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CN-121975365-A - Imidazole modified silanized graphene oxide, shape memory anti-corrosion resin based on imidazole modified silanized graphene oxide, and preparation method and application of imidazole modified silanized graphene oxide

CN121975365ACN 121975365 ACN121975365 ACN 121975365ACN-121975365-A

Abstract

The invention relates to the technical field of high polymer materials, discloses imidazole modified silanization graphene oxide and a preparation method thereof, uses imidazole containing amino and gamma- (2, 3-glycidoxy) propyl trimethoxy silane to modify graphene oxide, the imidazole modified silanization graphene oxide prepared by the method solves the technical problems that graphene oxide is easy to agglomerate and poor in compatibility with resin. The invention also discloses a shape memory anti-corrosion resin based on the imidazole modified graphene oxide, wherein epoxy cardanol mercaptopropionate, imidazole modified silanized graphene oxide containing epoxy groups and a disulfide bond curing agent are jointly introduced into a cross-linked network to obtain a composite coating with excellent mechanical properties, shape memory function and anti-corrosion performance, and the composite coating is suitable for long-acting protection of metal surfaces of ocean engineering, ships, chemical equipment and the like.

Inventors

  • HU YANG
  • LI YING
  • YANG ZHUOHONG
  • ZHOU YUHANG
  • SHEN XIYAN
  • DENG YITAO
  • CHU ZHUANGZHUANG

Assignees

  • 华南农业大学

Dates

Publication Date
20260505
Application Date
20260205

Claims (10)

  1. 1. The imidazole modified silanized graphene oxide is characterized by being prepared by the following steps: (1) 5-15 parts of tetraethyl silicate, 160 parts of ethanol and 30 parts of water are mixed according to parts by weight, 3-6 parts of gamma- (2, 3-glycidoxy) propyl trimethoxy silane is added into the mixture, and then the mixture is reacted at 65-75 ℃ to obtain silanized graphene oxide containing epoxy groups; (2) Dispersing 0.3-0.8 part of silanized graphene oxide containing epoxy groups into 200-400 parts of organic solvent, adding 5-8 parts of imidazole containing amino groups into the organic solvent, and reacting at 65-75 ℃ to obtain the epoxy-containing graphene oxide.
  2. 2. The imidazole-modified silanized graphene oxide according to claim 1, wherein the organic solvent is at least one selected from toluene, N-dimethylformamide and chloroform, and the amino-containing imidazole is at least one selected from 1- (3-aminopropyl) imidazole, 1-methyl-3- (3-aminopropyl) imidazole and 1-ethyl-3- (2-aminoethyl) imidazole.
  3. 3. The imidazole-modified silanized graphene oxide of claim 1, wherein the reaction time is 12-24 h.
  4. 4. The shape memory anti-corrosion resin based on imidazole modified silanized graphene oxide is characterized in that the raw materials of the resin consist of, by weight, 100 parts of epoxy resin, 5-15 parts of epoxy cardanol mercaptopropionate, 30-50 parts of disulfide bond-containing amine curing agent and 0.1-1.0 part of imidazole modified silanized graphene oxide according to any one of claims 1-3; wherein, the structural formula of the epoxy cardanol mercaptopropionate is shown as the following formula: 。
  5. 5. The shape memory anticorrosive resin based on imidazole modified silanized graphene oxide according to claim 4, wherein the epoxy resin is at least one selected from bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin, and the amine curing agent containing disulfide bonds is at least one selected from 2,2 '-dithiodiphenylamine and 4,4' -dithiodiphenylamine.
  6. 6. The imidazole-modified silanized graphene oxide-based shape memory anticorrosive resin according to claim 4, wherein the epoxy cardanol mercaptopropionate is prepared by the following steps in parts by weight: (1) Reacting 80-100 parts of cardanol, 110-130 parts of mercaptopropionic acid and 6-11 parts of photoinitiator under ultraviolet light for 3-7 h to obtain cardanol mercaptopropionic acid; (2) Mixing 90-110 parts of cardanol mercaptopropionic acid, 110-130 parts of epoxy chloropropane and 0.5-2 parts of phase transfer catalyst, reacting at 50-120 ℃ for 2-6 h parts, adding 100-400 parts of alkaline aqueous solution into the reacted product, reacting at 20-30 ℃ for 10-14 h parts, and purifying to obtain the finished product.
  7. 7. The shape memory anticorrosive resin based on imidazole modified silanized graphene oxide according to claim 6, wherein the photoinitiator is at least one selected from ITX photoinitiator, 1173 photoinitiator and TPO photoinitiator, the phase transfer catalyst is at least one selected from tetrabutylammonium bromide, tetrabutylammonium chloride and benzyltriethylammonium chloride, the alkaline aqueous solution is at least one selected from sodium hydroxide aqueous solution and potassium hydroxide aqueous solution, and the alkaline aqueous solution is an alkaline aqueous solution with a concentration of 20-40 wt%.
  8. 8. The shape memory anticorrosive resin based on imidazole modified silanized graphene oxide according to claim 6, wherein in the step (2), the purification method comprises extracting the reaction solution obtained by the reaction with an organic solvent, combining the organic phases, washing the organic phases with saturated saline solution until the organic phases are neutral, drying the organic phases with a desiccant, filtering the dried organic phases, and distilling the filtrate under reduced pressure.
  9. 9. The shape memory anticorrosive coating based on imidazole modified silanized graphene oxide is characterized by being prepared by the following steps: Mixing the raw materials of the imidazole-modified silanized graphene oxide-based shape memory anticorrosive resin according to any one of claims 4-8, then curing the mixture at 100 ℃ for 8 hours, curing at 130 ℃ for 3h, and curing at 170 ℃ for 2 h.
  10. 10. Use of the imidazole modified silanized graphene oxide-based shape memory anticorrosive resin according to any one of claims 4-8 for preparing metal anticorrosive coatings and shape memory materials.

Description

Imidazole modified silanized graphene oxide, shape memory anti-corrosion resin based on imidazole modified silanized graphene oxide, and preparation method and application of imidazole modified silanized graphene oxide Technical Field The invention relates to the technical field of high polymer materials, in particular to imidazole modified silanized graphene oxide, shape memory anti-corrosion resin based on the imidazole modified silanized graphene oxide, and a preparation method and application of the imidazole modified silanized graphene oxide. Background Metal corrosion is an important problem faced in the fields of ocean engineering, chemical equipment and the like. The traditional anti-corrosion coating has single function and can not realize self-adaptive protection in a complex environment. The shape memory material can restore the original shape under the external stimulus, and provides a new idea for the intelligent anti-corrosion coating. However, existing shape memory materials often have insufficient mechanical properties and lack long-term corrosion resistance. Graphene oxide is randomly and densely stacked in a coating to form countless physical barriers, corrosion is prevented by using a labyrinth effect, and the graphene oxide is widely applied to an anti-corrosion coating due to the excellent barrier property and mechanical reinforcing effect, but the graphene oxide is easy to agglomerate and has poor compatibility with resin, so that the application of the graphene oxide is limited. Therefore, the development of the composite coating with excellent mechanical property, shape memory capability and long-acting anti-corrosion function has important significance. Disclosure of Invention The invention aims to provide imidazole modified silanized graphene oxide to solve the technical problems that graphene materials are easy to agglomerate and poor in compatibility with resin in the prior art. The invention also provides a shape memory anticorrosive resin based on the imidazole modified silanized graphene oxide and application thereof. According to a first aspect of the present invention there is provided imidazole-modified silanized graphene oxide prepared by the steps of: (1) 5-15 parts of tetraethyl silicate, 160 parts of ethanol and 30 parts of water are mixed, 3-6 parts of gamma- (2, 3-glycidoxy) propyl trimethoxy silane is added into the mixture, and then the mixture is reacted at 65-75 ℃ to obtain silanized graphene oxide; (2) Dispersing 0.3-0.8 part of the product obtained in the step (1) into 200-400 parts of an organic solvent, adding 5-8 parts of imidazole containing amino into the organic solvent, and reacting at 65-75 ℃ to obtain the product. According to the preparation method, graphene oxide is subjected to two-step chemical modification, a layer of siloxane network is firstly constructed on the surface of the graphene oxide, epoxy groups are introduced, the sheet layer can be effectively isolated, the conductivity of the graphene oxide is reduced, the compatibility with organic resin is improved, and then imidazole rings with excellent metal ion chelating ability are firmly grafted to the surface of the graphene in a covalent bond mode by utilizing ring-opening reaction of imidazole containing amino groups and the epoxy groups. Imidazole modified silanized graphene oxide has the dual functions of physical barrier and chemical corrosion inhibition, and imidazole rings and metals are chelated to form a compact organic metal composite layer which is tightly covered on the exposed metal surface. In some embodiments, the organic solvent is selected from at least one of toluene, N-dimethylformamide, chloroform; In some embodiments, the amino-containing imidazole is selected from at least one of 1- (3-aminopropyl) imidazole, 1-methyl-3- (3-aminopropyl) imidazole, 1-ethyl-3- (2-aminoethyl) imidazole. In some embodiments, in step (1) and step (2), the reaction time is from 12 to 24h. According to a second aspect of the invention, there is provided a shape memory anticorrosive resin based on imidazole modified silanized graphene oxide, wherein the raw materials of the shape memory anticorrosive resin consist of, by weight, 100 parts of epoxy resin, 5-15 parts of epoxy cardanol mercaptopropionate, 30-50 parts of disulfide bond-containing amine curing agent and 0.1-1.0 part of imidazole modified silanized graphene oxide; wherein, the structural formula of the epoxy cardanol mercaptopropionate is shown as the following formula: 。 In the raw materials, the epoxy cardanol mercaptopropionate has both the long-chain toughening effect of cardanol and the reactivity of epoxy groups, and can participate in network formation in the curing process as a bio-based flexible epoxy active toughening agent, so that the crosslinking density and mechanical property of a resin system can be effectively regulated. The imidazole modified silanized graphene oxide is used as a functional nano filler, and an amine