CN112979921A - In-situ response corrosion-inhibition type epoxy resin and preparation method and application thereof - Google Patents
In-situ response corrosion-inhibition type epoxy resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN112979921A CN112979921A CN202110212928.6A CN202110212928A CN112979921A CN 112979921 A CN112979921 A CN 112979921A CN 202110212928 A CN202110212928 A CN 202110212928A CN 112979921 A CN112979921 A CN 112979921A
- Authority
- CN
- China
- Prior art keywords
- corrosion
- epoxy resin
- aqueous solution
- situ response
- dinitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to an in-situ response corrosion inhibition type epoxy resin and a preparation method and application thereof, belonging to the field of materials. The invention generates Fe in the initial stage of the corrosion of the substrate2+Under the condition, the metal ion can be quickly coordinated, and the corrosion is inhibited while a compact shielding layer is formed. Compared with the traditional epoxy resin, the epoxy resin has better heat resistance, excellent in-situ response corrosion inhibition characteristic and good corrosion resistance, and can be widely applied to marine equipment in severe environments of high temperature, high humidity and high saltAnd (5) corrosion protection.
Description
Technical Field
The invention belongs to the technical field of chemical materials, and particularly relates to an in-situ response corrosion-inhibition epoxy resin and a preparation method and application thereof.
Background
The service life of equipment in south sand island reefs in China is seriously influenced by corrosion in severe environments such as severe atmospheric environment, high temperature, high humidity, high salt, strong ultraviolet rays and the like. In China, the traditional protective primer is still adopted for corrosion protection measures of equipment (such as base stations, ocean platforms and the like) deployed to the south sand island reef, and micro defects such as cracks, bubbles, pinholes and the like are easy to occur in the coating and using processes. The microscopic defects easily cause direct contact between the metal base material and a corrosive medium to cause local corrosion, enlarge a corrosion area, seriously affect the corrosion protection period of the coating and shorten the service life of the base material. Therefore, in order to improve the corrosion protection capability of the coating on the metal substrate, appropriate protection measures are taken for the microscopic defects of the coating, and the method has important practical significance and economic benefit. The traditional coating repairing modes such as repairing, welding and the like can only repair macroscopically but cannot repair microscopically damaged coatings, and frequent maintenance work also increases the equipment operation cost. And the conventional epoxy resin and other anticorrosive materials have insufficient heat resistance and obvious high-temperature protection defects.
The self-healing method applied to the anticorrosive coating at present is mainly external self-healing, and the corrosion inhibitor is modified or introduced into a self-healing microcapsule technology to be physically compounded with a polymer matrix in the preparation process of the material. When the matrix is cracked, the microcapsules are cracked to enable the repairing agent to flow out, and the microcapsules penetrate into the cracks to enable the repairing agent to heal again. The technology needs to embed the microcapsule in the material in advance, does not need secondary maintenance, and becomes a research hotspot of crack repair technology in recent years. In addition, in the field of heavy corrosion prevention, the corrosion inhibitor is added into the epoxy resin, so that the material can have a certain self-repairing capacity, but the traditional corrosion inhibitor is mostly used in a direct feeding mode, so that not only is the resource waste caused, but also the corrosion inhibition efficiency of the corrosion inhibitor is reduced, the corrosion speed of a matrix is seriously accelerated, and the defects can be overcome by modifying the corrosion inhibitor.
The Chinese invention patent CN 107312140B discloses a self-repairing microcapsule for metal anticorrosive coatings and a preparation method thereof, the structure of the microcapsule is sequentially a capsule core material and a double-layer wall material from inside to outside, a corrosion inhibition material is loaded between the double-layer wall material, and a coupling agent is attached to the outer wall of the double-layer wall material. The capsule core adopts reactants of polyhydroxy or polyamino compounds and isocyanate, and the corrosion inhibition material is a nano particle and a metal corrosion inhibitor, so that the microcapsule has high repair efficiency and stable mechanical property, and can be widely applied to the fields of metal corrosion and self-repair materials in petrochemical industry, marine industry, automobile industry and the like. However, the existing microcapsule system still has the problems of low contact rate of the repairing agent and the curing agent, poor scale matching of the self-repairing microcapsule and the coating, difficulty in realizing effective repair of coating cracks in the micron scale of the microcapsule and the like.
Chinese patent CN 103031559 discloses a long-acting intelligent corrosion inhibitor controlled by pH and released, which is composed of a nontoxic pollution-free hydrogel sensitive to environmental pH and coated with imidazole corrosion inhibitors such as triazole, and the release condition of the corrosion inhibitor can be determined according to different properties of environmental media. However, the method needs to use the filler as a carrier, the addition amount of the corrosion inhibitor is less, and the corrosion inhibition effect still has certain defects.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide an in-situ response corrosion-inhibition epoxy resin, aims to provide a preparation method of the epoxy resin and aims to provide application of the epoxy resin in corrosion protection of a metal substrate. According to the method, a dinitrogen bisphenol fluorene compound is introduced into the epoxy resin in a covalent manner and is subjected to silane grafting modification, so that the in-situ response corrosion-inhibition type epoxy resin material with good heat resistance is obtained.
In order to achieve the purpose, the invention adopts the specific scheme that:
an in-situ response corrosion-inhibition type epoxy resin has the following structural formula:
the invention also discloses a preparation method of the epoxy resin, and the synthetic route is as follows:
the method specifically comprises the following steps:
(1) synthesis of silanized dinitrobisphenol fluorene: adding 1, 10-diazophenanthrene (diazobisphenol fluorene) into an alkaline aqueous solution, and stirring at 50-60 ℃ until the diazophenanthrene is completely dissolved; adding dichlorosilane, continuously reacting for 5-8 hours to obtain reaction liquid, and filtering the reaction liquid; adding an acid solution into the reaction solution to adjust the pH value to 7-8, filtering the precipitated solid, repeatedly washing the washing solution for multiple times, and drying to obtain silanized dinitrogen bisphenol fluorene;
(2) adding a mixed solvent into a three-neck flask with condensed water, adding metered silanized dinitrogen bisphenol fluorene under mechanical stirring, stirring until the mixture is completely dissolved, and then adding epoxy chloropropane until the mixture is uniformly mixed; continuously adding a catalyst, and reacting for 30-60 min at 60-100 ℃; cooling to 50-60 ℃, adding an alkaline aqueous solution, reacting for 4-6 h, and cooling to room temperature; washing the epoxy resin with deionized water to be neutral, adding a water absorbent, and filtering to obtain the in-situ response corrosion-inhibition epoxy resin;
the mixed solvent in the step (2) is two or more of toluene, xylene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
The alkaline aqueous solution is one or more of potassium hydroxide aqueous solution, sodium hydroxide aqueous solution and sodium bicarbonate aqueous solution.
The dichlorosilane is one or more of dimethyldichlorosilane and diphenyldichlorosilane.
The acid solution is one or more of dilute sulfuric acid, dilute hydrochloric acid and glacial acetic acid.
The washing liquid is one or more of deionized water, methanol and ethanol.
The catalyst is one or more of N-chlorosuccinimide, tetrabutylammonium bromide and dicyclohexyl carbodiimide.
The water absorbent is one or more of anhydrous magnesium sulfate, anhydrous sodium sulfate, calcium oxide and phosphorus pentoxide.
The invention further relates to the use of the epoxy resins for the corrosion protection of metal substrates.
Has the advantages that:
1. the invention provides an in-situ response corrosion-inhibition epoxy resin containing a 'bipyridine' structure, wherein a metal coordination compound 'dinitrogen bisphenol fluorene' with high-efficiency five-membered ring chelating effect is introduced into the epoxy resin structure. Fe is generated when the substrate is corroded at the initial stage2+Under the condition, the metal ion can be quickly coordinated, and the corrosion is inhibited while a compact shielding layer is formed. Meanwhile, after the dinitrogen bisphenol fluorene is subjected to silanization modification, the glass transition temperature of the epoxy resin can be further increased, the heat resistance of the material is improved, and effective protection of the metal substrate at high temperature is ensured. The result after the baking oven is placed for 2 hours at 220 ℃ shows that the epoxy resin has better heat resistance compared with the traditional epoxy resin; after 300h of salt spray test, corrosion is generated in a scratched area of a paint film, but no corrosion liquid flows down, the scratch sealing effect is obvious, the paint film in an unscored area does not bubble, fall or rust, the paint film has excellent in-situ response corrosion inhibition characteristic and good corrosion resistance, and can be widely applied to corrosion protection of marine equipment in a severe environment with high temperature, high humidity and high salt.
2. According to the invention, a common inhibitor, namely a dinitrogen bisphenol fluorene compound is introduced into the epoxy resin in a covalent manner and is subjected to silane grafting modification, so that the in-situ response corrosion inhibition epoxy resin material with good heat resistance is obtained. The method simultaneously utilizes the high-efficiency chelating effect and excellent heat-resisting property of metal ions of a bipyridine structure in the 1, 10-diazoniate, can overcome the defect of poor repairing efficiency of the traditional externally-applied microcapsule, simultaneously improves the addition amount and the corrosion inhibition effect of the corrosion inhibitor, and effectively enhances the in-situ repairability and the corrosion medium barrier property of the resin.
Drawings
FIG. 1 is a schematic structural diagram of an in-situ response corrosion-inhibition type epoxy resin;
FIG. 2 is a schematic diagram of an in-situ response etch-retarded epoxy resin synthesis;
FIG. 3 is a 1H-NMR spectrum of silylated bisphenol fluorene;
FIG. 4 is a 1H-NMR spectrum of an in situ response corrosion-retarded epoxy resin;
FIG. 5 is a graph of an in-situ response corrosion-retarded epoxy;
FIG. 6 is a graph of the in situ response 300h scratch salt spray test results for the buffered epoxy;
FIG. 7 is a graph of the results of a conventional epoxy 300h scratch salt spray test.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1:
a preparation method of in-situ response corrosion-inhibition epoxy resin comprises the following steps:
(1) 0.1mol of dinitrogen bisphenol fluorene is added into a 250mL three-neck flask, 0.2mol of NaOH aqueous solution is slowly dropped under magnetic stirring, and the temperature is heated to 50 ℃ until the dinitrogen bisphenol fluorene is completely dissolved. Slowly dropwise adding 0.05mol of dimethyldichlorosilane, continuously reacting for 6h within 10min, and detecting the reaction process by thin layer chromatography. After the reaction is finished, dropwise adding dilute sulfuric acid into the reaction liquid to adjust the pH value of the solution to be 7, separating out a light yellow solid, carrying out suction filtration, repeatedly washing water and ethanol for multiple times, and drying for 10 hours to obtain solid silylation dinitrogen bisphenol fluorene;
(2) adding 25mL of toluene and 25mL of N, N-dimethylformamide into a three-neck flask with condensed water, adding 0.05mol of methyl silanized dinitrobisphenol fluorene under mechanical stirring till complete dissolution, and then adding 0.9mol of epichlorohydrin till uniform mixing. Continuously adding 0.001mol of catalyst N-chlorosuccinimide, and reacting for 60min at 80 ℃. After cooling to 50 ℃, 5g of NaOH aqueous solution is added, reaction is carried out for 4h, and cooling to room temperature is carried out. Washing the epoxy resin with deionized water to neutrality, adding anhydrous magnesium sulfate as water absorbent, and filtering to obtain the in-situ response corrosion-inhibiting epoxy resin.
Example 2:
a preparation method of in-situ response corrosion-inhibition epoxy resin comprises the following steps:
(1) 0.1mol of dinitrogen bisphenol fluorene is added into a 250mL three-neck flask, 0.2mol of NaOH aqueous solution is slowly dropped under magnetic stirring, and the temperature is heated to 50 ℃ until the dinitrogen bisphenol fluorene is completely dissolved. Slowly dropwise adding 0.05mol of dimethyldichlorosilane, continuously reacting for 6h within 10min, and detecting the reaction process by thin layer chromatography. After the reaction is finished, dropwise adding dilute sulfuric acid into the reaction liquid to adjust the pH value of the solution to be 7, separating out a light yellow solid, carrying out suction filtration, repeatedly washing water and ethanol for multiple times, and drying for 10 hours to obtain solid silylation dinitrogen bisphenol fluorene;
(2) adding 20mL of toluene and 30mL of N, N-dimethylformamide into a three-neck flask with condensed water, adding 0.1mol of methyl silanized dinitrobisphenol fluorene under mechanical stirring till complete dissolution, and then adding 0.8mol of epichlorohydrin till uniform mixing. Continuously adding 0.001mol of catalyst N-chlorosuccinimide, and reacting for 60min at 80 ℃. After cooling to 50 ℃, 5g of NaOH aqueous solution is added, reaction is carried out for 4h, and cooling to room temperature is carried out. Washing the epoxy resin with deionized water to neutrality, adding anhydrous magnesium sulfate as water absorbent, and filtering to obtain the in-situ response corrosion-inhibiting epoxy resin.
Example 3:
a preparation method of in-situ response corrosion-inhibition epoxy resin comprises the following steps:
(1) 0.1mol of dinitrogen bisphenol fluorene is added into a 250mL three-neck flask, 0.2mol of NaOH aqueous solution is slowly dropped under magnetic stirring, and the temperature is heated to 50 ℃ until the dinitrogen bisphenol fluorene is completely dissolved. Slowly dropwise adding 0.05mol of dimethyldichlorosilane, continuously reacting for 6h within 10min, and detecting the reaction process by thin layer chromatography. After the reaction is finished, dropwise adding dilute hydrochloric acid into the reaction liquid to adjust the pH value of the solution to be 7, separating out a light yellow solid, carrying out suction filtration, repeatedly washing water and ethanol for multiple times, and drying for 10 hours to obtain solid silylation dinitrogen bisphenol fluorene;
(2) adding 15mL of toluene and 35mL of N, N-dimethylformamide into a three-neck flask with condensed water, adding 0.15mol of methyl silanized dinitrobisphenol fluorene under mechanical stirring till complete dissolution, and then adding 0.7mol of epichlorohydrin till uniform mixing. Continuously adding 0.001mol of catalyst N-chlorosuccinimide, and reacting for 60min at 80 ℃. After cooling to 50 ℃, 5g of NaOH aqueous solution is added, reaction is carried out for 4h, and cooling to room temperature is carried out. Washing the epoxy resin with deionized water to neutrality, adding anhydrous magnesium sulfate as water absorbent, and filtering to obtain the in-situ response corrosion-inhibiting epoxy resin.
Example 4:
a preparation method of in-situ response corrosion-inhibition epoxy resin comprises the following steps:
(1) 0.1mol of dinitrogen bisphenol fluorene is added into a 250mL three-neck flask, 0.2mol of NaOH aqueous solution is slowly dropped under magnetic stirring, and the temperature is heated to 50 ℃ until the dinitrogen bisphenol fluorene is completely dissolved. Slowly dropwise adding 0.05mol of dimethyldichlorosilane, continuously reacting for 6h within 10min, and detecting the reaction process by thin layer chromatography. After the reaction is finished, dropwise adding dilute sulfuric acid into the reaction liquid to adjust the pH value of the solution to be 7, separating out a light yellow solid, carrying out suction filtration, repeatedly washing water and ethanol for multiple times, and drying for 10 hours to obtain solid silylation dinitrogen bisphenol fluorene;
(2) adding 10mL of toluene and 40mL of N, N-dimethylformamide into a three-neck flask with condensed water, adding 0.2mol of methyl silanization dinitrobisphenol fluorene under mechanical stirring till complete dissolution, and then adding 0.6mol of epichlorohydrin till uniform mixing. Continuously adding 0.001mol of catalyst N-chlorosuccinimide, and reacting for 60min at 80 ℃. After cooling to 50 ℃, 5g of KOH aqueous solution is added, reacted for 4 hours, and cooled to room temperature. Washing the epoxy resin with deionized water to neutrality, adding anhydrous magnesium sulfate as water absorbent, and filtering to obtain the in-situ response corrosion-inhibiting epoxy resin.
Example 5:
a preparation method of in-situ response corrosion-inhibition epoxy resin comprises the following steps:
(1) 0.15mol of dinitrobisphenol fluorene is added into a 250mL three-neck flask, an aqueous solution of 0.3mol of KOH is slowly added dropwise under magnetic stirring, and the mixture is heated to 60 ℃ until the dinitrobisphenol fluorene is completely dissolved. Slowly dripping 0.075mol of diphenyldichlorosilane, continuing to react for 6 hours after finishing dripping within 20min, and detecting the reaction process by thin layer chromatography. After the reaction is finished, dropwise adding dilute sulfuric acid into the reaction liquid to adjust the pH value to 8, separating out a light yellow solid, carrying out suction filtration, repeatedly washing water and ethanol for multiple times, and drying for 10 hours to obtain solid phenylsilylated dinitrogen bisphenol fluorene;
(2) adding 25mL of toluene and 25mL of N, N-dimethylacetamide into a three-neck flask with condensed water, adding 0.05mol of phenyl silanization dinitrobisphenol fluorene under mechanical stirring till complete dissolution, and then adding 0.9mol of epichlorohydrin till uniform mixing. 0.001mol of tetrabutylammonium bromide as a catalyst is added continuously, and the reaction is carried out for 30min at 80 ℃. After cooling to 60 ℃,10 g of NaOH aqueous solution is added, reaction is carried out for 5h, and cooling to room temperature is carried out. Washing the epoxy resin with deionized water to neutrality, adding anhydrous magnesium sulfate as water absorbent, and filtering to obtain the in-situ response corrosion-inhibiting epoxy resin.
Example 6:
a preparation method of in-situ response corrosion-inhibition epoxy resin comprises the following steps:
(1) 0.15mol of dinitrobisphenol fluorene is added into a 250mL three-neck flask, an aqueous solution of 0.3mol of KOH is slowly added dropwise under magnetic stirring, and the mixture is heated to 60 ℃ until the dinitrobisphenol fluorene is completely dissolved. Slowly dripping 0.075mol of diphenyldichlorosilane, continuing to react for 6 hours after finishing dripping within 20min, and detecting the reaction process by thin layer chromatography. After the reaction is finished, dropwise adding dilute sulfuric acid into the reaction liquid to adjust the pH value to 8, separating out a light yellow solid, carrying out suction filtration, repeatedly washing water and ethanol for multiple times, and drying for 10 hours to obtain solid phenylsilylated dinitrogen bisphenol fluorene;
(2) 20mL of toluene and 30mL of N, N-dimethylacetamide are added into a three-neck flask with condensed water, 0.1mol of phenyl silanization dinitrogen bisphenol fluorene is added under mechanical stirring until the phenyl silanization dinitrogen bisphenol fluorene is completely dissolved, and then 0.8mol of epoxy chloropropane is added until the mixture is uniformly mixed. 0.001mol of tetrabutylammonium bromide as a catalyst is added continuously, and the reaction is carried out for 30min at 80 ℃. After cooling to 60 ℃,10 g of NaOH aqueous solution is added, reaction is carried out for 5h, and cooling to room temperature is carried out. Washing the epoxy resin with deionized water to be neutral, adding anhydrous sodium sulfate as a water absorbent, and filtering to obtain the in-situ response corrosion-inhibition epoxy resin.
Example 7:
a preparation method of in-situ response corrosion-inhibition epoxy resin comprises the following steps:
(1) 0.15mol of dinitrobisphenol fluorene is added into a 250mL three-neck flask, an aqueous solution of 0.3mol of KOH is slowly added dropwise under magnetic stirring, and the mixture is heated to 60 ℃ until the dinitrobisphenol fluorene is completely dissolved. Slowly dripping 0.075mol of diphenyldichlorosilane, continuing to react for 6 hours after finishing dripping within 20min, and detecting the reaction process by thin layer chromatography. After the reaction is finished, dropwise adding dilute hydrochloric acid into the reaction liquid to adjust the pH value to 8, precipitating a light yellow solid, carrying out suction filtration, repeatedly washing water and ethanol for multiple times, and drying for 10 hours to obtain solid methyl silanization dinitrogen bisphenol fluorene;
(2) adding 15mL of toluene and 35mL of N-methylpyrrolidone into a three-neck flask with condensed water, adding 0.15mol of phenyl silanization dinitrogen bisphenol fluorene under mechanical stirring till complete dissolution, and then adding 0.7mol of epoxy chloropropane till uniform mixing. 0.001mol of dicyclohexyl carbodiimide as a catalyst is added continuously, and the reaction is carried out for 60min at 60 ℃. After cooling to 50 ℃,10 g of NaOH aqueous solution is added, reaction is carried out for 6h, and cooling to room temperature is carried out. Washing the epoxy resin with deionized water to be neutral, adding anhydrous sodium sulfate as a water absorbent, and filtering to obtain the in-situ response corrosion-inhibition epoxy resin.
Example 8:
a preparation method of in-situ response corrosion-inhibition epoxy resin comprises the following steps:
(1) 0.1mol of dinitrobisphenol fluorene is added into a 250mL three-neck flask, and an aqueous solution of 0.2mol of KOH is slowly added dropwise under magnetic stirring and heated to 50 ℃ until the dinitrobisphenol fluorene is completely dissolved. Slowly dripping 0.05mol of diphenyl dichlorosilane, continuing to react for 5 hours after finishing dripping within 15min, and detecting the reaction process by thin layer chromatography. After the reaction is finished, dropwise adding dilute sulfuric acid into the reaction liquid to adjust the pH value to 8, separating out yellow solid, carrying out suction filtration, repeatedly washing water and ethanol for multiple times, and drying for 10 hours to obtain solid phenylsilylated dinitrogen bisphenol fluorene;
(2) adding 10mL of toluene and 40mL of dimethyl sulfoxide into a three-neck flask with condensed water, adding 0.2mol of phenyl silanization dinitrogen bisphenol fluorene under mechanical stirring until the phenyl silanization dinitrogen bisphenol fluorene is completely dissolved, and then adding 0.6mol of epoxy chloropropane until the mixture is uniformly mixed. Continuously adding 0.001mol of catalyst N-chlorosuccinimide, and reacting for 60min at 80 ℃. After cooling to 60 ℃, 5g of NaOH aqueous solution is added, reaction is carried out for 6h, and cooling to room temperature is carried out. Washing the epoxy resin with deionized water to neutrality, adding water absorbent calcium chloride, and filtering to obtain the in-situ response corrosion-inhibiting epoxy resin.
Example 9:
a preparation method of in-situ response corrosion-inhibition epoxy resin comprises the following steps:
(1) 0.1mol of dinitrobisphenol fluorene is added into a 250mL three-neck flask, 0.2mol of aqueous solution of sodium bicarbonate is slowly added dropwise with magnetic stirring, and the mixture is heated to 50 ℃ until the dinitrobisphenol fluorene is completely dissolved. Slowly dropwise adding 0.05mol of dimethyldichlorosilane, continuously reacting for 6h within 10min, and detecting the reaction process by thin layer chromatography. After the reaction is finished, dropwise adding dilute sulfuric acid into the reaction liquid to adjust the pH value of the solution to be 7, separating out a light yellow solid, carrying out suction filtration, repeatedly washing water and ethanol for multiple times, and drying for 10 hours to obtain solid silylation dinitrogen bisphenol fluorene;
(2) adding 10mL of dimethylbenzene and 40mL of dimethyl sulfoxide into a three-neck flask with condensed water, adding 0.2mol of methyl silanization dinitrogen bisphenol fluorene under mechanical stirring until the materials are completely dissolved, and then adding 0.6mol of epoxy chloropropane until the materials are uniformly mixed. Continuously adding 0.001mol of catalyst N-chlorosuccinimide, and reacting for 60min at 80 ℃. After cooling to 60 ℃, 5g of KOH aqueous solution is added, reaction is carried out for 6h, and cooling to room temperature is carried out. Washing the epoxy resin with deionized water to neutrality, adding water absorbent phosphorus pentoxide, and filtering to obtain the in-situ response corrosion-inhibiting epoxy resin.
The obtained silylation dinitrogen bisphenol fluorene is characterized by 1H-NMR, and as shown in figure 3, the compound is proved to have correct structure and higher purity; 1H-NMR characterization of the in-situ response etching-retarded epoxy resin obtained in example 1 was carried out, as shown in FIG. 4, to confirm that the polymer structure was correct; FIG. 5 is a brown-black viscous liquid of the in-situ response corrosion-retarded epoxy resin obtained in example 1; meanwhile, the epoxy resin obtained in the embodiment 1 and the traditional epoxy resin are molded and then placed in a 220 ℃ oven, and after 2 hours, a plurality of cracks appear on the surface of the traditional epoxy resin, but the surface of the epoxy resin still keeps flat, and no foaming or dropping phenomenon occurs, so that the material is proved to have more excellent heat resistance.
A sample coated with the in-situ response corrosion-inhibition epoxy resin of example 1 and a sample coated with the conventional epoxy resin were placed in a salt spray test box, and the surface state of a paint film after 300h of salt spray test was observed. The result shows that after the salt spray test for 300h, the material disclosed by the invention generates corrosion in the scratched area, but no corrosion liquid flows down, the scratch sealing effect is obvious, and a paint film in the non-scratched area does not have bubbling, shedding and corrosion (as shown in FIG. 6); the traditional epoxy coating has large-area corrosion after 300h of salt spray test, the corrosion liquid at the scratch position obviously flows downwards, and the foaming phenomenon is serious (as shown in figure 7). The invention is proved to have excellent in-situ response corrosion inhibition characteristic and good corrosion resistance.
It should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, which is defined by the appended claims. It will be apparent to those skilled in the art that certain insubstantial modifications and adaptations of the present invention can be made without departing from the spirit and scope of the invention.
Claims (9)
1. An in-situ response corrosion-inhibition type epoxy resin has the following structural formula:
2. the method for producing an epoxy resin according to claim 1, characterized in that: the synthetic route is as follows:
the method specifically comprises the following steps:
(1) synthesis of silanized dinitrobisphenol fluorene: adding 1, 10-phenanthroline into an alkaline aqueous solution, and stirring at 50-60 ℃ until the phenanthroline is completely dissolved; adding dichlorosilane, continuously reacting for 5-8 hours to obtain reaction liquid, and filtering the reaction liquid; adding an acid solution into the reaction liquid to adjust the pH to be 7-8, filtering the precipitated solid, repeatedly washing the washing liquid for many times, and drying to obtain silanized dinitrogen bisphenol fluorene;
(2) adding a mixed solvent into a three-neck flask with condensed water, adding silanized dinitrogen bisphenol fluorene under mechanical stirring, stirring until the mixture is completely dissolved, and then adding epoxy chloropropane until the mixture is uniformly mixed; continuously adding a catalyst, and reacting for 30-60 min at 60-100 ℃; cooling to 50-60 ℃, adding an alkaline aqueous solution, reacting for 4-6 h, and cooling to room temperature; washing the epoxy resin with deionized water to be neutral, adding a water absorbent, and filtering to obtain the in-situ response corrosion-inhibition epoxy resin;
the mixed solvent in the step (2) is two or more of toluene, xylene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
3. The method of claim 2, wherein: the alkaline aqueous solution is one or more of potassium hydroxide aqueous solution, sodium hydroxide aqueous solution and sodium bicarbonate aqueous solution.
4. The method of claim 2, wherein: the dichlorosilane is one or more of dimethyldichlorosilane and diphenyldichlorosilane.
5. The method of claim 2, wherein: the acid solution is one or more of dilute sulfuric acid, dilute hydrochloric acid and glacial acetic acid.
6. The method of claim 2, wherein: the washing liquid is one or more of deionized water, methanol and ethanol.
7. The method of claim 2, wherein: the catalyst is one or more of N-chlorosuccinimide, tetrabutylammonium bromide and dicyclohexyl carbodiamide.
8. The method of claim 2, wherein: the water absorbent is one or more of anhydrous magnesium sulfate, anhydrous sodium sulfate, calcium oxide and phosphorus pentoxide.
9. Use of the epoxy resin according to claim 1 for corrosion protection of metal substrates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110212928.6A CN112979921B (en) | 2021-02-25 | 2021-02-25 | In-situ response corrosion inhibition type epoxy resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110212928.6A CN112979921B (en) | 2021-02-25 | 2021-02-25 | In-situ response corrosion inhibition type epoxy resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112979921A true CN112979921A (en) | 2021-06-18 |
| CN112979921B CN112979921B (en) | 2023-06-23 |
Family
ID=76350772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110212928.6A Active CN112979921B (en) | 2021-02-25 | 2021-02-25 | In-situ response corrosion inhibition type epoxy resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112979921B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105925129A (en) * | 2016-05-19 | 2016-09-07 | 江苏固格澜栅防护设施有限公司 | Self-corrosion potential response type self-repairing anti-corrosion coating, preparation method and application |
| CN108864485A (en) * | 2018-08-02 | 2018-11-23 | 中国船舶重工集团公司第七二五研究所 | A kind of preparation method of the large volume segment modified graphene oxide of polymolecularity |
| CN109370157A (en) * | 2018-10-23 | 2019-02-22 | 福州大学 | A kind of siliceous response type epoxy fire retardant and its application in the epoxy |
| CN109400848A (en) * | 2018-10-23 | 2019-03-01 | 福州大学 | A kind of synthesis of fluorenyl epoxy resin and its application in thermosetting resin |
-
2021
- 2021-02-25 CN CN202110212928.6A patent/CN112979921B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105925129A (en) * | 2016-05-19 | 2016-09-07 | 江苏固格澜栅防护设施有限公司 | Self-corrosion potential response type self-repairing anti-corrosion coating, preparation method and application |
| CN108864485A (en) * | 2018-08-02 | 2018-11-23 | 中国船舶重工集团公司第七二五研究所 | A kind of preparation method of the large volume segment modified graphene oxide of polymolecularity |
| CN109370157A (en) * | 2018-10-23 | 2019-02-22 | 福州大学 | A kind of siliceous response type epoxy fire retardant and its application in the epoxy |
| CN109400848A (en) * | 2018-10-23 | 2019-03-01 | 福州大学 | A kind of synthesis of fluorenyl epoxy resin and its application in thermosetting resin |
Non-Patent Citations (1)
| Title |
|---|
| PENG YANG ET AL.: "Synthesis of a novel silicon-containing epoxy resin and its effect on flame retardancy, thermal, and mechanical properties of thermosetting resins", 《MATERIALS TODAY COMMUNICATIONS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112979921B (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109608985B (en) | Anticorrosive coating capable of being automatically repaired and preparation method thereof | |
| CN106243386B (en) | A kind of preparation method of the nm boehmite filler of surface grafting corrosion inhibitor | |
| CN111471389A (en) | Silicon dioxide microcapsule self-repairing anticorrosive coating and preparation method thereof | |
| CN110922855A (en) | Water-based high-temperature-resistant long-acting anticorrosive paint and preparation method thereof | |
| CN115286767B (en) | Antibacterial fluorine modified epoxy vinyl ester resin, preparation method thereof and multi-mechanism synergistic general anti-corrosion coating | |
| CN113388311A (en) | Preparation method of nano titanium dioxide modified hexagonal boron nitride modified coating | |
| CN106433368A (en) | Preservative coating for solar water storage tank | |
| CN115746661A (en) | Preparation method of self-repairing hydrophobic antibacterial anticorrosive coating | |
| CN114292413A (en) | Preparation method and application of self-repairing material based on aromatic carboxylic acids MOFs | |
| CN112979921B (en) | In-situ response corrosion inhibition type epoxy resin and preparation method and application thereof | |
| CN113337210A (en) | Corrosion inhibitor-loaded pH-responsive silicon dioxide nano container composite silane film and preparation and application thereof | |
| CN116285461B (en) | Photo-thermal and pH responsive self-repairing anti-corrosion coating, and preparation method and application thereof | |
| CN106630872A (en) | Special fire-resistant paint for tunnels | |
| CN113667377B (en) | Anticorrosive coating under heat-insulating layer, application thereof, coating process and anticorrosive coating | |
| CN105462430B (en) | Thick coated type polyether-ether-ketone composite coating and preparation method and application | |
| CN108441116A (en) | A kind of preparation method of fire resistant water-thinned nanometer paint | |
| CN114574062A (en) | Preparation method of modified fluorine-containing polyacrylate coating | |
| CN112500791A (en) | Single-component moisture curing polysiloxane coating for color steel tile | |
| JP2900762B2 (en) | Organic composite coated steel sheet | |
| CN114479618A (en) | Organic-inorganic hybrid material, preparation method thereof, coating and electronic display device | |
| CN115505308B (en) | Multiple stimulus response type aggregation-induced emission coating and preparation method thereof | |
| CN118005911B (en) | Preparation method of scale inhibitor | |
| CN114806478B (en) | Anticorrosive monocomponent silane modified polyether sealant and preparation method thereof | |
| CN115806763B (en) | High-pigment-ratio water-based epoxy paint and preparation method and application thereof | |
| CN116891671B (en) | Anti-scale anticorrosive paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |