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CN-119490726-B - Flame-retardant epoxy resin composition, flame-retardant epoxy resin material, and preparation method and application thereof

CN119490726BCN 119490726 BCN119490726 BCN 119490726BCN-119490726-B

Abstract

The invention relates to the technical field of high polymer materials, and discloses a flame-retardant epoxy resin composition, which comprises, based on the total amount of the composition, 30-40wt% of epoxy resin, 20-40wt% of curing agent, 0.5-2wt% of accelerator, 20-30wt% of flame retardant, 1-10wt% of diluent, 1-5wt% of coupling agent and 0-1wt% of defoamer. The flame-retardant epoxy resin composition has the effects of high flame-retardant efficiency and good mechanical property, meets the highest flame-retardant level requirements of UL94 and other standard requirements, and has excellent manufacturability in the processing process of the composite material, and the obtained product has attractive appearance.

Inventors

  • XU AINA
  • ZHANG BINBO
  • XIONG WEI
  • HUANG YONG
  • SUN JUN

Assignees

  • 中国石油化工股份有限公司
  • 中国石化上海石油化工股份有限公司

Dates

Publication Date
20260512
Application Date
20230818

Claims (20)

  1. 1. A flame retardant epoxy resin composition, characterized in that the composition comprises the following components, based on the total amount of the composition: 33-38wt% of epoxy resin, 28-35wt% of curing agent, 1-1.5wt% of accelerator, 25-28wt% of flame retardant, 4-6wt% of diluent, 2-3wt% of coupling agent and 0.2-0.6wt% of defoamer; Wherein the mass ratio of the coupling agent to the flame retardant is 2-4:24-28; Wherein the coupling agent is selected from phosphazene silane coupling agents shown in a structural formula (1), (1) Wherein R 1 is selected from the group consisting of alkylene of C 2 -C 4 , and R 2 and R 3 are each independently selected from the group consisting of alkoxy of C 2 -C 3 .
  2. 2. The composition of claim 1, wherein the epoxy resin is selected from at least one of a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a glycidyl amine epoxy resin, a phenolic epoxy resin, and a hybrid epoxy resin.
  3. 3. The composition of claim 2, wherein the glycidyl ether epoxy resin is selected from at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin.
  4. 4. The composition according to claim 1, wherein the curing agent is selected from anhydride curing agents and/or amine curing agents.
  5. 5. The composition of claim 4, wherein the anhydride-based curing agent is selected from at least one of monofunctional anhydrides, difunctional anhydrides, and phenolic novolac resins.
  6. 6. The composition of claim 4, wherein the amine curing agent is selected from at least one of diamines, aromatic amines, dicyandiamide, and organic hydrazides.
  7. 7. The composition of claim 1, wherein the accelerator is selected from at least one of tertiary amine salt complexes, imidazoles, and modified imidazoles.
  8. 8. Composition according to claim 1, characterized in that the diluent is selected from glycidyl ethers and/or glycidyl amines.
  9. 9. The composition of claim 1, wherein the defoamer is selected from at least one of tributyl phosphate, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, and BYKA530,530.
  10. 10. The composition according to any one of claims 1 to 9, wherein the flame retardant comprises component a and component B; Wherein the component A is at least one selected from phosphazene flame retardant, alkyl phosphinate, phosphaphenanthrene flame retardant, phosphate flame retardant, phosphorus-containing ionic liquid and phosphate flame retardant; The component B is at least one selected from organosilicon compounds, metal oxides, metal hydroxides and graphite substances.
  11. 11. The composition according to claim 10, wherein the mass ratio of component a to component B is 80-20:99-1.
  12. 12. The composition of claim 10, wherein component a is selected from at least one of polydiphenoxyphosphazene, hexaphenoxycyclotriphosphazene, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphaphenanthrenetriazine compounds, DOPO ester compounds, triphenyl phosphate, resorcinol bis (diphenyl) phosphate, toluene diphenyl phosphate, 2,4,7, 9-tetramethyl-5-decyne-4, 7-diol, ammonium polyphosphate, melamine polyphosphate.
  13. 13. The composition of claim 10, wherein component B is selected from at least one of antimony oxide, zinc borate, magnesium hydroxide, aluminum hydroxide, molybdenum oxide, ammonium molybdate, zirconium phosphate, polysiloxane, polysilazane, silica, graphite, carbon nanotubes, and graphene.
  14. 14. The preparation method of the flame-retardant epoxy resin material is characterized by comprising the following steps of: (1) Uniformly mixing epoxy resin and a diluent under a first stirring condition to obtain a mixture I; (2) Adding a flame retardant and a defoaming agent into the mixture I, and uniformly mixing under a second stirring condition to obtain a mixture II; (3) Adding a coupling agent, a curing agent and an accelerator into the mixture II, uniformly mixing under a third stirring condition, and curing to obtain a flame-retardant epoxy resin material; 33-38wt% of epoxy resin, 28-35wt% of curing agent, 1-1.5wt% of accelerator, 25-28wt% of flame retardant, 4-6wt% of diluent, 2-3wt% of coupling agent and 0.2-0.6wt% of defoamer; Wherein the mass ratio of the coupling agent to the flame retardant is 2-4:24-28; Wherein the coupling agent is selected from phosphazene silane coupling agents shown in a structural formula (1), (1) Wherein R 1 is selected from the group consisting of alkylene of C 2 -C 4 , and R 2 and R 3 are each independently selected from the group consisting of alkoxy of C 2 -C 3 .
  15. 15. The method of claim 14, wherein the first agitation condition comprises an agitation temperature of 50-80 ℃ and an agitation speed of 200-400rpm.
  16. 16. The method of claim 14, wherein the second stirring conditions include a stirring temperature of 80-200 ℃ and a stirring speed of 200-500rpm.
  17. 17. The method of claim 14, wherein the third stirring condition comprises a stirring temperature of 30-50 ℃ and a stirring speed of 100-300rpm.
  18. 18. The method according to any one of claims 14 to 17, wherein the curing conditions include heat preservation at 80 to 100 ℃ for 60 to 120min under normal pressure, and then heating to 130 to 150 ℃ for 90 to 180min.
  19. 19. A flame retardant epoxy resin material prepared by the method of any one of claims 14-18, wherein the viscosity of the flame retardant epoxy resin material at 25 ℃ is less than 1000 mPa s, the limiting oxygen index is 25-35%, the tensile property is 40-70MPa, the tensile modulus is 2.5-3.4GPa, the flexural property is 90-135MPa, and the flexural modulus is 2.5-3GPa.
  20. 20. Use of the flame retardant epoxy resin material of claim 19 in carbon fiber composite.

Description

Flame-retardant epoxy resin composition, flame-retardant epoxy resin material, and preparation method and application thereof Technical Field The invention relates to the technical field of high polymer materials, in particular to a flame-retardant epoxy resin composition, a flame-retardant epoxy resin material, a preparation method and application thereof. Background Epoxy resins are widely used in various fields as the main thermosetting resins. Epoxy resins have significant advantages, especially as a composite resin matrix. However, epoxy resin is a relatively flammable type of thermosetting resin, and the oxygen index of the common epoxy resin is only about 19.8%, so that the epoxy resin can continuously burn after a fire source is evacuated, and the risk of fire is increased. Meanwhile, substances such as toxic fog and toxic gas generated by ablation can cause casualties of surrounding people. Aiming at the application of the composite material in the fields of transportation, construction, electronic appliances and the like with flame retardant requirements, the epoxy resin needs to be endowed with flame retardant property for flame retardant treatment. The common technical approach for preparing the flame-retardant epoxy resin is mainly to add a flame retardant into an epoxy resin system. Flame retardants are generally classified into halogen-containing flame retardants and halogen-free flame retardants. Halogen-containing flame retardants have high flame retardant efficiency, but are not friendly to products and environment, so currently, halogen-free flame retardants are used in a large number. Compared with halogen-containing flame retardants, the halogen-free flame retardant has relatively low flame retardant efficiency, and the use amount of the flame retardant needs to be increased to achieve a certain flame retardant effect, so that on one hand, the viscosity of an epoxy resin system is increased, the processing performance of the resin is reduced, and on the other hand, the excessive use of the flame retardant can have adverse effects on the mechanical and thermodynamic properties of the resin. How to balance the flame retardant property and the mechanical property of an epoxy resin system is one of the difficulties in the current research. Therefore, it is necessary to research a high-performance flame-retardant epoxy resin, which has high flame-retardant efficiency and excellent mechanical properties so as to meet the requirements of various process processing. Disclosure of Invention The invention aims to solve the problem that the mechanical property of epoxy resin is reduced due to excessive use of a flame retardant in the prior art, and provides a flame-retardant epoxy resin composition, a flame-retardant epoxy resin material, a preparation method and application thereof. The resin has the effects of high flame retardant efficiency and good mechanical property, meets the highest-grade flame retardant requirement in the requirements of UL94 and other standards, and has excellent manufacturability in the processing process of the composite material, and the obtained product has attractive appearance. In order to achieve the above object, the first aspect of the present invention provides a flame retardant epoxy resin composition comprising, based on the total amount of the composition, 30 to 40wt% of an epoxy resin, 20 to 40wt% of a curing agent, 0.5 to 2wt% of an accelerator, 20 to 30wt% of a flame retardant, 1 to 10wt% of a diluent, 1 to 5wt% of a coupling agent and 0 to 1wt% of an antifoaming agent. The second aspect of the present invention provides a method for preparing a flame retardant epoxy resin material, comprising the steps of: (1) Uniformly mixing epoxy resin and a diluent under a first stirring condition to obtain a mixture I; (2) Adding a flame retardant and a defoaming agent into the mixture I, and uniformly mixing under a second stirring condition to obtain a mixture II; (3) Adding a coupling agent, a curing agent and an accelerator into the mixture II, uniformly mixing under a third stirring condition, and curing to obtain the flame-retardant epoxy resin material. The third aspect of the invention provides a flame-retardant epoxy resin material prepared by the method of the second aspect of the invention, wherein the limiting oxygen index of the flame-retardant epoxy resin material is 25-35%, the viscosity is less than 1000 mPa.s at 25 ℃, the tensile property is 40-70MPa, the tensile modulus is 2.5-3.4GPa, the bending property is 90-135MPa, and the bending modulus is 2.5-3GPa. The fourth aspect of the invention provides an application of the flame-retardant epoxy resin material in the carbon fiber composite material. Through the technical scheme, the invention has the following beneficial effects: (1) The flame-retardant epoxy resin composition provided by the invention has the advantages of high flame-retardant efficiency, less consumption of flame retardant, less infl