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CN-121975322-A - Carbon fiber reinforced polyphenylene sulfide composite material and preparation method thereof

CN121975322ACN 121975322 ACN121975322 ACN 121975322ACN-121975322-A

Abstract

The invention discloses a carbon fiber reinforced polyphenylene sulfide composite material which comprises, by weight, 58.1-78.1 parts of polyphenylene sulfide resin, 10-40 parts of surface modified carbon fibers, 0.1-0.5 part of internal lubrication flow improver, 0.2-0.5 part of compound antioxidant and 0.4-1.2 parts of compound lubricant. The carbon fiber reinforced polyphenylene sulfide composite material has the characteristics of high mechanical property, high strength, high heat resistance and permanent antistatic property. The preparation method comprises the steps of adopting a strong oxidizing agent to treat the surface of the carbon fiber, introducing polar groups such as hydroxyl, carboxyl, epoxy and the like to strengthen the surface activity, then utilizing hydrobromic acid and thiourea to carry out secondary modification to convert part of the polar groups into mercapto groups to prepare the surface modified carbon fiber with the surface rich in the mercapto groups, and finally uniformly dispersing the surface modified carbon fiber into a polyphenylene sulfide matrix by a melt blending method to prepare the carbon fiber reinforced polyphenylene sulfide composite material, wherein the heat resistance, the heat conductivity and the electric conductivity are synchronously optimized by improving the content of the surface modified carbon fiber.

Inventors

  • RAO DESHENG
  • CHEN YUNFENG
  • Chen Ruoken
  • TANG NING

Assignees

  • 广东奇德新材料股份有限公司

Dates

Publication Date
20260505
Application Date
20260317

Claims (10)

  1. 1. A carbon fiber reinforced polyphenylene sulfide composite material is characterized by comprising, by weight, 58.1-78.1 parts of polyphenylene sulfide resin, 10-40 parts of surface modified carbon fibers, 0.1-0.5 part of internal lubrication flow improver, 0.2-0.5 part of compound antioxidant and 0.4-1.2 parts of compound lubricant; The surface modified carbon fiber is prepared through oxidation treatment and sulfhydrylation treatment steps.
  2. 2. The carbon fiber reinforced polyphenylene sulfide composite material according to claim 1, wherein the surface-modified carbon fiber is prepared by: (a) Adding 80mL of concentrated sulfuric acid into a three-neck flask of an ice water bath, sequentially adding 5g of sodium nitrate and 50g of carbon fiber base material, stirring at a low speed for 10min, slowly dripping 8g of potassium permanganate into the three-neck flask within 1h, soaking in the ice water bath for 1h, removing the ice water bath, heating to 40 ℃ to continue to react for 1.5h to fully oxidize the surface of the carbon fiber, slowly dripping 500mL of deionized water to terminate the reaction, adding 16mL of 30wt% hydrogen peroxide solution and 12mL of hydrochloric acid under low-speed stirring to remove redundant potassium permanganate and manganese dioxide, and finally repeatedly washing, filtering and drying by a large amount of deionized water to obtain a modified carbon fiber intermediate product with the surface rich in carboxyl and hydroxyl groups; (b) The sulfhydrylation treatment step comprises the steps of sequentially adding 200mL of deionized water and 30mL of HBr (40%) into a 500mL three-neck flask with a condenser tube, stirring at room temperature for 5 minutes, adding a pretreated modified carbon fiber intermediate product, heating to 80 ℃, adding 15g of thiourea, reacting at constant temperature for 20 hours, adding 10g of sodium hydroxide for neutralization after the reaction is finished, and carrying out ultrasonic washing and filtering to obtain the surface modified carbon fiber with the surface rich in sulfhydryl groups.
  3. 3. The carbon fiber reinforced polyphenylene sulfide composite material according to claim 2, wherein the ultrasonic washing adopts 40kHz ultrasonic waves, the washing solvent is a mixed solution of deionized water and ethanol, and the washing times are 3-5 times.
  4. 4. The carbon fiber reinforced polyphenylene sulfide composite material according to claim 1, wherein the compound lubricant is two or more of polyethylene wax, montan wax, ester wax, and silicone.
  5. 5. The carbon fiber reinforced polyphenylene sulfide composite material according to claim 4, wherein the compound lubricant is prepared by compounding polyethylene wax and silicone powder according to a mass ratio of 1:1.
  6. 6. The carbon fiber reinforced polyphenylene sulfide composite material according to claim 1, wherein the compound antioxidant is two or more of GA-80, revonox 608,608 and S-9228.
  7. 7. The carbon fiber reinforced polyphenylene sulfide composite material according to claim 6, wherein the compound antioxidant is prepared by compounding GA-80 and S-9228 according to a mass ratio of 1:1.
  8. 8. The carbon fiber reinforced polyphenylene sulfide composite material according to claim 2, wherein the carbon fiber substrate is T400, T700 or T800 chopped fiber.
  9. 9. A method for preparing the carbon fiber reinforced polyphenylene sulfide composite material according to any one of claims 1 to 8, comprising the steps of: 1) After the polyphenylene sulfide resin is dried for 4 hours at 120 ℃, the polyphenylene sulfide resin, a compound antioxidant, a compound lubricant and an internal lubrication flow improver are mixed in a high-speed mixer at room temperature, the rotating speed is 400-600 rpm, and the mixture is stirred for 5-10 minutes, so that all components are uniformly dispersed, and a premix is obtained; 2) Adding the surface modified carbon fiber into a double-screw extruder through a side feeding device, adding premix into a main feeding port, controlling extrusion conditions to be that the length-diameter ratio is 48:1, the melting temperature is 280-310 ℃, the rotating speed of the main screw is 300-500 rpm, and the rotating speed of the side feeding screw is 20-100 rpm, so as to obtain an extruded material; 3) And (3) sequentially cooling, air-drying, granulating and sieving the extruded material to obtain the finished product of the carbon fiber reinforced polyphenylene sulfide composite material.
  10. 10. The carbon fiber reinforced polyphenylene sulfide composite material according to claim 9, wherein the cooling is water-cooled or air-cooled, the cooling water temperature is 20-30 ℃, the cooling time is 1-3 minutes, the surface moisture is removed by air blowing in the air drying, the air speed is 2-5m/s, the granulating is achieved by a rotary granulating cutter, the granulating length is 2-4mm, and the sieving is achieved by a 20-40 mesh screen to remove overlong or overlong particles.

Description

Carbon fiber reinforced polyphenylene sulfide composite material and preparation method thereof Technical Field The invention relates to the technical field of polyphenylene sulfide composite materials, in particular to a carbon fiber reinforced polyphenylene sulfide composite material and a preparation method thereof. Background Carbon Fiber (CF) is a high performance Fiber material with Carbon content over 95%, and has the dual advantages of high strength and high modulus. The microstructure is formed by arranging flaky graphite microcrystals along the axial direction of the fiber, and the graphite material with a regular microcrystal structure is finally formed through carbonization and graphitization process treatment of an organic fiber precursor. The material perfectly combines the unique properties of 'outer softness and inner rigidity', namely, the density is only about half of that of aluminum, but the strength is far superior to that of steel, the intrinsic characteristics of the carbon material, such as high temperature resistance, corrosion resistance, high modulus and the like, are reserved, and the material has soft processability of textile fibers, and is known as a new generation of high-performance reinforcing fibers. Polyphenylene Sulfide (PPS) is one of the sixth engineering plastics and the eighth aerospace materials in the world, and by virtue of the high crystallinity, corrosion resistance, intrinsic flame retardance (UL-94-V0 level) and high cost performance which are given by the rigid structure of the benzene ring and the flexible structure of the thioether bond, the polyphenylene sulfide (PPS) shows the potential of strongly replacing metals and other engineering plastics in the fields of mechanical industry, new energy (automobile lightening, battery components), 5G communication (low dielectric/heat conducting materials) and the like, and particularly the development of new energy automobiles provides a wide space for the application thereof, however, in order to meet the higher strength requirement (replacing metal structural members), the low-density high-strength composite material needs to be prepared by enhancing by Carbon Fibers (CF), but the interfacial performance is a key bottleneck, namely, the conventional sizing agent such as the prior epoxy and polyurethane is difficult to decompose due to poor heat resistance (PPS processing temperature is required to exceed 300 ℃), and the effective interfacial bonding between CF and PPS cannot be promoted at high temperature, so that the interfacial bonding force is weak, CF is not dispersed uniformly, and the mechanical property of the composite material is insufficient. Therefore, the key technical problem to be solved is how to construct strong interface interaction by carrying out chemical modification on the CF surface under the PPS high-temperature processing condition so as to improve the interface binding force and the comprehensive mechanical property of the CF/PPS composite material. Disclosure of Invention The invention aims to provide a carbon fiber reinforced polyphenylene sulfide composite material and a preparation method thereof, and aims to solve the problems in the background technology. In order to achieve the above purpose, the present invention provides the following technical solutions: A carbon fiber reinforced polyphenylene sulfide composite material comprises, by weight, 58.1-78.1 parts of polyphenylene sulfide resin, 10-40 parts of surface modified carbon fiber, 0.1-0.5 part of internal lubrication flow improver, 0.2-0.5 part of compound antioxidant and 0.4-1.2 parts of compound lubricant; The surface modified carbon fiber is prepared through oxidation treatment and sulfhydrylation treatment steps. Further, the surface-modified carbon fiber is prepared by the steps of: (a) Adding 80mL of concentrated sulfuric acid into a three-neck flask of an ice water bath, sequentially adding 5g of sodium nitrate and 50g of carbon fiber base material, stirring at a low speed for 10min, slowly dripping 8g of potassium permanganate into the three-neck flask within 1h, soaking in the ice water bath for 1h, removing the ice water bath, heating to 40 ℃ to continue to react for 1.5h to fully oxidize the surface of the carbon fiber, slowly dripping 500mL of deionized water to terminate the reaction, adding 16mL of 30wt% hydrogen peroxide solution and 12mL of hydrochloric acid under low-speed stirring to remove redundant potassium permanganate and manganese dioxide, and finally repeatedly washing, filtering and drying by a large amount of deionized water to obtain a modified carbon fiber intermediate product with the surface rich in carboxyl and hydroxyl groups; (b) The sulfhydrylation treatment step comprises the steps of sequentially adding 200mL of deionized water and 30mL of HBr (40%) into a 500mL three-neck flask with a condenser tube, stirring at room temperature for 5 minutes, adding a pretreated modified carbon fiber i