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CN-122011765-A - High-temperature-resistant reinforced polyphenylene sulfide composite material and preparation process thereof

CN122011765ACN 122011765 ACN122011765 ACN 122011765ACN-122011765-A

Abstract

The invention belongs to the technical field of polymer composite materials, and discloses a high-temperature-resistant reinforced polyphenylene sulfide composite material and a preparation process thereof. The composite material comprises, by mass, 65% -85% of polyphenylene sulfide resin, 10% -25% of functionalized graphene aerogel, 2% -8% of a nucleation auxiliary agent and 1% -3% of a heat stabilizer, wherein a three-dimensional limited-domain nano reaction environment is constructed by the functionalized graphene aerogel, and a penetrating type sh-kebab crystal structure is formed in situ by combining ultrasonic or magnetic field external field induction. According to the high-temperature-resistant reinforced polyphenylene sulfide composite material and the preparation process thereof, three technical elements of nano-confinement, surface functionalization and external field induction are innovatively fused, so that a novel high-performance composite material system with excellent comprehensive performance is successfully constructed, the heat resistance, mechanical strength and thermal cycle dimensional stability of the material are remarkably improved, and the high-temperature-resistant reinforced polyphenylene sulfide composite material is suitable for high-end electronic and aviation components.

Inventors

  • LIU ZIZHAO
  • CAO LEI
  • JIA CHANGFEI
  • Wen Xiaojia
  • CHEN FENG

Assignees

  • 河南省第五地质勘查院有限公司

Dates

Publication Date
20260512
Application Date
20260305

Claims (10)

  1. 1. The high temperature resistant reinforced polyphenylene sulfide composite material is characterized by comprising the following components in percentage by mass: 65% -85% of polyphenylene sulfide resin; 10% -25% of functionalized graphene aerogel; 2% -8% of nucleation auxiliary agent; 1% -3% of a heat stabilizer; The composite material is internally and in situ constructed with a through type shish-kebab crystal structure, the structure is composed of a straight chain crystal shish phase which extends continuously along the axial direction of a functional graphene aerogel pore canal and a folded chain crystal kebab phase which grows on the surface of the straight chain crystal shish phase vertically, and the shish phases are mutually connected through an aerogel framework to form three-dimensional network distribution.
  2. 2. The high temperature resistant reinforced polyphenylene sulfide composite material according to claim 1, wherein the functionalized graphene aerogel is a three-dimensional porous network structure body subjected to sulfonation treatment, the pore size distribution is concentrated in a 10-100nm range, the porosity is greater than 95%, sulfonic acid groups are grafted on the surface, and the grafting density is 0.8-1.2 sulfonic acid groups per square nanometer.
  3. 3. The high temperature resistant reinforced polyphenylene sulfide composite material according to claim 1, wherein the nucleation auxiliary agent is a composite formed by talcum powder and sodium terephthalate according to a mass ratio of 3:1.
  4. 4. The high temperature resistant reinforced polyphenylene sulfide composite material according to claim 1, wherein the heat stabilizer is formed by compounding hindered phenols and phosphites according to a mass ratio of 1:1, and the melting point range is 120-150 ℃.
  5. 5. The high temperature resistant reinforced polyphenylene sulfide composite material according to claim 1, wherein the length of a shish phase in the functionalized graphene aerogel is greater than 50 μm, the diameter is 20-50nm, the platelet thickness of the kebab phase is 10-30nm, and the interlayer spacing is 0.54nm.
  6. 6. The high temperature resistant reinforced polyphenylene sulfide composite material according to claim 1, wherein the intrinsic viscosity of the polyphenylene sulfide resin is 0.45-0.65dL/g, the melting point is 280-290 ℃, and the moisture content is lower than 0.05%.
  7. 7. The high temperature resistant reinforced polyphenylene sulfide composite material according to claim 1, wherein weak coordination is formed between a sulfonic acid group on the skeleton surface of the functionalized graphene aerogel and a sulfur atom on a main chain of the polyphenylene sulfide, and coordination bond energy is 15-25kJ/mol.
  8. 8. The high temperature resistant reinforced polyphenylene sulfide composite material according to claim 1, wherein ferroferric oxide nanoparticles are doped in the functionalized graphene aerogel, the doping amount is 3% of the mass of the ferroferric oxide nanoparticles, and the ferroferric oxide nanoparticles are subjected to oleic acid surface modification.
  9. 9. A process for preparing a high temperature resistant reinforced polyphenylene sulfide composite material according to any one of claims 1 to 8, comprising the steps of: s1, preparing a functionalized graphene aerogel, namely reacting graphene oxide aqueous dispersion liquid with the concentration of 2mg/mL with sulfanilic acid, and performing thermal reduction in a nitrogen atmosphere after freeze drying; s2, premixing, namely uniformly mixing polyphenylene sulfide resin, functionalized graphene aerogel, a nucleation auxiliary agent and a heat stabilizer at a high speed; S3, melt blending and external field induced crystallization, namely adding the premix into a double-screw extruder, performing melt extrusion at the conditions of 260 ℃ in a feeding section, 280 ℃ in a compression section, 290 ℃ in a metering section and 285 ℃ in a die head, and applying an external field at the tail end of the metering section to induce the formation of a shish-kebab crystal structure in situ; s4, granulating and forming, namely performing water-cooled granulation on the extruded material, and then performing injection molding or mould pressing to obtain the product.
  10. 10. The process according to claim 9, wherein the external field in step S3 is an ultrasonic field with a frequency of 40kHz, a power density of 3-7W/cm 2 , and a duration of action of more than 30 seconds.

Description

High-temperature-resistant reinforced polyphenylene sulfide composite material and preparation process thereof Technical Field The invention belongs to the technical field of polymer composite materials, and relates to a high-temperature-resistant reinforced polyphenylene sulfide composite material and a preparation process thereof. Background Polyphenylene sulfide, which is used as a high-performance thermoplastic engineering plastic, has been widely applied to high-end fields of electronics and electrics, automobile manufacturing, aerospace and the like with strict requirements on the service stability of materials because of excellent chemical corrosion resistance, flame retardance and good electrical insulation property. Polyphenylene sulfide is considered as an ideal candidate material for replacing conventional metals or common engineering plastics, particularly in structural components that operate for a long period of time in a high temperature environment, due to its relatively high glass transition temperature (Tg: 90 ℃) and melting point (Tm: 285 ℃). In the prior art, conventional strategies for improving the heat resistance of polyphenylene sulfide mainly depend on improving the crystallinity of the polyphenylene sulfide. In theory, the higher crystallinity can effectively enhance the packing density among molecular chains, thereby inhibiting the thermal motion of chain segments at high temperature and delaying the softening and creep behaviors of the material. Means such as nucleating agent addition, heat treatment annealing or cooling rate control are commonly adopted in the industry to promote crystallization perfection. Such methods do significantly improve the heat distortion temperature and short term thermal stability of polyphenylene sulfide articles at specific historical stages. However, although the temperature resistance upper limit of the polyphenylene sulfide can be enhanced by improving the crystallinity of the polyphenylene sulfide, the volume shrinkage and internal stress accumulation of the material in the forming process are inevitably aggravated, and the product is obviously warped, cracked and even failed after being in high-temperature service or undergoing thermal cycle. The traditional crystallization regulation and control mode often induces a large number of isolated, disordered and unevenly distributed spherulitic structures, the crystals have remarkable anisotropic expansion effect when heated, and are difficult to realize the dimensional cooperative stability on a macroscopic scale, and the spherulitic interfaces are easy to become weak areas of stress concentration and microcrack initiation under the high-temperature load coupling effect, so that the integral structural integrity of the material is weakened. Disclosure of Invention In order to achieve the aim of the invention, the invention provides a high temperature resistant reinforced polyphenylene sulfide composite material and a preparation process thereof. The composite material guides the polyphenylene sulfide molecular chain to realize directional extension and ordered crystallization in a limited space by constructing a nano reaction environment with a three-dimensional finite field effect and combining with controllable external field intervention, so that a penetrating type shish-kebab crystal structure is constructed in situ to synchronously realize the collaborative optimization of high temperature resistance, high dimensional stability and excellent mechanical property. The high temperature resistant reinforced polyphenylene sulfide composite material comprises, by mass, 65% -85% of polyphenylene sulfide resin, 10% -25% of functionalized graphene aerogel, 2% -8% of nucleation auxiliary agent and 1% -3% of heat stabilizer. The functionalized graphene aerogel is a three-dimensional porous network structure body subjected to sulfonation treatment, the specific surface area of the three-dimensional porous network structure body is larger than 500m 2/g, the pore size distribution is concentrated in a 10-100nm interval, the porosity is larger than 95%, sulfonic acid groups are grafted on the surface of the three-dimensional porous network structure body, and the grafting density is 0.8-1.2 sulfonic acid groups per square nanometer. The nucleation auxiliary agent is a compound of talcum powder and sodium terephthalate, the mass ratio of the talcum powder to the sodium terephthalate is 3:1, and the average grain diameter is 0.5-1.5 mu m. The heat stabilizer is a compound system of hindered phenols and phosphites, the mass ratio is 1:1, and the melting point range is 120-150 ℃. The functionalized graphene aerogel is used as a nano reactor, and a continuous and through three-dimensional finite field space is formed inside the composite material. The geometric dimension of the finite space is matched with the radius of gyration of the polyphenylene sulfide molecular chain, so that the molecular chain is constrai