Search

CN-122011774-A - High-temperature-resistant resin, composite material, preparation method and application thereof

CN122011774ACN 122011774 ACN122011774 ACN 122011774ACN-122011774-A

Abstract

The invention provides a high-temperature-resistant resin, a composite material, a preparation method and application thereof, and relates to the technical field of high polymer materials. The high-temperature resistant resin organically combines organic silicon resin with good flexibility and heat resistance with phenolic resin with high carbon residue rate and ceramic precursor with high-temperature ceramic capability through molecular design, realizes molecular hybrid crosslinking, forms a unique three-dimensional network structure, realizes a synergistic high-temperature resistant effect, and improves comprehensive performance by adding nano reinforcing filler, composite curing agent, interface modifier and the like, the obtained high-temperature resistant resin has excellent high-temperature resistant performance, can resist high temperature of more than 400 ℃ for a long time, can resist high temperature of 600 ℃ for a short time, has excellent mechanical property, overcomes the defect of high brittleness of the traditional high-temperature resistant resin, and has good molding process performance. The invention also provides a preparation method of the high-temperature-resistant resin and a composite material prepared from the high-temperature-resistant resin.

Inventors

  • LEI YU
  • He Jinbi
  • LIU XIANHAO
  • JIANG BING

Assignees

  • 海鹰空天材料研究院(苏州)有限责任公司

Dates

Publication Date
20260512
Application Date
20251231

Claims (10)

  1. 1. The high-temperature resistant resin is characterized by comprising the following raw materials in parts by weight: 40-60 parts of organic silicon resin, 20-40 parts of phenolic resin, 10-30 parts of ceramic precursor, 5-25 parts of nano reinforcing filler, 3-15 parts of composite curing agent and 1-8 parts of interface modifier; wherein the total weight parts of the organic silicon resin, the phenolic resin and the ceramic precursor are 100 parts.
  2. 2. The high temperature resistant resin according to claim 1, wherein the silicone resin comprises a phenyl and/or vinyl-containing silicone resin; and/or the phenolic resin comprises an allylated phenolic resin and/or a boron modified phenolic resin; And/or, the ceramic precursor comprises polycarbosilane and/or polysilazane.
  3. 3. The high temperature resistant resin according to claim 1, wherein the nano reinforcing filler comprises at least two of carbon nanotubes, graphene, nano alumina, hollow glass microspheres, boron nitride, nano zirconia or calcined kaolin, preferably comprises carbon nanotubes, graphene and nano alumina; And/or the composite curing agent comprises a platinum catalyst, an amine curing agent and a free radical initiator, wherein the amine curing agent preferably comprises at least one of 4,4' -diaminodiphenyl sulfone, dicyandiamide, m-phenylenediamine or diaminodiphenyl methane, and the free radical initiator preferably comprises at least one of dicumyl peroxide, 1-bis (tert-butylperoxy) -3, 5-trimethylcyclohexane, tert-butyl peroxybenzoate or 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane; And/or the interface modifier comprises a silane coupling agent and/or a titanate coupling agent.
  4. 4. A high temperature resistant resin according to any one of claims 1-3, characterized in that the thermal decomposition temperature Td 5 % >450 ℃, 800 ℃ carbon residue >70% under nitrogen atmosphere; And/or, the bending strength of the high-temperature resistant resin is more than or equal to 420MPa, and the elongation at break is more than or equal to 2.8%.
  5. 5. The method for producing a high temperature resistant resin according to any one of claims 1 to 4, comprising the steps of: (a) Dissolving the organic silicon resin in a solvent, adding the nano reinforcing filler, and uniformly mixing to obtain modified organic silicon resin; (b) Heating phenolic resin to a molten state, adding a ceramic precursor, and reacting in an inert atmosphere to form a phenolic-ceramic prepolymer; (c) Mixing the modified organic silicon resin, the phenolic-ceramic prepolymer and the interface modifier, and reacting to obtain an intermediate product; (d) And removing the solvent in the intermediate product, adding a composite curing agent, and uniformly mixing to obtain the high-temperature-resistant resin.
  6. 6. The method of producing a high temperature resistant resin according to claim 5, wherein in step (a), the solvent comprises at least one of xylene, toluene or tetrahydrofuran; And/or, in the step (b), the phenolic resin reacts with the ceramic precursor at a temperature of 120-150 ℃ for 0.5-2 hours; And/or in step (C), the reaction temperature is 120-140 ℃ and the reaction time is 2-4 hours.
  7. 7. A composite material prepared by using the high temperature resistant resin and reinforcing material according to any one of claims 1 to 4; Preferably, the reinforcing material comprises fibres; preferably, the interlaminar shear strength of the composite material is more than or equal to 35MPa.
  8. 8. A method of preparing a composite material according to claim 7, comprising the steps of: After the reinforced material is impregnated with the high-temperature resistant resin, curing treatment and post-curing treatment are carried out to obtain a composite material; wherein the curing treatment comprises a medium temperature curing stage and a high temperature curing stage.
  9. 9. The method of producing a composite material according to claim 8, wherein the curing temperature in the medium temperature curing stage is 120 to 150 ℃ and the curing time is 2 to 4 hours; and/or the curing temperature in the high-temperature curing stage is 200-250 ℃ and the curing time is 2-3 hours; and/or the temperature of the post-curing treatment is 300-350 ℃ and the time is 1-2 hours.
  10. 10. Use of the high temperature resistant resin of any one of claims 1-4 or the composite material of claim 7 in the aerospace, new energy or electronics industries.

Description

High-temperature-resistant resin, composite material, preparation method and application thereof Technical Field The invention belongs to the technical field of high polymer materials, and particularly relates to a high-temperature-resistant resin, a composite material, a preparation method and application thereof. Background The high-temperature resistant resin has wide application requirements in the fields of aerospace, new energy, electronic industry and the like. The traditional high-temperature resistant resin such as epoxy resin, phenolic resin, organic silicon resin and the like has the advantages and disadvantages that the epoxy resin has good mechanical property but limited temperature resistance (generally below 300 ℃), the phenolic resin has good heat resistance but large brittleness, and the organic silicon resin has excellent temperature resistance but insufficient mechanical strength. In recent years, resin modification studies have been advanced. The organic silicon modified epoxy resin realizes molecular level synergy through chemical grafting or physical blending, the toughness can be improved by more than 40%, and the thermal decomposition temperature breaks through 300 ℃. The Hyperbranched Polysiloxane (HPS) modified epoxy resin system has both good heat resistance (glass transition temperature >190 ℃) and toughness (elongation at break > 3%). The residual carbon rate of the boron modified phenolic resin reaches 70 percent at 900 ℃, and the decomposition peak temperature reaches 625 percent. However, it is still difficult for the existing modified resins to meet the requirement of long-term use at 400 ℃ or more. Although the organic silicon resin has excellent thermal stability, the mechanical strength is insufficient, the residual carbon rate of the phenolic resin is high, but the toughness is poor, and the ceramic precursor resin has excellent temperature resistance but difficult processing. It is difficult for a single resin system to meet the requirements of high temperature performance, mechanical strength and manufacturability simultaneously. In view of this, the present invention has been made. Disclosure of Invention The present invention aims to provide a high temperature resistant resin, a composite material, a preparation method and application thereof, so as to improve the above problems existing in the prior art. In order to achieve the above purpose, the following technical scheme is adopted: the invention provides a high-temperature resistant resin, which comprises the following raw materials in parts by weight: 40-60 parts of organic silicon resin, 20-40 parts of phenolic resin, 10-30 parts of ceramic precursor, 5-25 parts of nano reinforcing filler, 3-15 parts of composite curing agent and 1-8 parts of interface modifier, The total weight of the organic silicon resin, the phenolic resin and the ceramic precursor is 100 parts. Further, on the basis of the technical scheme of the invention, the organic silicon resin comprises organic silicon resin containing phenyl and/or vinyl; and/or the phenolic resin comprises an allylated phenolic resin and/or a boron modified phenolic resin; And/or, the ceramic precursor comprises polycarbosilane and/or polysilazane; And/or the nano reinforcing filler comprises at least two of carbon nanotubes, graphene, nano alumina, hollow glass beads, boron nitride, nano zirconia or calcined kaolin, preferably comprises carbon nanotubes, graphene and nano alumina; and/or the composite curing agent comprises a platinum catalyst, an amine curing agent and a free radical initiator; And/or the interface modifier comprises a silane coupling agent and/or a titanate coupling agent. Further, on the basis of the technical scheme, the thermal decomposition temperature Td 5 percent of the high-temperature resin is more than 450 ℃, and the carbon residue rate at 800 ℃ is more than 70% under the nitrogen atmosphere; And/or, the bending strength of the high-temperature resistant resin is more than or equal to 420MPa, and the elongation at break is more than or equal to 2.8%. The second object of the present invention is to provide a method for preparing the above high temperature resistant resin, comprising the steps of: (a) Dissolving the organic silicon resin in a solvent, adding the nano reinforcing filler, and uniformly mixing to obtain modified organic silicon resin; (b) Heating phenolic resin to a molten state, adding a ceramic precursor, and reacting in an inert atmosphere to form a phenolic-ceramic prepolymer; (c) Mixing the modified organic silicon resin, the phenolic-ceramic prepolymer and the interface modifier, and reacting to obtain an intermediate product; (d) And removing the solvent in the intermediate product, adding a composite curing agent, uniformly mixing, and curing to obtain the high-temperature-resistant resin. Further, on the basis of the above technical solution of the present invention, in the step (a), the solvent includes at least o