A PPE / PSU composite material and preparation method thereof

Abstract

The present invention relates to the field of polymer composite materials, and specifically relates to a PPE / PSU composite material and a preparation method thereof. The composite material comprises the following components, measured in parts by weight: 40-60 parts of polyphenylene ether, 15-30 parts of bisphenol A polysulfone, 5-10 parts of bisphenol A polysulfone-nylon block copolymer, 10-20 parts of glass fiber, and 0.5-1.5 parts of an antioxidant GA-80. The composite material prepared by the present invention has excellent mechanical properties and good solvent resistance in alcohol solvents.

Description

Technical Field

[0001] The present invention relates to the field of polymer composite materials, in particular to a PPE / PSU composite material and a preparation method thereof. Background Art

[0002] Polyphenylene ether (PPE) has excellent electrical and thermal properties, boiling water resistance, radiation resistance, dimensional stability, and flame retardancy, but has disadvantages such as poor fluidity and difficulty in processing. Therefore, it appears in the market in the form of modified materials. Currently, the most common polyphenylene ether blend systems are polyphenylene ether / polystyrene systems, polyphenylene ether / polyamide systems, and polyphenylene ether / polyester systems. Polysulfone (PSU) is a polymer compound with excellent thermal stability, weather resistance, chemical stability, and mechanical properties, but there are currently few reports on PPE / PSU composite materials. Summary of the Invention

[0003] Purpose of the invention: In order to solve the above technical problems, the present invention proposes a PPE / PSU composite material and a preparation method thereof.

[0004] The technical solutions adopted are as follows:

[0005] A PPE / PSU composite material, comprising the following components in parts by weight:

[0006] 40-60 parts of polyphenylene ether, 15-30 parts of bisphenol A polysulfone, 5-10 parts of bisphenol A polysulfone-nylon block copolymer, 10-20 parts of glass fiber, and 0.5-1.5 parts of antioxidant GA-80.

[0007] Furthermore, the polyphenylene ether includes thermosetting polyphenylene ether resin and thermoplastic polyphenylene ether resin.

[0008] Furthermore, the weight ratio of the thermosetting polyphenylene ether resin to the thermoplastic polyphenylene ether resin is 1-5:1-5.

[0009] Furthermore, the preparation method of the bisphenol A type polysulfone-nylon block copolymer is as follows:

[0010] Mix caprolactam and bisphenol A polysulfone, evacuate the mixture and raise the temperature to 180-200°C to dissolve bisphenol A polysulfone in the caprolactam. Then add the catalyst, maintain the vacuum state, stir and react for 5-15 hours, then return to room temperature. Grind the obtained product and dry it.

[0011] Furthermore, the weight ratio of the caprolactam to the bisphenol A polysulfone is 30:1-5.

[0012] Furthermore, the catalyst is sodium hydroxide and / or potassium hydroxide.

[0013] Furthermore, the glass fiber is treated with plasma activation, silane coupling agent KH-570 and glycidyl methacrylate.

[0014] Furthermore, the preparation method of the glass fiber is as follows:

[0015] After plasma activation, the glass fiber is added to an ethanol aqueous solution, and the pH of the system is adjusted to 4-5 with acetic acid. After adding silane coupling agent KH-570 dropwise, the temperature is raised to reflux and stirred for 10-15 hours, centrifuged, washed with water, and dried. Then, the glass fiber is added to ethanol, and glycidyl methacrylate and a free radical initiator are added. The reaction is heated to reflux for 1-10 hours, then returned to room temperature, filtered, and dried.

[0016] Furthermore, the free radical initiator is any one or more combinations of azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, and lauroyl peroxide.

[0017] The present invention also provides a method for preparing a PPE / PSU composite material:

[0018] The raw materials are weighed according to the weight ratio and mixed evenly, and then melt-blended and extruded through a twin-screw extruder, cooled, pelletized, and dried. The temperature of the twin-screw extruder is set at 285-315° C. and the screw speed is 80-120 r / min.

[0019] Beneficial effects of the present invention:

[0020] The present invention provides a PPE / PSU composite material. The thermosetting polyphenylene ether resin has a low molecular weight, low viscosity after melting, good compatibility with other components, and is not prone to phase separation. At the same time, its end groups or side chains contain unsaturated double bonds that can undergo cross-linking and curing, which can form an interpenetrating polymer network structure, reduce the defects and internal stress of the composite material, and improve the mechanical properties. The aromatic group in the main chain of bisphenol A type polysulfone has high rigidity, but the presence of ether group as a flexible component makes it both rigid and flexible. After addition, the impact resistance of the polyphenylene ether material can be improved. The structure of bisphenol A type polysulfone-nylon block copolymer contains the same rigid groups and polymer long chain groups as bisphenol A type polysulfone. Through hydrogenation, the aromatic group in the main chain of bisphenol A type polysulfone has high rigidity, but the presence of ether group as a flexible component makes it both rigid and flexible. After addition, the impact resistance of the polyphenylene ether material can be improved. The addition of the silane coupling agent and the GMA copolymer coating layer on the surface of the treated glass fiber can further improve the dispersion of the glass fiber in the resin matrix, and the residual GMA and free radical initiator in the coating layer can further cross-link with the double bonds in the thermosetting polyphenylene ether, thereby better dispersing and fixing the glass fiber and preventing its agglomeration. According to tests, the composite material prepared by the present invention has excellent mechanical properties and good solvent resistance in alcohol solvents. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is an SEM photograph of the impact cross section of the composite material prepared in Example 1. No obvious phase separation is observed, the glass fibers are evenly distributed in the composite material, and there is resin adhesion on the surface, indicating that the glass fibers have good compatibility with the resin matrix. DETAILED DESCRIPTION

[0022] Unless otherwise specified, the following examples and comparative examples were conducted in parallel, using the same processing steps and parameters.

[0023] Thermosetting polyphenylene ether resin: polyphenylene methacrylate, SA9000, SABIC Innovative Plastics;

[0024] Thermoplastic polyphenylene ether resin: LXR045, Ruicheng Bluestar Chemical New Materials Co., Ltd.

[0025] Bisphenol A polysulfone: Dongguan Prius Plastic Raw Materials Co., Ltd.

[0026] Bisphenol A type polysulfone-nylon block copolymer: homemade;

[0027] Glass fiber: length 100-500 μm, homemade;

[0028] Antioxidant GA-80: Hubei Qiniu Chemical Technology Co., Ltd.

[0029] Example 1:

[0030] A PPE / PSU composite material, comprising the following components in parts by weight:

[0031] 20 parts of thermosetting polyphenylene ether resin, 30 parts of thermoplastic polyphenylene ether resin, 20 parts of bisphenol A polysulfone, 10 parts of bisphenol A polysulfone-nylon block copolymer, 15 parts of glass fiber, and 1 part of antioxidant GA-80.

[0032] The preparation method of bisphenol A type polysulfone-nylon block copolymer is as follows:

[0033] Mix 300g of caprolactam and 30g of bisphenol A polysulfone, evacuate the mixture and raise the temperature to 180°C to dissolve the bisphenol A polysulfone in the caprolactam. Then add 0.5g of sodium hydroxide as a catalyst, maintain the vacuum state, stir and react for 10 hours, then return to room temperature and normal pressure. Grind the product into 80 mesh and dry it in an oven at 80°C for 10 hours.

[0034] The preparation method of glass fiber is as follows:

[0035] 10g of glass fiber was placed in an ultrasonic cleaning machine containing acetone for 30min to remove surface dirt, placed in an 80℃ oven for 10h, and then placed in a low-temperature plasma treatment device for plasma activation in room temperature air at a power frequency of 11kHz, an applied voltage peak of 20kV, a discharge power of 70W, and a treatment time of 300s at an action distance of 3mm. The glass fiber after plasma activation was added to 500ml of ethanol aqueous solution (V 乙醇 :V 水 =7:3), the pH of the system was adjusted to 4 with acetic acid, and then silane coupling agent KH-570 was added dropwise. After the addition, the temperature was raised to reflux and stirred for reaction for 15 hours, and then returned to room temperature and centrifuged. The glass fiber was washed with water and dried, and then added to 500 ml of ethanol, and 5 g of glycidyl methacrylate and 0.05 g of AIBN were added. The mixture was heated to reflux and reacted for 5 hours, then returned to room temperature, filtered, and dried.

[0036] The preparation method of the above-mentioned PPE / PSU composite material is as follows:

[0037] The raw materials were weighed and mixed evenly according to the weight ratio, and then melt-blended and extruded through a twin-screw extruder, cooled, cut into pellets, and placed in an oven to dry at 80°C for 24 hours. The temperature of the twin-screw extruder was set at 285-315°C and the screw speed was 120r / min.

[0038] Example 2:

[0039] A PPE / PSU composite material, comprising the following components in parts by weight:

[0040] 30 parts of thermosetting polyphenylene ether resin, 30 parts of thermoplastic polyphenylene ether resin, 20 parts of bisphenol A polysulfone, 10 parts of bisphenol A polysulfone-nylon block copolymer, 20 parts of glass fiber, and 1.5 parts of antioxidant GA-80.

[0041] The preparation method of bisphenol A type polysulfone-nylon block copolymer and glass fiber is the same as that in Example 1.

[0042] The preparation method of the above-mentioned PPE / PSU composite material is as follows:

[0043] The raw materials were weighed according to the weight ratio and mixed evenly, then melt-blended and extruded through a twin-screw extruder, cooled, and dried in an oven at 80°C for 24 hours. The temperature of the twin-screw extruder was set at 285-315°C and the screw speed was 120 r / min.

[0044] Example 3:

[0045] A PPE / PSU composite material, comprising the following components in parts by weight:

[0046] 30 parts of thermosetting polyphenylene ether resin, 20 parts of thermoplastic polyphenylene ether resin, 15 parts of bisphenol A polysulfone, 5 parts of bisphenol A polysulfone-nylon block copolymer, 10 parts of glass fiber, and 1 part of antioxidant GA-80.

[0047] The preparation method of bisphenol A type polysulfone-nylon block copolymer and glass fiber is the same as that in Example 1.

[0048] The preparation method of the above-mentioned PPE / PSU composite material is as follows:

[0049] The raw materials were weighed and mixed evenly according to the weight ratio, and then melt-blended and extruded through a twin-screw extruder, cooled, cut into pellets, and placed in an oven to dry at 80°C for 24 hours. The temperature of the twin-screw extruder was set at 285-315°C and the screw speed was 120r / min.

[0050] Comparative Example 1:

[0051] The method is basically the same as Example 1, except that the thermosetting polyphenylene ether resin is replaced by the thermoplastic polyphenylene ether resin of the same weight.

[0052] Comparative Example 2:

[0053] The process is basically the same as Example 1, except that bisphenol A polysulfone is not added.

[0054] Comparative Example 3:

[0055] The process is basically the same as Example 1, except that the bisphenol A type polysulfone-nylon block copolymer is not added.

[0056] Comparative Example 4:

[0057] The method is basically the same as Example 1, except that the glass fiber is added directly without being treated.

[0058] Performance testing:

[0059] The composite materials prepared in Examples 1-3 and Comparative Examples 1-4 were injection molded into standard test specimens on an injection molding machine and subjected to performance tests;

[0060] Tensile properties are tested according to GB / T 1040-2006;

[0061] Bending properties are tested according to GB / T 9341-2000;

[0062] Izod impact strength is tested in accordance with GB / T 1843-2008;

[0063] The standard sample was placed in anhydrous ethanol and heated to reflux. After holding for 24 hours, it was taken out and dried in an oven at 80°C for 10 hours. The above mechanical properties test was then performed again. The change rate of tensile properties, flexural properties and impact strength was calculated. (Note: "+" indicates an increase, "-" indicates a decrease)

[0064] The test results are shown in Table 1;

[0065] Table 1:

[0066]

[0067] As can be seen from Table 1, the composite material prepared by the present invention has excellent mechanical properties and good solvent resistance in alcohol solvents.

[0068] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A PPE / PSU composite material, characterized in that: In parts by weight, it comprises the following components: 40-60 parts of polyphenylene ether, 15-30 parts of bisphenol A polysulfone, 5-10 parts of bisphenol A polysulfone-nylon block copolymer, 10-20 parts of glass fiber, 0.5-1.5 parts of antioxidant GA-80; The polyphenylene ether includes thermosetting polyphenylene ether resin SA9000 and thermoplastic polyphenylene ether resin LXR045; The weight ratio of the thermosetting polyphenylene ether resin SA9000 to the thermoplastic polyphenylene ether resin LXR045 is 1-5:1-5; The preparation method of the bisphenol A type polysulfone-nylon block copolymer is as follows: Mix caprolactam and bisphenol A polysulfone, evacuate the mixture and raise the temperature to 180-200°C to dissolve the bisphenol A polysulfone in the caprolactam. Then add the catalyst, maintain the vacuum state, stir and react for 5-15 hours, then return to room temperature. Grind the obtained product and dry it. The weight ratio of caprolactam to bisphenol A polysulfone is 30:1-5; The glass fiber is treated with plasma activation, silane coupling agent KH-570 and glycidyl methacrylate; The preparation method of the glass fiber is as follows: After plasma activation, add the glass fiber to an ethanol-water solution, adjust the pH of the system to 4-5 with acetic acid, add silane coupling agent KH-570 dropwise, heat to reflux and stir for 10-15 hours, centrifuge, wash with water and dry, then add to ethanol, add glycidyl methacrylate and free radical initiator, heat to reflux and react for 1-10 hours, then return to room temperature, filter and dry; The catalyst is sodium hydroxide and / or potassium hydroxide; The free radical initiator is any one or more combinations of azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, and lauroyl peroxide; Preparation method of the above-mentioned PPE / PSU composite material: The raw materials are weighed according to the weight ratio and mixed evenly, and then melt-blended and extruded through a twin-screw extruder, cooled, pelletized, and dried. The temperature of the twin-screw extruder is set at 285-315° C. and the screw speed is 80-120 r / min.

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