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CN-119193064-B - Comb type poly (arylene ether nitrile) modified epoxy resin adhesive and preparation method thereof

CN119193064BCN 119193064 BCN119193064 BCN 119193064BCN-119193064-B

Abstract

A comb-type poly (arylene ether nitrile) modified epoxy resin adhesive and a preparation method thereof relate to the field of epoxy resin adhesives and aim to solve the problems that the prior poly (arylene ether nitrile) is used as a toughening modifier to be introduced into an epoxy resin system, has higher viscosity and is not beneficial to coating construction. The comb type poly (arylene ether nitrile) modified epoxy resin adhesive comprises a first component and a second component, wherein the first component comprises epoxy resin, modified heterocyclic resin, comb type poly (arylene ether nitrile), thermosetting PI fiber powder, a coupling agent, epoxy phosphate and a thixotropic agent, and the second component comprises an aromatic amine curing agent, a polyamide curing agent, an accelerator and a grafting agent. The method comprises the steps of uniformly stirring the component A and the component B to obtain the comb-type poly (arylene ether nitrile) modified epoxy resin adhesive. The comb-type poly (arylene ether nitrile) powder is used as the toughening modifier of the epoxy resin, the viscosity of the epoxy resin adhesive is not greatly changed due to the introduction of the powder, the comb-type poly (arylene ether nitrile) powder is favorable for smearing construction during use, and the comb-type poly (arylene ether nitrile) powder can be used for filling, repairing and bonding holes, grooves and gaps on various material workpieces.

Inventors

  • LIU CAIZHAO
  • SONG CAIYU
  • YUAN ZHIGANG
  • Xue Shuangle
  • ZHAO YILEI
  • SUN MINGMING
  • ZHANG XUGANG
  • SHI LILI
  • ZHANG BIN
  • LI JIANHUI
  • WANG LEI
  • XUE GANG
  • ZHAO MING

Assignees

  • 黑龙江省科学院石油化学研究院

Dates

Publication Date
20260512
Application Date
20240925

Claims (9)

  1. 1. The comb type polyarylether nitrile modified epoxy resin adhesive is characterized by comprising, by mass, 40-65 parts of epoxy resin, 6-20 parts of modified heterocyclic resin, 8-30 parts of comb type polyarylether nitrile, 2-10 parts of thermosetting PI fiber powder, 0.2-1.5 parts of coupling agent, 0.5-2 parts of epoxy phosphate and 1-5 parts of thixotropic agent, and an ethyl component, wherein the ethyl component comprises, by mass, 15-25 parts of aromatic amine curing agent, 20-40 parts of polyamide curing agent, 0.3-1.0 parts of accelerator and 0.6-1.5 parts of grafting agent; the structural formula of the comb-type polyarylether nitrile is as follows: , the mesh number of the comb-type poly (arylene ether nitrile) is 120-180 meshes, and the glass transition temperature is 127 ℃; the modified heterocyclic resin is prepared by prepolymerizing 4-methyl-1, 3-phenyl bismaleimide, 3-aminophenylacetylene and 4-vinylaniline for 4 hours at 130 ℃ according to the mass ratio of 2:1:1; the preparation method of the component A comprises the steps of mixing epoxy resin, modified heterocyclic resin, coupling agent and epoxy phosphate, stirring uniformly at room temperature, adding thermosetting PI fiber powder, comb-type polyarylethernitrile and thixotropic agent, and grinding and dispersing to obtain the component A.
  2. 2. The comb-type polyarylethernitrile modified epoxy resin adhesive according to claim 1, wherein the epoxy resin is one or a mixture of a plurality of E-44, F-44, E-51, AG-70, AG-80, TDE-85, AFG-90 and hydantoin epoxy.
  3. 3. The comb-type poly (arylene ether nitrile) -modified epoxy resin adhesive of claim 1, wherein the thermosetting PI fiber powder has a mesh number of 100 mesh and a glass transition temperature of 425 ℃.
  4. 4. The comb-type poly (arylene ether nitrile) -modified epoxy resin adhesive of claim 1, wherein, the aromatic amine curing agent is 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, 2-bis (4-aminophenyl) hexafluoropropane, 4 '-diaminodiphenyl methane, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2' -bis (4- (3-aminophenoxy) phenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) propane, 4 '-bis (3-aminophenoxy) diphenylsulfone, 4' -bis (3-aminophenoxy) benzophenone.
  5. 5. The comb-type polyarylethernitrile modified epoxy resin adhesive of claim 1, wherein the polyamide curing agent is one or a mixture of several of polyamide resin 651, polyamide resin 650, polyamide resin V115, polyamide resin V125, polyamide resin V140, polyamide resin 200, polyamide resin 300.
  6. 6. The comb-type polyarylethernitrile modified epoxy resin adhesive according to claim 1, wherein the accelerator is obtained by mixing an imidazole derivative and triphenylphosphine according to a mass ratio of 1:1.
  7. 7. The comb-type polyaryl ether nitrile modified epoxy resin adhesive according to claim 6, wherein the imidazole derivative is 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole or 1- (2-cyanoethyl) -2-undecylimidazole.
  8. 8. The comb-type polyarylethernitrile modified epoxy resin adhesive according to claim 1, wherein the grafting agent is polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 4-butanediol diglycidyl ether, triethylene glycol diglycidyl ether, or diethylene glycol diglycidyl ether.
  9. 9. The preparation method of the comb-type polyarylethernitrile modified epoxy resin adhesive according to claim 1, which is characterized by comprising the following steps: 1. 40-65 parts of epoxy resin, 6-20 parts of modified heterocyclic resin, 8-30 parts of comb-shaped polyarylether nitrile, 2-10 parts of thermosetting PI fiber powder, 0.2-1.5 parts of coupling agent, 0.5-2 parts of epoxy phosphate, 1-5 parts of thixotropic agent, 15-25 parts of aromatic amine curing agent, 20-40 parts of polyamide curing agent, 0.3-1.0 part of accelerator and 0.6-1.5 parts of grafting agent are weighed according to parts by mass; 2. Mixing the epoxy resin, the modified heterocyclic resin, the coupling agent and the epoxy phosphate which are weighed in the first step, uniformly stirring at room temperature, adding thermosetting PI fiber powder, comb-shaped polyarylether nitrile and thixotropic agent, and grinding and dispersing to obtain a component A; 3. Stirring an aromatic amine curing agent, a polyamide curing agent, an accelerator and a grafting agent in a reaction kettle at 80-100 ℃ for 4-8 hours, and cooling to room temperature for standby to obtain a component B; 4. And (3) uniformly stirring the component A obtained in the step (II) and the component B obtained in the step (III) at room temperature to obtain the comb-type polyarylether nitrile modified epoxy resin adhesive.

Description

Comb type poly (arylene ether nitrile) modified epoxy resin adhesive and preparation method thereof Technical Field The invention relates to the field of epoxy resin adhesives, in particular to a comb type poly (arylene ether nitrile) modified epoxy resin adhesive and a preparation method thereof. Background The epoxy resin has excellent adhesive property, mechanical property and chemical stability, and meanwhile, the epoxy resin has good processability and low cost, and has been widely used in different fields as an adhesive material. However, epoxy resins also have disadvantages such as hard and brittle properties and poor impact resistance, and therefore, when used as an adhesive material, they often need to be toughened and modified. The epoxy resin has more toughening modification methods, and common modifiers include thermoplastic resin, thermosetting resin, macromolecular rubber, core-shell nano particles, inorganic fiber powder and the like. Among them, poly (arylene ether nitrile) is a novel high-performance thermoplastic resin, and has been widely studied and reported in the field of modified epoxy resins. However, most students adopt a solvent method or a hot-melting method to introduce the polyarylether nitrile into an epoxy resin system, the solvent method has high toxicity, is not safe and environment-friendly enough, the hot-melting method needs to be heated to a higher temperature to be uniformly mixed, the manufacturability is poor, meanwhile, the method leads to obvious increase of the viscosity of the epoxy resin adhesive, the smearing construction is not facilitated, the interface selectivity of the prepared adhesive to the adhered material is strong, and the application range is narrow. In addition, researches have also shown that the combination of an aromatic amine curing agent, a polyamide curing agent, a polyether amine curing agent, an aliphatic amine curing agent, an imidazole curing agent, a mercaptan curing agent and the like in various combination modes can improve the comprehensive performance of the epoxy resin adhesive. Most of the components are added in multi-component form, which brings trouble to practical operation. Disclosure of Invention The invention aims to solve the problems that the prior polyarylether nitrile is introduced into an epoxy resin system as a toughening modifier, has higher viscosity and is unfavorable for coating construction, and provides a comb type polyarylether nitrile modified epoxy resin adhesive and a preparation method thereof. The comb type polyarylether nitrile modified epoxy resin adhesive comprises, by mass, 40-65 parts of epoxy resin, 6-20 parts of modified heterocyclic resin, 8-30 parts of comb type polyarylether nitrile, 2-10 parts of thermosetting PI fiber powder, 0.2-1.5 parts of coupling agent, 0.5-2 parts of epoxy phosphate and 1-5 parts of thixotropic agent, and 20-40 parts of polyamide curing agent, 0.3-1.0 part of accelerator and 0.6-1.5 parts of grafting agent; the comb type poly (arylene ether nitrile) has the structural formula: , the mesh number of the comb-type poly (arylene ether nitrile) is 120-180 meshes, and the glass transition temperature is 127 ℃. Further, the epoxy resin is one or a mixture of more of E-44, F-44, E-51, AG-70, AG-80, TDE-85, AFG-90 and hydantoin epoxy. Further, the modified heterocyclic resin is prepared by prepolymerizing 4-methyl-1, 3-phenyl bismaleimide, 3-aminophenylacetylene and 4-vinylaniline for 4 hours at 130 ℃ according to a mass ratio of 2:1:1. Further, the mesh number of the thermosetting PI fiber powder is 100 mesh, and the glass transition temperature is 425 ℃. Further, the coupling agent is gamma-mercaptopropyl methyl dimethoxy silane, bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide or bis- [ gamma- (triethoxysilyl) propyl ] disulfide. Further, the epoxy phosphate is CM-801 or 4901. Further, the thixotropic agent is fumed silica R972, A300, A380 or R202. Further, the method comprises the steps of, the aromatic amine curing agent is 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, 2-bis (4-aminophenyl) hexafluoropropane, 4 '-diaminodiphenyl methane, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2' -bis (4- (3-aminophenoxy) phenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) propane, 4 '-bis (3-aminophenoxy) diphenylsulfone, 4' -bis (3-aminophenoxy) benzophenone. Further, the polyamide curing agent is one or a mixture of more than one of polyamide resin 651, polyamide resin 650, polyamide resin V115, polyamide resin V125, polyamide resin V140, polyamide resin 200 and polyamide resin 300. Further, the accelerator is obtained by mixing an imidazole derivative and triphenylphosphine according to a mass ratio of 1:1. Wherein the imidazole derivative is 1