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CN-121991465-A - Degradable epoxy resin composition and preparation method and application thereof

CN121991465ACN 121991465 ACN121991465 ACN 121991465ACN-121991465-A

Abstract

The invention discloses a degradable epoxy resin composition, a preparation method and application thereof, and relates to the technical field of high polymer materials. The degradable epoxy resin composition comprises, by weight, 40-60 parts of aromatic disulfide bond-containing solid epoxy resin, 30-50 parts of silicone bond-containing liquid epoxy resin, 8-12 parts of toughening agent, 4-6 parts of curing agent and 1-3 parts of accelerator. According to the invention, a silica bond/disulfide bond synergistic catalytic degradation structure is formed through the composition of the components, so that the epoxy resin in the carbon fiber reinforced composite material can be rapidly degraded, and the difficult problem of difficult fiber recovery is solved. And the silica bond/disulfide bond synergistic catalytic degradation structure has excellent wet performance, so that the composite material is ensured to have recoverable performance without sacrificing the wet performance of the composite material. Meanwhile, the degradable epoxy resin system is suitable for the existing hot pressing impregnation process for preparing the prepreg, and has wide industrial application value.

Inventors

  • WANG HAOPENG
  • LI ZHITAO
  • YIN GUOQIANG
  • GUO ZIHAO
  • LIU XINGBAO
  • YANG JUNQI

Assignees

  • 江苏恒神股份有限公司

Dates

Publication Date
20260508
Application Date
20260228

Claims (10)

  1. 1. The degradable epoxy resin composition is characterized by comprising, by weight, 40-60 parts of aromatic disulfide bond-containing solid epoxy resin, 30-50 parts of silicone bond-containing liquid epoxy resin, 8-12 parts of toughening agent, 4-6 parts of curing agent and 1-3 parts of accelerator.
  2. 2. The degradable epoxy resin composition of claim 1, wherein the aromatic disulfide bond containing solid epoxy resin has a structural formula as shown in I: Wherein R is selected from 、 、 And At least one of them.
  3. 3. The degradable epoxy resin composition of claim 1, wherein the liquid epoxy resin containing siloxane bonds comprises at least one of tetraepoxycyclosiloxane, 1, 5-bis (glycidoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane, epoxy-terminated phenyltrisiloxane, tris (glycidoxypropyl dimethylsiloxy) phenylsilane, bis [ (epoxycyclohexyl) ethyl ] tetramethyldisiloxane, and tetraepoxycyclohexylethyl-2, 4,6, 8-tetramethylcyclotetrasiloxane.
  4. 4. The degradable epoxy resin composition of claim 1, wherein the toughening agent comprises at least one of liquid rubber, thermoplastic resin, and core shell rubber particles; and/or the curing agent comprises at least one of DDS, DICY, 2-ethyl-4-methylimidazole and 594 curing agent; And/or the accelerator comprises at least one of a modified amine accelerator, a urea accelerator and an imidazole accelerator.
  5. 5. The degradable epoxy resin composition of claim 1, wherein the glass transition temperature of the degradable epoxy resin composition is 120-137 ℃.
  6. 6. A method of preparing the degradable epoxy resin composition of any one of claims 1-5, comprising: Mixing 85% -90% of the total mass of the solid epoxy resin containing the aromatic disulfide bonds, the liquid epoxy resin containing the siloxane bonds and the toughening agent, heating to 80-90 ℃, stirring and reacting for 1-3 hours, and cooling to room temperature to obtain a first component resin; mixing 10% -15% of the total mass of the liquid epoxy resin containing the siloxane bond, the curing agent and the accelerator to obtain a second component resin; And mixing and dispersing the first component resin and the second component resin to obtain the degradable epoxy resin composition.
  7. 7. Use of a degradable epoxy resin composition according to any one of claims 1-5 or a degradable epoxy resin composition obtained by a method for preparing a degradable epoxy resin composition according to claim 6 for the preparation of a carbon fiber reinforced composite.
  8. 8. The carbon fiber reinforced epoxy resin composite material is characterized in that the preparation method comprises the following steps: Forming a resin film from the degradable epoxy resin composition according to any one of claims 1 to 5 or the degradable epoxy resin composition prepared by the preparation method of the degradable epoxy resin composition according to claim 6 by a film calendaring method; arranging carbon fibers between two layers of resin adhesive films, and preparing carbon fiber epoxy resin prepreg through hot-pressing impregnation compounding; and forming the carbon fiber epoxy resin prepreg to prepare the carbon fiber reinforced epoxy resin composite material.
  9. 9. The carbon fiber reinforced epoxy resin composite material according to claim 8, wherein the glue coating temperature of the glue film calendaring method is 70-80 ℃; And/or the surface density of the resin adhesive film is 66.5-66.9 g/m 2 ; And/or the surface density of the carbon fiber is 195-205g/m 2 ; And/or the temperature of the hot pressing impregnation compounding is 80-95 ℃; And/or the resin content of the carbon fiber epoxy resin prepreg is 40%; And/or the molding comprises autoclave molding, hot-press molding or OOA curing molding, wherein when hot-press molding is selected, the hot-press molding temperature is 120-150 ℃, the pressure is 1.5-2.5MPa, and the hot-press time is 30-60min; And/or the glass transition temperature of the carbon fiber reinforced epoxy resin composite material is 120-137 ℃, the tensile strength is 610-720MPa, and the compressive strength is 650-750MPa.
  10. 10. The carbon fiber reinforced epoxy resin composite material according to claim 8, wherein the carbon fiber reinforced epoxy resin composite material is soaked in a degradation liquid at normal temperature, and the resin part in the carbon fiber reinforced epoxy resin composite material is completely degraded for 4-10 h hours; Preferably, the degradation liquid is an alkaline aqueous solution with ph=12-14; Preferably, the alkaline aqueous solution includes at least one of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous sodium carbonate solution.

Description

Degradable epoxy resin composition and preparation method and application thereof Technical Field The invention relates to the technical field of high polymer materials, in particular to a degradable epoxy resin composition and a preparation method and application thereof. Background The carbon fiber reinforced composite material has the advantages of light weight, high strength, corrosion resistance, good conductivity and the like, and is widely applied to the fields of aerospace, electronics, electrics, rail transit, civil construction and the like. The epoxy resin has the advantages of good fiber wettability, high mechanical strength, excellent mechanical properties and the like, so the epoxy resin is mainly used as a matrix of the carbon fiber reinforced composite material. The carbon fiber/epoxy resin prepreg is an intermediate layering material in the manufacturing link of a composite material, has the advantages of strong designability, controllable fiber volume fraction, low product void ratio and the like, and is widely applied to the manufacturing of an advanced carbon fiber reinforced composite material. Epoxy resins are thermosetting resins that have the characteristic of a three-dimensional network cross-linked structure that is insoluble, which makes it impossible to process and reuse them as thermoplastic resins. Therefore, the high-value carbon fiber materials in the composite material formed by compounding the thermosetting epoxy resin and the carbon fiber face great challenges in recycling. Meanwhile, the epoxy resin and the carbon fiber belong to petroleum-based materials, a large amount of energy and petroleum resources are consumed in the preparation process, and the composite material cannot be recycled when reaching the retired period, so that the energy crisis and the environmental pollution are aggravated. Therefore, there is an urgent need to find a solution for efficiently treating waste epoxy resins and recovering high-value carbon fibers. Currently, fiber recovery means for epoxy/carbon fiber composites include pyrolysis and mechanical comminution. The pyrolysis method and the mechanical pulverizing method not only damage the fibers, but also consume a large amount of energy. In view of this, the present invention has been made. Disclosure of Invention The invention aims to provide a degradable epoxy resin composition, a preparation method and application thereof. The invention is realized in the following way: in a first aspect, the invention provides a degradable epoxy resin composition, which comprises, by weight, 40-60 parts of aromatic disulfide bond-containing solid epoxy resin, 30-50 parts of silicone bond-containing liquid epoxy resin, 8-12 parts of toughening agent, 4-6 parts of curing agent and 1-3 parts of accelerator. In an alternative embodiment, the aromatic disulfide bond containing solid epoxy resin has the structural formula shown in I: Wherein R is selected from 、、AndAt least one of them. In alternative embodiments, the liquid epoxy resin containing siloxane bonds comprises at least one of tetraepoxycyclosiloxane, 1, 5-bis (glycidoxypropyl) -3-phenyl-1,1,3,5,5-pentamethyltrisiloxane, epoxy-terminated phenyltrisiloxane, tris (glycidoxypropyl dimethylsiloxy) phenylsilane, bis [ (epoxycyclohexyl) ethyl ] tetramethyldisiloxane, and tetraepoxycyclohexylethyl-2, 4,6, 8-tetramethylcyclotetrasiloxane. In an alternative embodiment, the toughening agent includes at least one of a liquid rubber, a thermoplastic resin, and core shell rubber particles; and/or the curing agent comprises at least one of DDS, DICY, 2-ethyl-4-methylimidazole and 594 curing agent; And/or the accelerator comprises at least one of a modified amine accelerator, a urea accelerator and an imidazole accelerator. In an alternative embodiment, the degradable epoxy resin composition has a glass transition temperature of 120-137 ℃. In a second aspect, the present invention provides a method for preparing a degradable epoxy resin composition according to any one of the preceding embodiments, comprising: Mixing 85% -90% of the total mass of the solid epoxy resin containing the aromatic disulfide bonds, the liquid epoxy resin containing the siloxane bonds and the toughening agent, heating to 80-90 ℃, stirring and reacting for 1-3 hours, and cooling to room temperature to obtain a first component resin; mixing 10% -15% of the total mass of the liquid epoxy resin containing the siloxane bond, the curing agent and the accelerator to obtain a second component resin; And mixing and dispersing the first component resin and the second component resin to obtain the degradable epoxy resin composition. In a third aspect, the present invention provides a degradable epoxy resin composition according to any one of the preceding embodiments or a degradable epoxy resin composition obtained by the preparation method of the degradable epoxy resin composition according to any one of the preceding embodiments, and the use of t