Hydrophobic glass fiber reinforced polyphenylene sulfide composite material

Abstract

The invention discloses a hydrophobic glass fiber reinforced polyphenylene sulfide composite material, which has good mechanical property and long-term hydrophobic property, and can be applied to the fields with hydrophobic, anti-corrosion and anti-fouling requirements. The material comprises the following components in parts by mass: 30-75 parts of polyphenylene sulfide, 20-60 parts of glass fiber, 0.2-2 parts of a coupling agent, 2-8 parts of modified montmorillonite, 0.2-2 parts of reactive silicone oil and 0.5-2 parts of a lubricant, and the glass fiber reinforced polyphenylene sulfide composite material with hydrophobic performance is obtained by melt blending, extrusion and granulation and then electron beam irradiation.

Description

Technical Field

[0001] The invention relates to the field of polymer modification, and in particular to a hydrophobic glass fiber reinforced polyphenylene sulfide composite material. Background Art

[0002] Polyphenylene sulfide has excellent dielectric properties, flame retardancy, high heat resistance, high dimensional stability, and chemical resistance. It is widely used in the fields of electronics, automobiles, aerospace, etc. With the diversification and complexity of application fields, a single material function cannot meet the use requirements. Polyphenylene sulfide itself has medium strength and certain brittleness. Generally, the mechanical properties are improved by adding glass fiber, but the addition of glass fiber has a great impact on the corrosion resistance and hydrophobicity of the composite material.

[0003] Patent No. CN114456598B discloses a glass fiber reinforced polyphenylene sulfide composition and its preparation method, which has good mechanical properties and a small performance change rate under high and low temperature conditions. Patent No. CN112795190B discloses a high-toughness glass fiber reinforced polyphenylene sulfide composite material and its preparation method, using ultra-low molecular weight polyethylene as a dispersant, so that the dispersant, dispersant, phenolphthalein polyether ketone and glass fiber form independent ternary entities, which can improve the adhesion between the glass fiber and the substrate on the one hand, and on the other hand, the ternary entity forms a cavity under the action of external force, effectively absorbing the impact of external force, thereby achieving synergistic toughening and greatly improving the impact performance of glass fiber reinforced polyphenylene sulfide. However, the above patents do not consider the hydrophobicity of glass fiber reinforced polyphenylene sulfide composite materials. The patent number CN113817318B discloses a corrosion-resistant, high-temperature-resistant, super-hydrophobic polyphenylene sulfide composite material and its preparation method. After the inorganic particles are hydrophobically modified, the obtained polyphenylene sulfide composite material has high heat resistance, corrosion resistance and hydrophobicity. The patent number CN117050524A discloses a wear-resistant double-repellent polyphenylene sulfide composite material and its preparation method. By compounding fluorinated modified polyphenylene sulfide and hydrophobically modified nano-SiO2, as well as short-cut carbon fibers, and adding a certain amount of aminosilane coupling agent, the obtained polyphenylene sulfide composite material has both double repellent performance and wear resistance. The above patents study the hydrophobicity of polyphenylene sulfide, but do not involve the hydrophobic properties of glass fiber reinforced polyphenylene sulfide composite materials. Summary of the invention

[0004] In view of the above problems, the present invention proposes a hydrophobic glass fiber reinforced polyphenylene sulfide composite material, which is suitable for application scenarios with certain requirements for hydrophobicity, antifouling and anticorrosion. Polyphenylene sulfide, modified montmorillonite, reactive silicone oil, coupling agent and lubricant are mixed evenly and put into the main feed of a twin-screw extruder, short chopped glass fibers are added from the side feed, melt blended, extruded and granulated, and then electron beam irradiated to obtain a glass fiber reinforced polyphenylene sulfide composite material with long-term hydrophobic properties.

[0005] A hydrophobic glass fiber reinforced polyphenylene sulfide composite material, calculated by weight, the raw material composition includes: Polyphenylene sulfide: 30-75 Glass fiber: 20-60 Coupling agent: 0.2-2 Modified montmorillonite: 2-8 Reactive silicone oil: 0.2-4 Lubricant: 0.5-2.

[0006] The polyphenylene sulfide is a linear polyphenylene sulfide having a melt index of 200-800 g / 10min when tested at 316°C and 5kg.

[0007] The glass fiber is alkali-free chopped glass fiber with a length of 2-6 mm and a diameter of 7-13 μm.

[0008] The coupling agent is one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent, or a mixture of several of them.

[0009] The modified montmorillonite is sodium-montmorillonite modified by a silane coupling agent or sodium-montmorillonite modified by an organic quaternary ammonium salt.

[0010] The reactive silicone oil is one of epoxy silicone oil, carboxyl silicone oil and amino silicone oil, or a mixture of several of them.

[0011] The lubricant is one of silicone, tetrapentyl stearate and montan wax or a mixture of several of them.

[0012] The above materials except glass fiber are mixed evenly, and then fed into the main feed of a twin-screw extruder. The glass fiber is added into the side feed, melt blended and extruded. After cooling and pelletizing, polyphenylene sulfide composite material particles are obtained. The particles are then subjected to electron beam irradiation treatment to finally obtain a hydrophobic glass fiber reinforced polyphenylene sulfide composite material. The melt blending extrusion temperature is 280-310°C.

[0013] Preferably, the coupling agent is a silane coupling agent. Preferably, the modified montmorillonite is sodium-montmorillonite modified by a silane coupling agent.

[0014] Preferably, the reactive silicone oil is epoxy silicone oil.

[0015] Preferably, the lubricant is silicone; Preferably, the irradiation dose is 100-200 kGy.

[0016] Under the above preferred conditions, the hydrophobic glass fiber reinforced polyphenylene sulfide composite material preferably comprises, by weight, the raw material composition: Polyphenylene sulfide: 35-70 Glass fiber: 20-60 Silane coupling agent: 0.2-1 Silane coupling agent modified montmorillonite: 2-5 Epoxy silicone oil: 1-3 Silicone: 0.5-1.5 Compared with the prior art, the present invention has the following characteristics: In the present invention, modified montmorillonite and epoxy silicone oil cooperate with each other, and the unique nano-layered structure of modified montmorillonite is utilized. The modified montmorillonite has good hydrophobicity and lipophilicity and adsorption capacity, so that the epoxy silicone oil is better adsorbed on the layered structure of the modified montmorillonite to form a layered hydrophobic structure. Then, after the co-mixing and extrusion, the PPS and the epoxy silicone oil are subjected to irradiation grafting treatment to cause a grafting reaction, thereby achieving long-term hydrophobicity and anti-fouling and anti-corrosion capabilities. DETAILED DESCRIPTION

[0017] The present invention is further described below in conjunction with specific examples. These examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. All raw materials used in the following examples and comparative examples are commercially available unless otherwise specified.

[0018] The raw material information and auxiliary agent information used in the examples and comparative examples are as follows: PPS: 3450, Xinhecheng Glass fiber: ECS309A-3-H, CPIC Silane coupling agent: KH-560, commercially available Montmorillonite: Sodium Montmorillonite, Guangzhou Xijia Chemical Hexadecyltrimethylammonium bromide modified montmorillonite: Commercially available Epoxy silicone oil: Dow Carboxyl silicone oil: Dow Amino silicone oil: Dow Silicone: GM-100 Chengdu Chenguang Material characterization method: The tensile properties are in accordance with ISO 527, the sample size is 170mm×10mm×4mm, and the tensile speed is 10mm / min; the bending properties are in accordance with ISO 178, the sample size is 80mm×10mm×4mm, the bending speed is 2mm / min, and the span is 64mm; the hydrophobicity is tested in accordance with GB / T 24368; the double 85 experiment is to place the sample at 85℃, 85 RH% for 1000h before performing the contact angle test.

[0019] To prepare modified montmorillonite, weigh KH-560 and montmorillonite at a mass ratio of 7:10 respectively for use. First, add KH-560 to an ethanol solution prepared with acetic acid to a pH of 4, hydrolyze for 4 hours, and then add montmorillonite to the above mixture and reflux at 70°C for 24 hours. Then dilute the product with anhydrous ethanol, wash, and filter. Finally, vacuum dry the solid product at 90°C for 24 hours to obtain silane coupling agent grafted modified montmorillonite.

[0020] According to the formula in Table 1, weigh the corresponding materials, mix the raw materials except glass fiber evenly and put them into the main feed, put the glass fiber into the side feed, melt blend, extruder temperature: 260-320℃, then draw and cool and pelletize to obtain glass fiber reinforced PPS composite material particles. Then irradiate the obtained particles with a 5MeV electron accelerator, and the irradiation dose is shown in Table 1.

[0021] formula Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 3450 55 53 55 54 56 54 54 54 59 54 44 54 54 54 309A 40 40 40 40 40 40 40 40 40 40 40 40 40 40 KH-560 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Modified montmorillonite (KH-560 modified) 3 5 3 3 2 0 3 3 0 3 10 3 3 0 Modified montmorillonite (modified with hexadecyltrimethylammonium bromide) 0 0 0 0 0 3 0 0 0 0 0 0 0 0 Unmodified montmorillonite 0 0 0 0 0 0 0 0 0 0 0 0 0 3 Epoxy silicone oil 1 1 1 2 1 2 0 0 0 2 5 2 2 2 Carboxyl silicone oil 0 0 0 0 0 0 2 0 0 0 0 0 0 0 Amino silicone oil 0 0 0 0 0 0 0 2 0 0 0 0 0 0 Silicone 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Irradiation dose kGy 100 200 200 200 200 200 200 200 0 0 200 300 50 200 The performance test results of Examples 1-8 and Comparative Examples 1-6 are shown in Table 2.

[0022] Test items Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Tensile strength / MPa 192 198 187 183 181 176 179 178 173 176 179 169 188 176 Bending strength / MPa 259 267 251 255 249 243 246 250 243 247 269 243 261 247 Contact angle / ° 120.6 122.8 129.8 136.4 128.1 124 124 127 74.2 108.2 112.2 116.6 109.3 78.3 Double 85 rear contact angle / ° 115.6 118.4 127.9 134.6 127.1 117.8 121 124.2 73.6 96.3 110.5 113.7 100.4 80.1 From the test results of Examples 1-8 and Comparative Examples 1-6 in Table 2, it can be seen that with the addition of modified montmorillonite and epoxy silicone oil, after melt blending and then irradiation grafting, good mechanical properties are obtained, and the hydrophobicity of the glass fiber reinforced polyphenylene sulfide composite material can be effectively improved, and the hydrophobicity does not decrease after long-term use. Preferably, the content of modified montmorillonite is 2-5 parts, and the content of epoxy silicone oil is 1-3 parts. Too low a dose does not react well, and too high an irradiation dose will also damage the internal structure of the composite material. The preferred irradiation dose is 100-200 kGy.

[0023] The above description of the embodiments is to facilitate the understanding and application of the present invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the embodiments herein, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A hydrophobic glass fiber reinforced polyphenylene sulfide composite material, the raw material composition of which is calculated by weight: Polyphenylene sulfide: 30-75 Glass fiber: 20-60 Coupling agent: 0.2-2 Modified montmorillonite: 2-8 Reactive silicone oil: 0.2-4 Lubricant: 0.5-2.

2. The hydrophobic glass fiber reinforced polyphenylene sulfide composite material according to claim 1, characterized in that: The polyphenylene sulfide is a linear polyphenylene sulfide having a melt index of 200-800 g / 10min when tested at 316°C and 5kg.

3. The hydrophobic glass fiber reinforced polyphenylene sulfide composite material according to claim 1, characterized in that: The glass fiber is alkali-free chopped glass fiber with a length of 2-6 mm and a diameter of 7-13 μm.

4. The hydrophobic glass fiber reinforced polyphenylene sulfide composite material according to claim 1, characterized in that: The coupling agent is one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent, or a mixture of several of them.

5. The hydrophobic glass fiber reinforced polyphenylene sulfide composite material according to claim 1, characterized in that: The modified montmorillonite is sodium-montmorillonite modified by a silane coupling agent or sodium-montmorillonite modified by an organic quaternary ammonium salt.

6. The hydrophobic glass fiber reinforced polyphenylene sulfide composite material according to claim 1, characterized in that: The reactive silicone oil is one of epoxy silicone oil, carboxyl silicone oil and amino silicone oil, or a mixture of several of them.

7. The hydrophobic glass fiber reinforced polyphenylene sulfide composite material according to claim 1, characterized in that: The lubricant is one of silicone, tetrapentyl stearate and montan wax or a mixture of several of them.

8. A method for preparing a hydrophobic glass fiber reinforced polyphenylene sulfide composite material according to any one of claims 1 to 7, comprising: uniformly mixing the components except the glass fiber, feeding the components into the main feed of a twin-screw extruder, adding the glass fiber into the side feed, performing melt blending and extruding, cooling and pelletizing to obtain polyphenylene sulfide composite material particles, and then subjecting the particles to electron beam irradiation treatment to obtain a hydrophobic glass fiber reinforced polyphenylene sulfide composite material, wherein the melt blending and extrusion temperature is 280 to 310°C.

9. The method for preparing a hydrophobic glass fiber reinforced polyphenylene sulfide composite material according to claim 8, characterized in that: The irradiation dose is 100-200 kGy.