properties, a high heat resistance temperature, excellent chemical resistance, extremely low water absorption and excellent flame retardation, and is widely used in new energy, electronic appliances, automotive electronics, OA (office automation) and other fields.

[0003] However, during the processing or use of PPE at high temperatures, the molecular chains thereof may undergo a Fries rearrangement reaction, change the molecular chain structure, and generate quinone and other color-causing substances, resulting in yellowing of the material and affecting the color stability of the product. Therefore, it is necessary to develop a technology to effectively solve the yellowing problem of PPE at high temperatures. SUMMARY

[0004] Based on the defects of the prior art, the purpose of the present application is to provide a PPE composite material and a preparation method and application thereof, which has excellent high-temperature yellowing resistance.

[0005] In order to achieve the above purpose, in a first aspect, the present application provides a PPE composite material, which comprises the following components by weight: PPE resin 100 parts, Antioxidant 0.1-1.5 parts, benzoin 0.1-1.5 parts, inorganic color powder 0.5-2 parts; The inorganic color powder is at least one of a tungstate and an acetate.

[0006] The inventors found in the research process that adding appropriate amount of antioxidant, benzoin and specific inorganic color powder in PPE resin can effectively avoid yellowing at high temperature, wherein the antioxidant can inhibit the oxidation behavior of PPE resin; as a high-efficiency reducing agent, benzoin can quench the oxygen free radicals generated by the high-temperature oxidation of PPE resin, and prevent the production of color-causing substances; at least one of tungstate and acetate is used as inorganic color powder, which can exhibit temperature response under the action of temperature, and can neutralize the color change of the matrix resin by changing its own color, thereby inhibiting the change of the red phase (a value) of the material, and the cation of the inorganic color powder can also complex with the PPE resin, thereby inhibiting the movement of the molecular chain of the PPE resin to the oxygen free radicals, and also reducing the influence of the oxidation reaction on the color of the product to a certain extent. By adding antioxidant, benzoin and specific inorganic color powder in PPE resin and controlling their amount within the above-mentioned appropriate range, the three can synergistically improve the high-temperature yellowing resistance of the material, so that the material is not easy to yellow at high temperature, and the amount of the three is relatively low, the cost is low, and the material also has excellent mechanical properties.

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

[0008] The antioxidant is 0.1-1.5 parts by weight, such as 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 1.1 part by weight, 1.2 part by weight, 1.3 part by weight, 1.4 part by weight, 1.5 part by weight or any range formed by any two of the above. Preferably, the antioxidant is 0.3-0.8 parts by weight, so as to make the yellowing resistance of the composite material more excellent at a lower cost.

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

[0010] The inorganic toner is 0.5-2 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 any two of the above. Preferably, the inorganic toner is 1.2-1.5 parts by weight, to make the yellowing resistance of the composite material more optimal at a lower cost.

[0011] Preferably, the mass percentage content of the antioxidant in the PPE composite material is 0.1%-1.3%, 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%, or any range formed by any two of the above.

[0012] Preferably, the mass percentage content of the antioxidant in the PPE composite material is 0.1%-1.3%, 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%, or any range formed by any two of the above.

[0013] Preferably, the mass percentage content of the inorganic toner in the PPE composite material is 0.2%-1.7%, such as 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%, or any range formed by any two of the above.

[0014] Preferably, the inorganic toner includes at least one of sodium tungstate, potassium tungstate, magnesium tungstate, calcium tungstate, cobalt tungstate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate, to make the high-temperature yellowing resistance of the PPE composite material more optimal.

[0015] More preferably, the inorganic toner 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 a symmetrical hindered phenolic antioxidant, an asymmetrical hindered phenolic antioxidant, a phosphite antioxidant.

[0017] More preferably, the antioxidant comprises at least one of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide) (i.e., RIANOX 1098), 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[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), pentaerythrityl tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (i.e., Antioxidant 1010), bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythrityl diphosphite (i.e., PEP-36).

[0018] Preferably, the PPE resin has a viscosity of 0.43 dL / g or less to avoid excessive melt viscosity during processing, reduce the shear strength of the material during processing (e.g., in the barrel), avoid overheat degradation of the material leading to performance decay and excessive yellowing, and thus ensure the color stability of the composite material.

[0019] More preferably, the PPE resin has a viscosity of 0.35-0.4 dL / g to make the melt viscosity more suitable during processing, not only reduce the overheat degradation caused by the shear plasticization of the material, but also the PPE resin itself has good thermal stability, thus making the high-temperature yellowing resistance of the composite material more optimal.

[0020] The viscosity of the PPE resin is tested as follows: determined by an Ubbelohde viscometer, the solvent is chloroform, the test temperature is 25°C, and the test solution viscosity is 0.5 g / dL.

[0021] Preferably, the PPE composite material further comprises the following components by weight: 0-30 parts of HIPS (high impact polystyrene) resin. For example, the HIPS is 0, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, or any interval range formed by any two of the above. In some embodiments, the HIPS is 10-30 parts by weight. In an embodiment, the HIPS is 5-15 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 further comprises the following components in parts by weight: 0-18 parts of a toughening agent. For example, the toughening agent is 0, 2 parts by weight, 5 parts by weight, 7 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, or any range formed by any two of the above. Preferably, the toughening agent is a thermoplastic elastomer, which comprises at least one of ethylene-propylene-diene terpolymer (EPDM), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene rubber (SBR), styrene-ethylene / butylene-styrene block copolymer (SEBS), and graft of styrene-ethylene / butylene-styrene block copolymer (graft of SEBS).

[0024] Preferably, the PPE composite further comprises the following components in parts by weight: 0-12 parts of a flame retardant. For example, the flame retardant is 0, 2 parts by weight, 5 parts by weight, 7 parts by weight, 10 parts by weight, 12 parts by weight, or any range formed by any two of the above. In an embodiment, the flame retardant is 0.01-12 parts by weight.

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

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

[0027] If necessary, at least one of heat stabilizer, light stabilizer, lubricant, ultraviolet absorber can also be added in the PPE composite, but not limited thereto.

[0028] For example, the heat stabilizer comprises at least one of calcium-zinc type, barium-zinc type, organic tin type, and the like. The heat stabilizer can be selected from 0-0.2 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 any two of the above.

[0029] For example, the light stabilizer comprises at least one of hindered phenol type, hindered amine type, and the like. The light stabilizer can be selected from 0-0.2 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 any two of the above.

[0030] For example, the lubricant comprises at least one of ester type, hydrocarbon type, amide type, and the like. The lubricant can be selected from 0-0.2 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 any two of the above.

[0031] Exemplarily, the ultraviolet absorber includes at least one of benzotriazole, hydroxybenzophenone, triazine, and the like. The ultraviolet absorber can be selected as 0-0.2 parts by weight, such as 0.01 parts by weight, 0.1 parts by weight, 0.2 parts by weight, or any interval range formed by any two of the above.

[0032] In a second aspect, the application provides a preparation method of the PPE composite material, including the following steps: mixing and dispersing the raw materials, melt extrusion, granulation, and obtaining the PPE composite material.

[0033] In some embodiments, the melt extrusion is performed 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-diameter ratio: (40-56):1.

[0034] In a third aspect, the application provides an application of the PPE composite material in the field of electronic and electrical engineering, such as industrial control shell, heat dissipation fan shell and fan blade, photovoltaic energy storage upper cover, and the like.

[0035] Compared with the prior art, the application has the beneficial effects that: by adding a specific amount of anti-yellowing agent in the PPE resin, and controlling the ratio of the antioxidant, benzoin, and specific types of inorganic color powder in the anti-yellowing agent within a specific range, the high-temperature yellowing resistance of the material is improved, and the addition amount of the three is low, the cost is low, which is beneficial to maintaining excellent mechanical properties of the material, so that the obtained material is suitable for products in the field of electronic and electrical engineering. DETAILED DESCRIPTION

[0036] In order to better illustrate the purpose, technical scheme and advantages of the application, the application will be further described below in combination with specific examples and comparative examples, the purpose of which is to understand the content of the application in detail, rather than to limit the application. All other examples obtained by those of ordinary skill in the art without creative labor are within the scope of protection of the application. The experimental reagents and instruments involved in the implementation of the application are common ordinary reagents and instruments unless otherwise specified. In the application, the open description of the technical features includes the closed technical solution consisting of the listed features, and also includes the open technical solution containing the listed features.

[0037] The raw material information used in the following examples and comparative examples is shown below, and unless otherwise specified, all are commercially available raw materials, and in addition, the component raw materials used in each parallel experiment are the same: PPE resin 1: purchased from Dalian Zhongmu Chemical Co., Ltd., brand PPE ZM035, viscosity 0.35 dL / g; PPE resin 2: purchased from Nantong Xingchen Synthetic Material Co., Ltd., brand PPE LXN040, viscosity 0.40 dL / g; PPE resin 3: purchased from Asahi Kasei Corporation, brand XYRON S203A, viscosity 0.32 dL / g; PPE resin 4: purchased from Asahi Kasei Corporation, brand 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 toner 1: sodium tungstate, commercially available; Inorganic toner 2: magnesium acetate, commercially available; Inorganic toner 3: cobalt tungstate, commercially available; Inorganic toner 4: sodium acetate, commercially available; Inorganic toner 5: sodium sulfate, commercially available; HIPS resin: purchased from Yashida Chemical (Jiangsu) Co., Ltd., brand PS MA5201 (Jiangsu), melt index 4.5 g / 10 min at temperature 200 °C and load 5 kg; Toughening agent: SEBS, purchased from Tai Xiang Co., Ltd., SEBS 6151; Flame retardant: BDP, purchased from Zhejiang Wansheng Technology Co., Ltd., brand WSFR-BDP-N2.

[0038] Each of the following examples and comparative examples provides a PPE composite material, the specific composition is shown in Table 1 or Table 2, and the preparation method thereof comprises the following steps: The raw materials of each component are mixed and dispersed, and then melt-extruded in a twin-screw extruder, granulated to obtain a PPE composite material, wherein the length-diameter ratio of the twin-screw extruder is 52:1, the rotation speed is 480 rpm, and the temperature of each zone is as follows: Zone 1: 260 °C, zone 2: 270 °C, zone 3: 280 °C, zone 4: 270 °C, zone 5: 270 °C, and zone 6: 260 °C.

[0039] Table 1 Table 2 The PPE composite materials in the above examples and the comparative examples PPE were injection molded into 2mm*45mm*80mm color plates, the injection molding temperature was 280℃, and then the performance of the color plates was tested by the following method: Initial color: the Lab value of the color plate was tested by using a color difference meter, wherein the L0 value represented the initial brightness, the a0 value represented the initial redness, and the b0 value represented the initial blueness; Color after aging: the color plate was high-temperature aged at 120℃ and 170℃ for 48h, and the color of the color plate after aging was tested by using a color difference meter, the brightness, redness and blueness after aging were recorded as L, a and b respectively, and the color change ΔE before and after aging was calculated according to 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 From the above data, it can be seen that the PPE composite materials of the embodiments have excellent high-temperature yellowing resistance, for example, ΔE is less than 3.5 after aging at 120℃ for 48h, and ΔE is less than 6.5 after aging at 170℃ for 48h.

[0042] It can be seen from the comparison of Examples 1~10 and Comparative Examples 1~4 that when any of benzoin, inorganic color powder is missing, or any of benzoin and antioxidant is missing, the high-temperature yellowing resistance of the composite material will be significantly deteriorated, which shows that the antioxidant, benzoin and inorganic color powder can synergistically improve the high-temperature yellowing resistance of the composite material, and when the antioxidant is 0.1~1.5 parts by weight, the benzoin is 0.1~1.5 parts by weight, and the inorganic color powder 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 part by weight, and the inorganic color powder is 1.2~1.5 parts by weight, the high-temperature yellowing resistance of the composite material is more excellent, and the cost is low.

[0043] It can be seen from the comparison of Examples 1, 14~16 and Comparative Example 5 that when other inorganic color powders such as sulfate are used, the color is not sensitive to temperature change, and cannot neutralize the color change of the matrix resin through its own color change, thereby leading to poor yellowing resistance of the composite material at high temperature, while when at least one of tungstate and acetate is used as the inorganic color powder, the inorganic color powder will respond to the temperature change appropriately, and can neutralize the color change of the matrix resin through its own color change, thereby inhibiting the change of the red phase (a value) of the material, so that the high-temperature yellowing resistance of the composite material is excellent.

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

[0045] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A PPE composite material, characterized by, The PPE composite material comprises the following components by weight: PPE resin 100 parts, Antioxidant 0.1~1.5 parts, Benzoin 0.1~1.5 parts, Inorganic color powder 0.5~2 parts. The inorganic color powder is at least one of tungstate, acetate.

2. The PPE composite material of claim 1, wherein, The PPE composite material comprises the following components by weight: PPE resin 100 parts, Antioxidant 0.3~0.8 parts, Benzoin 0.3~1 parts, Inorganic color powder 1.2~1.5 parts.

3. The PPE composite material of claim 1, wherein, The inorganic color powder comprises at least one of sodium tungstate, potassium tungstate, magnesium tungstate, calcium tungstate, cobalt tungstate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate; preferably, the inorganic color powder comprises sodium tungstate.

4. The PPE composite of claim 1, wherein, The antioxidant comprises at least one of symmetric hindered phenolic antioxidant, asymmetric hindered phenolic antioxidant, phosphite antioxidant; preferably, the antioxidant comprises at least one of N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxybenzylamide), tetra-(beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid) pentaerythritol ester, 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.

5. The PPE composite material of claim 1, wherein, The PPE resin has an intrinsic viscosity of 0.43 dL / g or less; preferably, the PPE resin has a viscosity of 0.35~0.4 dL / g.

6. The PPE composite material of claim 1, wherein, The PPE composite material further comprises the following components by weight: HIPS resin 10~30 parts; preferably, the HIPS resin has a melt index of 3~10 g / 10 min under the condition of temperature 200°C and load 5 kg.

7. The PPE composite material of claim 1, wherein, The PPE composite material further comprises the following components by weight: toughening agent 5~18 parts; preferably, the toughening agent is a thermoplastic elastomer, which comprises at least one of ethylene-propylene-diene terpolymer, styrene-butadiene-styrene block copolymer, styrene-butadiene rubber, styrene-ethylene / butylene-styrene block copolymer, graft of styrene-ethylene / butylene-styrene block copolymer.

8. The PPE composite material of claim 1, wherein, The PPE composite material comprises the following components by weight: flame retardant 0.01~12 parts; preferably, the flame retardant comprises at least one of halogen-free phosphorus flame retardant, phosphorus-nitrogen flame retardant.

9. A method of making a PPE composite material as claimed in any one of claims 1 to 8, comprising the steps of: The raw materials are mixed and dispersed, melt-extruded, and granulated to obtain the PPE composite material.

10. Use of the PPE composite material according to any one of claims 1~8 in the field of electronics and electrical appliances.

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