CN114539551B - Modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosion resin and preparation method and application thereof - Google Patents
Modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosion resin and preparation method and application thereof Download PDFInfo
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- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- 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
- C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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- 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
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosion resin, and a preparation method and application thereof. According to the invention, a modified graphene oxide which is covered by silicon dioxide and contains terminal epoxy groups is synthesized, the modified graphene oxide is ultrasonically dispersed in epoxy resin, unsaturated monobasic acid is used for semi-end sealing, tung oil acid maleic anhydride is used for chain extension, and finally an active diluent is added for adjusting viscosity, so that the finished resin is obtained. According to the invention, the modified graphene oxide is introduced into the tung oil acid maleic anhydride vinyl ester anti-corrosion resin, and uniformly dispersed in the resin, so that the anti-corrosion performance of the resin is greatly improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosion resin and application thereof.
Background
The surface coating technology plays an important role in daily life, and the surface substrate can be protected, decorated, protected and the like by coating the coating on the surface of a metal, textile and plastic substrate. The ocean area occupies 71% of the earth area, and the ocean environment is a high-corrosion environment due to the fact that the ocean environment contains more metal ions, so that research on the ocean anticorrosive paint is very important.
The vinyl ester paint is a metal anti-corrosion paint which is developed in recent years, and has certain anti-corrosion performance because the structure of the paint contains a plurality of benzene ring rigid structures. In the prior art, the patent application of CN113637146A discloses a tung oil acid maleic anhydride modified vinyl ester resin which is prepared from the following raw materials in parts by weight: 4-22 parts of tung acid, 1.6-7.8 parts of maleic anhydride, 140-150 parts of epoxy resin, 20-50 parts of monohydric unsaturated carboxylic acid containing ethylenic bonds, 80-90 parts of reactive diluent, 0.9-1.1 parts of catalyst and 0.03-0.04 part of polymerization inhibitor. The tensile and bending properties, the glass transition temperature and the thermal stability of the composite material are good, but the corrosion resistance is poor, and the composite material is difficult to use in a marine high-corrosion environment, so that the application range of the composite material is limited.
Graphene is a novel two-dimensional carbon material which has a lamellar structure and has larger electric conductivity, mechanical property and heat conduction property, so that the graphene is called a new material for changing the 21 st century. In recent years, research on combining graphene with paint for marine anticorrosive paint has been increased year by year, and by dispersing graphene in paint, labyrinth effect of corrosion circuit of paint can be increased, thereby increasing anticorrosive performance of paint. However, since graphene has better conductivity, the application of graphene in corrosion prevention is not facilitated, and the compatibility of graphene and resin is poor, so that the graphene is difficult to uniformly disperse in the resin. Therefore, how to reduce the conductivity of graphene and increase the dispersibility of graphene in resin, so as to enhance the corrosion resistance of the resin, has become a difficult problem.
Disclosure of Invention
The first aim of the invention is to provide a preparation method of the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosion resin, the second aim of the invention is to provide the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosion resin prepared by the preparation method, and the third aim of the invention is to provide application of the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosion resin.
According to a first aspect of the invention, there is provided a method for preparing a modified graphene oxide/tung oil acid maleic anhydride vinyl ester preservative resin, comprising the steps of:
firstly mixing monobasic unsaturated carboxylic acid, a polymerization inhibitor, a catalyst and modified graphene oxide, performing ultrasonic dispersion for 30-60 minutes, then adding epoxy resin, reacting for 2-5 hours at 90-110 ℃ until the acid value is less than 30mgKOH/g, then adding eleostearic acid maleic anhydride, continuously reacting for 2-5 hours at 90-110 ℃ until the acid value is less than 30mgKOH/g, then cooling to below 70 ℃, adding an active diluent, diluting, and stirring for 1-2 hours to obtain the catalyst.
According to the invention, the active functional groups on the surface of the modified graphene oxide are utilized to perform chemical reaction with the eleostearic acid maleic anhydride and the monobasic unsaturated carboxylic acid in the resin synthesis process, so that the combination between the modified graphene oxide and the resin is increased, the modified graphene oxide can be uniformly dispersed in the resin, the labyrinth effect in the resin corrosion process is increased, and the corrosion resistance of the resin is further increased. Meanwhile, the epoxy groups on the modified graphene oxide can form double bonds through reaction in the resin curing process, so that the modified graphene oxide can also participate in the subsequent polymerization curing process, and the dispersibility of the graphene oxide in the resin is further improved.
According to the invention, the epoxy resin is modified by using the eleostearic acid maleic anhydride, and the bio-based long carbon chain is introduced into the epoxy resin structure, so that the resin is toughened, and carboxylic acid and anhydride groups on the eleostearic acid maleic anhydride can react with epoxy groups on the surface of the modified graphene oxide, so that the dispersion performance of the graphene can be further increased, and the labyrinth effect in the resin corrosion process is enhanced by using the dispersion of the graphene, so that the aim of enhancing the anticorrosion performance of the resin is fulfilled.
In some embodiments, the molar ratio of epoxy resin, monounsaturated carboxylic acid, eleostearic acid maleic anhydride is 1 (1.10-1.85): (0.05-0.30), preferably 1 (1.55-1.70): (0.10-0.15); the amount of the modified graphene oxide is 0.01-0.5wt% of the total mass of the epoxy resin, the monounsaturated carboxylic acid and the eleostearic acid maleic anhydride, and preferably 0.03-0.1wt%.
In some embodiments, a method of preparing modified graphene oxide (GO-560) includes the steps of:
mixing 5-15 parts by weight of tetraethyl silicate (TEOS), 160 parts by weight of ethanol and 30 parts by weight of water, stirring for 3-5 hours, then adding 0.05 part by weight of Graphene Oxide (GO), performing ultrasonic dispersion for 30-60 minutes, then adding 3-6 parts by weight of gamma- (2, 3-glycidoxy) propyl trimethoxysilane (namely silane coupling agent KH-560), stirring for 12-24 hours, then reacting for 5-8 hours under the condition of 65-75 ℃ and stirring, cooling to room temperature after the reaction is finished, centrifuging a reaction product, washing a solid substance obtained by centrifugation, and performing freeze drying to obtain the compound. The synthetic route of the modified graphene oxide is shown in figure 1.
According to the invention, a silane coupling agent is introduced into a graphene oxide system to modify the graphene oxide system, so that a modified graphene oxide particle which is covered by silicon dioxide and contains terminal epoxy groups is synthesized, the conductivity of the modified graphene oxide particle is reduced by generating a silicon dioxide insulating layer on the surface of the graphene oxide, and the dispersibility of the modified graphene oxide particle in resin is increased by introducing the epoxy groups on the surface of the silicon dioxide.
In some embodiments, the modified graphene oxide (GO-560) is prepared from the following raw materials in parts by weight: 10 parts of tetraethyl silicate, 160 parts of ethanol, 30 parts of water, 0.05 part of graphene oxide and 4 parts of silane coupling agent KH-560.
In some embodiments, the solid material resulting from centrifugation is washed 3 times with deionized water and ethanol, respectively.
The eleostearic acid maleic anhydride of the present invention can be prepared according to the preparation method disclosed in the patent application publication No. CN 113637146A.
In some embodiments, the method of making eleostearic acid maleic anhydride comprises the steps of: and (3) reacting tungstic acid with maleic anhydride for 3-4 hours at 130-150 ℃, testing a reaction product, wherein the reaction product is tested to obtain a reaction end point after the conjugated double bond peak is completely disappeared, adding ethyl acetate into the obtained reaction product for dissolution, then washing with deionized water until the effluent liquid is neutral, and then removing the ethyl acetate by rotary evaporation at 45 ℃ to obtain the catalyst. Wherein the dosage ratio of tung acid to maleic anhydride is 1mol: (1.0 to 1.5) mol, preferably 1mol: (1.0-1.2) mol.
In some embodiments, the epoxy resin is any one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, tetrabromobisphenol a type epoxy resin; the monounsaturated carboxylic acid is one or more of acrylic acid, methacrylic acid, butenoic acid and phenylacrylic acid.
In some embodiments, the catalyst is any one or more of benzyl triethyl ammonium chloride, triethylamine and triphenylphosphine in any proportion, and the catalyst is used in an amount of 0.4-2.0wt%, preferably 0.4-1.0wt%, of the total mass of the epoxy resin, the mono-unsaturated carboxylic acid and the eleostearic acid maleic anhydride.
In some embodiments, the polymerization inhibitor is any one or more of hydroquinone, p-tert-butylcatechol and catechol, and the amount of the polymerization inhibitor is 0.015-0.05wt%, preferably 0.015-0.025wt% of the total mass of epoxy resin, mono-unsaturated carboxylic acid and eleostearic acid maleic anhydride.
In some embodiments, the reactive diluent may be selected from any one of styrene, isobornyl acrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, and the reactive diluent is used in an amount of 30-45wt%, preferably 43wt%, of the total mass of epoxy resin, monounsaturated carboxylic acid, eleostearic acid maleic anhydride.
In some embodiments, the reactive diluent is styrene. Therefore, on one hand, the thermosetting anticorrosive paint resin needs lower viscosity, styrene is one of the reactive diluents with the lowest viscosity, the diluting effect of using the styrene as the reactive diluent is good, and the prepared resin has uniform appearance without layering and moderate viscosity; on the other hand, the styrene has a better rigid structure, and can ensure that the resin has good mechanical properties.
According to a second aspect of the invention, there is provided a modified graphene oxide/eleostearic acid maleic anhydride vinyl ester corrosion-resistant resin prepared by the preparation method.
According to a third aspect of the invention, there is provided the use of the modified graphene oxide/maleic anhydride vinyl ester anticorrosive resin as described above in the preparation of a UV curable coating, UV curable ink or thermally curable anticorrosive coating.
When the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anticorrosive resin is used for preparing the anticorrosive paint, the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anticorrosive resin is uniformly mixed with an accelerator accounting for 0.1 to 0.5 weight percent of the mass of the resin, and then a curing agent accounting for 0.5 to 1.5 weight percent of the mass of the resin is added, and bubbles are removed after uniform mixing.
In some embodiments, the promoter is cobalt naphthenate.
In some embodiments, the accelerator is used in an amount of 0.3 to 0.5wt% based on the mass of the resin.
In some embodiments, the curing agent is methyl ethyl ketone peroxide.
In some embodiments, the curing agent is used in an amount of 0.5 to 1.0wt% based on the mass of the resin.
The beneficial effects are that:
(1) According to the invention, modified graphene oxide is ultrasonically dispersed in epoxy resin, unsaturated monobasic acid is used for semi-end capping, tung oil acid maleic anhydride is used for chain extension, and finally an active diluent is added for adjusting viscosity, so that the anti-corrosion resin is obtained. According to the invention, the active functional groups on the surface of the GO-560 are utilized to carry out chemical reaction with the tung oil maleic anhydride and the monobasic unsaturated carboxylic acid in the resin synthesis process, so that the combination between the modified graphene oxide and the resin is increased, and the GO-560 can be uniformly dispersed in the resin, so that the labyrinth effect in the resin coating corrosion process is increased, and the corrosion resistance of the resin coating is further enhanced. Meanwhile, the epoxy groups on the modified graphene oxide can form double bonds through reaction in the resin curing process, so that the modified graphene oxide can also participate in the subsequent polymerization curing process, and the dispersibility of the graphene oxide in the resin is further improved. The modified graphene oxide can be uniformly dispersed in the resin, so that the labyrinth effect in the corrosion process of the resin coating is increased, and the corrosion resistance of the resin is greatly improved.
(2) The resin prepared by the invention has uniform appearance, is not layered, has moderate viscosity, and is suitable for preparing products with high requirements on anti-corrosion performance, such as UV coating, printing ink, anti-corrosion coating and the like.
Drawings
FIG. 1 is a synthetic route diagram of the modified graphene oxide of the present invention.
Fig. 2 is a block diagram of the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosive resin of example 1.
Fig. 3 is a fourier transform infrared spectrum of graphene oxide and modified graphene oxide of example 1.
FIG. 4 is a scanning electron microscope image of the fracture surface of the thermosetting film prepared from the resins of example 1 and comparative example 2.
FIG. 5 is an EIS circuit diagram of heat-cured films immersed for various times in an electrochemical impedance EIS test.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto. The starting materials referred to in the examples below are available commercially unless otherwise specified.
The tung oil acid maleic anhydride is prepared by the following method:
239.26g of eleostearic acid, 84.66g of maleic anhydride and magnetic stirring are put into a 1000mL round-bottom flask, the temperature is raised to 140 ℃ and the reaction is carried out for 3.5 hours, and the end point of the reaction is reached after the peak of the conjugated double bond is completely disappeared when the infrared appearance is tested. Then 300g of ethyl acetate was put into a round bottom flask for dissolution, the solution was transferred to a separating funnel and washed with deionized water until the effluent was neutral. Then the organic phase is distilled off at 45 ℃ to remove the solvent, thus obtaining the reddish brown transparent eleostearic acid maleic anhydride.
The molecular weight of the obtained eleostearic acid maleic anhydride is 376.22g/mol.
Example 1
The preparation method of the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosion resin comprises the following steps:
(1) 160g of ethanol, 30g of deionized water and 10g of tetraethyl silicate (TEOS) are added into a 500mL round bottom flask, stirred at room temperature for 3 hours, then 0.05g of Graphene Oxide (GO) is added, ultrasonic dispersion is carried out for 30 minutes, then 4g of silane coupling agent KH-560 is added, stirring is carried out overnight, then the mixture is reacted for 8 hours under the condition of 70 ℃ and magnetic stirring, the reaction product is cooled to room temperature after the reaction, the reaction product is centrifuged, the solid matters obtained by centrifugation are washed with water and ethanol for 3 times respectively, and then freeze drying is carried out, thus obtaining modified graphene oxide (GO-560).
(2) 39.20g of acrylic acid, 0.0394g of hydroquinone serving as a polymerization inhibitor, 0.9846g of benzyl triethyl ammonium chloride serving as a catalyst and 0.1980g of GO-560 are added into a 1000mL round bottom flask, ultrasonic dispersion is carried out for 30 minutes, then 145.68g of epoxy resin E-44 is added, the temperature is raised to 90 ℃ for reaction until the acid value is less than 30mgKOH/g, then 12.04g of maleic anhydride of eleostearic acid is added, the reaction is continued at 90 ℃ until the acid value is less than 30mgKOH/g, then cooling is carried out to below 70 ℃, 84.39g of styrene is added for dilution, and stirring is carried out for 1 hour, thus obtaining the catalyst.
The structure of the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosive resin of this example is shown in fig. 2.
Fourier transform infrared spectra of graphene oxide and modified graphene oxide of the embodiment are shown in fig. 3. As can be seen from the comparison of fig. 3, the raw graphene oxide (denoted as GO), the product is modified graphene oxide (denoted as GO-560), specifically:
in the Fourier transform infrared spectrum of GO, it is seen at 3390cm -1 Up to 2300cm -1 The long peak of (C) corresponds to the O-H stretching vibration of hydroxyl and carboxylic acid, at 1729cm -1 Peak of (2) corresponds to C=O stretching vibration at 1621cm -1 Peak of (2) corresponds to C=C stretching vibration at 1051cm -1 The peak of (2) corresponds to C-OH bending vibration. After the hydroxyl on GO is hydrolyzed with tetraethyl silicate and a silane coupling agent KH-560, 2932cm is seen in the Fourier transform infrared spectrum of GO-560 -1 The peak of (C) corresponds to the stretching vibration of alkyl C-H on the silane coupling agent KH-560, 1048cm -1 Peak of (C) corresponds to Si-O-C flexural vibration of 950cm -1 The occurrence of peaks corresponding to C-O-C bending vibrations of the epoxy bond, which peaks indicate successful hydrolysis of the silane coupling agent KH-560 with the hydroxyl groups on GOAnd (3) reacting, and successfully grafting the GO on the silane coupling agent. The FT-IR results therefore indicated that the product was GO-560.
Example 2
The preparation method of the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosion resin comprises the following steps:
(1) 160g of ethanol, 30g of deionized water and 10g of tetraethyl silicate (TEOS) are added into a 500mL round bottom flask, stirred at room temperature for 3 hours, then 0.05g of Graphene Oxide (GO) is added, ultrasonic dispersion is carried out for 30 minutes, then 4g of silane coupling agent KH-560 is added, stirring is carried out overnight, then the mixture is reacted for 8 hours under the condition of 70 ℃ and magnetic stirring, the reaction product is cooled to room temperature after the reaction, the reaction product is centrifuged, the solid matters obtained by centrifugation are washed with water and ethanol for 3 times respectively, and then freeze drying is carried out, thus obtaining modified graphene oxide (GO-560).
(2) 39.20g of acrylic acid, 0.0394g of hydroquinone serving as a polymerization inhibitor, 0.9846g of benzyl triethyl ammonium chloride serving as a catalyst and 0.0594g of GO-560 are added into a 1000mL round bottom flask, ultrasonic dispersion is carried out for 30 minutes, then 145.68g of epoxy resin E-44 is added, the temperature is raised to 90 ℃ for reaction until the acid value is less than 30mgKOH/g, then 12.04g of maleic anhydride of eleostearic acid is added, the reaction is continued at 90 ℃ until the acid value is less than 30mgKOH/g, then cooling is carried out to below 70 ℃, 84.39g of styrene is added for dilution, and stirring is carried out for 1 hour, thus obtaining the catalyst.
Comparative example 1
The preparation method of the graphene oxide/tung oil acid maleic anhydride vinyl ester resin of the comparative example is as follows:
39.20g of acrylic acid, 0.0394g of hydroquinone serving as a polymerization inhibitor, 0.9846g of benzyl triethyl ammonium chloride serving as a catalyst and 0.1980g of Graphene Oxide (GO) are added into a 1000mL round-bottom flask, ultrasonic dispersion is carried out for 30 minutes, then 145.68g of epoxy resin E-44 is added, the temperature is raised to 90 ℃ for reaction until the acid value is less than 30mgKOH/g, then 12.04g of maleic anhydride of eleostearic acid is added, the reaction is continued at 90 ℃ until the acid value is less than 30mgKOH/g, then the mixture is cooled to below 70 ℃, 84.39g of styrene is added for dilution, and stirring is carried out for 1 hour, thus obtaining the catalyst.
Comparative example 2
The preparation method of the tung oil acid maleic anhydride vinyl ester resin of the comparative example is as follows:
39.20g of acrylic acid, 0.0394g of hydroquinone serving as a polymerization inhibitor and 0.9846g of benzyl triethyl ammonium chloride serving as a catalyst are added into a 1000mL round-bottom flask, ultrasonic dispersion is carried out for 30 minutes, 145.68g of epoxy resin E-44 is added, the temperature is raised to 90 ℃ for reaction until the acid value is less than 30mgKOH/g, 12.04g of maleic anhydride of eleostearic acid is added, the reaction is continued at 90 ℃ until the acid value is less than 30mgKOH/g, then cooling is carried out to below 70 ℃, 84.39g of styrene is added for dilution, and stirring is carried out for 1 hour, thus obtaining the catalyst.
In order to detect the dispersibility of GO-560 in the modified graphene oxide/eleostearic acid maleic anhydride vinyl ester anticorrosive resin prepared by the invention and the anticorrosive performance of the modified graphene oxide/eleostearic acid maleic anhydride vinyl ester anticorrosive resin prepared by the invention, the resins prepared in examples 1-2 and comparative examples 1-2 are prepared into a thermosetting film, and then the prepared thermosetting film is subjected to fracture surface scanning and electrochemical impedance EIS test.
1. Preparation of thermally cured films
The tinplate purchased in the market is respectively polished by 400 meshes and 1500 meshes of sand paper, scrubbed by deionized water and absolute ethyl alcohol, and dried in an oven for standby. The resins prepared in examples 1-2 and comparative examples 1-2 were added with 0.4wt% of cobalt naphthenate, the weight of the resin, and mixed uniformly, and then with 0.8wt% of methyl ethyl ketone peroxide, the weight of the resin, and the mixture was subjected to vacuum bubble removal. And then preparing a film on a tinplate by using a 250um wet film preparation device, curing for 24 hours at room temperature, and then placing the film in a 100 ℃ oven for curing for about 5 hours to obtain the heat-cured film.
2. Thermal curing film fracture surface scanning
The thermosetting films prepared from the resins of example 1 and comparative example 2 were subjected to a fracture treatment by: brittle failure is carried out on the solidified film sample by liquid nitrogen, and then the side face of the obtained sample is stuck on conductive adhesive to carry out metal spraying.
Then, the fracture surface of the thermosetting film was scanned by a scanning electron microscope (instrument model: EVO MA 15, manufacturer: ZEISS), and the result is shown in FIG. 4, wherein FIG. 4 (a) is a scanning electron microscope (500X) of the fracture surface of the resin thermosetting film of comparative example 2, and FIG. 4 (b) is a scanning electron microscope (800X) of the fracture surface of the resin thermosetting film of example 1.
As can be seen from fig. 4 (a), the cracks in the fracture surface of the resin thermosetting film of comparative example 2 have a remarkable directional fracture law, showing a remarkable brittle fracture. FIG. 4 (b) shows that the agglomerated GO-560 particles are not seen on the fracture surface of the resin thermoset film of example 1, nor is there a significant phase separation, indicating that GO-560 has been modified to be uniformly dispersed in the resin; in addition, the cracks of the resin cured film of example 1 exhibited multiple cracks and the cracks were irregular because the GO-560 particles were closely combined with the resin as they reacted, so that during the breaking of the heat cured film, the force was dispersed along with the connection point of the inorganic particles with the resin, resulting in irregular dispersion of the cracks, which further illustrates that the GO-560 particles were uniformly dispersed in the resin.
3. Electrochemical impedance EIS test
The heat-cured films prepared from the resins of examples 1-2 and comparative examples 1-2 were subjected to electrochemical impedance EIS test by: electrochemical behavior of the coated tin electrode in 3.5wt% NaCl solution was collected using a CHI-660E electrochemical workstation equipped with a counter electrode (area 2.5cm 2 A platinum plate) of the electrode assembly, a reference electrode (saturated Ag/AgCl electrode) and a working electrode (exposed area of 1 cm) 2 Coated tin plate). Electrochemical Impedance Spectroscopy (EIS) frequency range of 10 5 Hz to 10 -2 Hz, sinusoidal perturbations of 20mV amplitude are used at Open Circuit Potential (OCP). EIS circuit diagrams of test samples at 0, 10 and 20 days of immersion. To ensure reproducibility, three parallel samples were required for each trial.
The EIS circuit diagrams of the resin-made thermosetting films of examples 1-2 and comparative examples 1-2 soaked for different times are shown in FIG. 5, wherein FIG. 5 (a) is an EIS circuit diagram of the resin-made thermosetting film of example 1 soaked for different times, FIG. 5 (b) is an EIS circuit diagram of the resin-made thermosetting film of comparative example 1 soaked for different times, FIG. 5 (c) is an EIS circuit diagram of the resin-made thermosetting film of comparative example 2 soaked for different times, and FIG. 5 (d) is an EIS circuit diagram of the resin-made thermosetting film of example 2 soaked for different times.
The thermosetting films prepared from the resins of examples 1-2 and comparative examples 1-2 were immersed in the low frequency impedance modulus |Z| for various periods of time 0.01 The values are shown in table 1.
TABLE 1 Low frequency impedance modulus of Heat-cured films immersed for various times |Z| 0.01 Value of
| Soaking time | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 |
| Day 0 | 1.18×10 11 | 1.57×10 11 | 7.03×10 9 | 8.67×10 9 |
| For 10 days | 1.06×10 11 | 1.71×10 11 | 6.22×10 9 | 3.82×10 9 |
| For 20 days | 7.48×10 10 | 1.24×10 11 | 2.46×10 9 | 7.89×10 9 |
The low-frequency impedance modulus |Z| of the thermosetting film obtained from the resins of example 1 and comparative examples 1-2 0.01 As can be seen from comparison of the values, after 0.1wt% of modified graphene oxide GO-560 is added into the tung oil acid maleic anhydride vinyl ester resin, compared with the pure resin and the resin added with 0.1wt% of graphene oxide GO, the low-frequency impedance modulus |Z| of the prepared thermosetting film is equal when the soaking time is the same 0.01 The value is improved by about two orders of magnitude, which indicates that the corrosion resistance of the resin is greatly improved.
According to the invention, the silane coupling agent KH560 is introduced into a graphene oxide system to modify the graphene oxide system, the surface of the graphene oxide has more active functional groups, epoxy groups are formed to surround the graphene oxide after modification, and the modified graphene oxide has better compatibility with epoxy resin, so that GO-560 is uniformly dispersed in the resin, the labyrinth effect of the resin coating for corroding a circuit is increased, and the corrosion resistance of the resin coating is greatly improved. In addition, graphene oxide GO has excellent conductivity in addition to poor dispersibility, so that the corrosion resistance of the resin coating prepared by adding GO resin tends to be lower than that of the resin coating prepared by pure resin. After being modified by the silane coupling agent KH560, the surface of the GO-560 is coated by a layer of silicon dioxide, so that the conductivity is reduced, and the reduction of the conductivity is beneficial to the improvement of the corrosion resistance of the resin.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anticorrosive resin is characterized by comprising the following steps of:
firstly mixing monobasic unsaturated carboxylic acid, a polymerization inhibitor, a catalyst and modified graphene oxide, performing ultrasonic dispersion for 30-60 minutes, then adding epoxy resin, reacting for 2-5 hours at 90-110 ℃ until the acid value is less than 30mgKOH/g, then adding eleostearic acid maleic anhydride, continuously reacting for 2-5 hours at 90-110 ℃ until the acid value is less than 30mgKOH/g, then cooling to below 70 ℃, adding an active diluent for dilution, and stirring for 1-2 hours to obtain the catalyst;
the preparation method of the modified graphene oxide comprises the following steps:
mixing 5-15 parts of tetraethyl silicate, 160 parts of ethanol and 30 parts of water by weight, stirring for 3-5 hours, adding 0.05 part of graphene oxide, performing ultrasonic dispersion for 30-60 minutes, adding 3-6 parts of gamma- (2, 3-glycidoxy) propyl trimethoxy silane, stirring for 12-24 hours, reacting for 5-8 hours under the condition of 65-75 ℃ and stirring, cooling to room temperature after the reaction is finished, centrifuging a reaction product, washing a solid substance obtained by centrifugation, and performing freeze drying to obtain the nano-crystalline silicon dioxide.
2. The preparation method of the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anticorrosive resin according to claim 1, wherein the molar ratio of the epoxy resin to the monounsaturated carboxylic acid to the tung oil acid maleic anhydride is 1 (1.10-1.85) (0.05-0.30), and the dosage of the modified graphene oxide is 0.01-0.5wt% of the total mass of the epoxy resin, the monounsaturated carboxylic acid and the tung oil acid maleic anhydride.
3. The method for preparing the modified graphene oxide/maleic anhydride vinyl ester corrosion-resistant resin according to claim 1 or 2, wherein the method for preparing the maleic anhydride comprises the following steps:
tung oleic acid and maleic anhydride are mixed according to a mole ratio of 1: (1.0-1.5) reacting for 3-4h at 130-150 ℃ to obtain the catalyst.
4. The method for preparing a modified graphene oxide/maleic anhydride vinyl ester corrosion-resistant resin according to claim 1 or 2, wherein the epoxy resin is any one of bisphenol a epoxy resin, bisphenol F epoxy resin, tetrabromobisphenol a epoxy resin; the monounsaturated carboxylic acid is any one or more than one of acrylic acid, methacrylic acid, butenoic acid and phenylacrylic acid in any proportion.
5. The preparation method of the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosion resin according to claim 1 or 2, wherein the catalyst is any one or a mixture of more than one of benzyl triethyl ammonium chloride, triethylamine and triphenylphosphine in any proportion, and the dosage of the catalyst is 0.4-2.0wt% of the total mass of epoxy resin, monobasic unsaturated carboxylic acid and tung oil acid maleic anhydride.
6. The method for preparing modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosive resin according to claim 1 or 2, wherein the polymerization inhibitor is any one or a mixture of more than one of hydroquinone, p-tert-butyl catechol and catechol in any proportion, and the amount of the polymerization inhibitor is 0.015-0.05wt% of the total mass of epoxy resin, mono-unsaturated carboxylic acid and tung oil acid maleic anhydride.
7. The preparation method of the modified graphene oxide/eleostearic acid maleic anhydride vinyl ester corrosion-resistant resin according to claim 1 or 2, wherein the reactive diluent is styrene, and the amount of the reactive diluent is 30-45wt% of the total mass of epoxy resin, monounsaturated carboxylic acid and eleostearic acid maleic anhydride.
8. The modified graphene oxide/eleostearic acid maleic anhydride vinyl ester anticorrosive resin prepared by the preparation method of any one of claims 1 to 7.
9. Use of the modified graphene oxide/tung oil acid maleic anhydride vinyl ester anti-corrosive resin according to claim 8 in the preparation of UV-curable coatings, UV-curable inks or heat-curable anti-corrosive coatings.
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