CN110577655A - modified epoxy resin emulsion and preparation method and application thereof - Google Patents
modified epoxy resin emulsion and preparation method and application thereof Download PDFInfo
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- CN110577655A CN110577655A CN201810591984.3A CN201810591984A CN110577655A CN 110577655 A CN110577655 A CN 110577655A CN 201810591984 A CN201810591984 A CN 201810591984A CN 110577655 A CN110577655 A CN 110577655A
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- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
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- 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
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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
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Abstract
the invention discloses a modified epoxy resin emulsion, a preparation method and application thereof. The preparation method comprises the following steps: heating a mixed reaction system containing N, N, N ', N' -tetramethyl-1, 6-hexanediamine, bisphenol A epoxy resin and an organic solvent for reaction, adjusting the pH value of the obtained reaction mixture to be neutral or weakly acidic, and adding water to obtain the modified epoxy resin emulsion. Compared with the prior art, the modified epoxy resin emulsion has the advantages of excellent stability, simple and convenient preparation method, no deterioration after long-time placement, small influence on the environment, easy dissolution and dispersion in the preparation process of the coating, simple preparation method, convenient batch production, and simultaneously solves the problems of uneven dispersion of pigment and filler, serious sedimentation and the like when the traditional epoxy resin is used as a film forming substance. The conductive coating prepared by the modified epoxy resin emulsion has lasting conductive performance, can slow or prevent the damage of a metal matrix, and can be applied to the protection of the grounding grid metal under different working conditions.
Description
Technical Field
The invention relates to the technical field of metal protection, in particular to a modified epoxy resin emulsion, a preparation method thereof and application thereof in a grounding grid.
background
The metal components which are buried in the soil for a long time are often corroded by the soil, so that the metal components are damaged in different degrees due to corrosion, the maintenance is difficult, the cost is high, and meanwhile, serious potential safety hazards exist. The corrosion of metal materials in soil is mainly affected by factors such as moisture, oxygen concentration, acidity and alkalinity, microorganisms and the like, and the corrosion mainly comprises three types, namely chemical corrosion, electrochemical corrosion and microbial corrosion. According to statistics, the developed countries consume about 10-20% of metals due to corrosion every year, so that the economic loss accounts for about 2-4% of the total value of national economic production, and the economic loss caused by corrosion every year in China is 4% of the total value of national production. Therefore, the study of metal corrosion protection is currently an important issue.
At present, the conductive anticorrosive paint is a main protection measure for solving the corrosion damage of a grounding grid. Most of the currently used conductive coatings have the problems of poor stability and poor conductivity, and the conductive coatings are used for a long time to increase the resistance of the conductive coatings so as to increase the heat productivity. The grounding grid anticorrosive paint prepared by using nickel powder as the conductive filler in an enterprise has poor anticorrosive performance, poor sealing performance and poor conductivity, and the conductive filler of a metal powder series is also easily oxidized. In the preparation process of the conductive coating in the prior art, the problem that the conductive performance and the corrosion resistance can not have good performance simultaneously exists.
Disclosure of Invention
The invention mainly aims to provide a modified epoxy resin emulsion, a preparation method and application thereof, so as to overcome the defects in the prior art. In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of modified epoxy resin emulsion, which comprises the following steps: heating a mixed reaction system containing N, N, N ', N' -tetramethyl-1, 6-hexamethylene diamine, bisphenol A type epoxy resin and an organic solvent to 50-70 ℃, reacting for more than 2 hours, adjusting the pH value of the obtained reaction mixture to 6.5-7, and adding water to obtain the modified epoxy resin emulsion.
The embodiment of the invention also provides a modified epoxy resin emulsion which is prepared by any one of the preparation methods of the modified epoxy resin emulsion.
The embodiment of the invention also provides a conductive coating which comprises the modified epoxy resin emulsion, conductive pigment and filler, an auxiliary agent, a solvent and an epoxy curing agent.
The embodiment of the invention also provides a preparation method of the conductive coating, which comprises the following steps:
Fully dissolving the modified epoxy resin emulsion by using a solvent to form a solution, sequentially adding a conductive pigment filler and an auxiliary agent into the solution, and fully mixing to form slurry;
And grinding the slurry, filtering by using a screen of 800-1200 meshes, and mixing the filtered slurry with an epoxy curing agent to obtain the conductive coating.
The embodiment of the invention also provides the application of the modified epoxy resin emulsion or the conductive coating in a grounding grid. Compared with the prior art, the invention has the beneficial effects that:
1) the modified epoxy resin emulsion provided by the embodiment of the invention has the advantages of simple preparation method, no deterioration after long-time placement, small influence on the environment and convenience for batch production;
2) The modified epoxy resin emulsion provided by the embodiment of the invention is used as a film forming substance when preparing a conductive coating, has excellent dispersibility on pigments and fillers, high crosslinking degree and compact network structure, and has outstanding function of the pigments and fillers. Solves the problems of uneven dispersion of pigment and filler, serious sedimentation and the like when the traditional epoxy resin is used as a film forming substance;
3) when the conductive coating provided by the embodiment of the invention is applied to a grounding grid, the conductive coating has lasting conductive performance, can improve the bonding strength of a paint film and a base material, slow or prevent the damage of a metal matrix, and can be widely applied to the protection of grounding grid metal under different working conditions.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
Aiming at the problems, the invention starts with the main film forming material epoxy resin and modifies the structure of the epoxy resin, the modified epoxy resin emulsion has better stability, has good compatibility when being mixed with pigments and fillers, highlights the inherent performance of the fillers, solves the problems that the pigments and fillers are easy to settle, deposit, are not easy to disperse and the like, and has important significance for researching green and environment-friendly coatings with excellent performance.
The preparation method of the modified epoxy resin emulsion provided by the embodiment of the invention comprises the following steps: heating a mixed reaction system containing N, N, N ', N' -tetramethyl-1, 6-hexamethylene diamine, bisphenol A type epoxy resin and an organic solvent to 50-70 ℃, reacting for more than 2 hours, adjusting the pH value of the obtained reaction mixture to 6.5-7, and adding water to obtain the modified epoxy resin emulsion.
Wherein the modified epoxy resin emulsion can be obtained by mixing and heating N, N, N ', N' -tetramethyl-1, 6-hexanediamine, bisphenol A epoxy resin and a solvent to carry out the reaction, thereby opening the epoxy bond in the bisphenol A epoxy resin and introducing a hydroxyl group and an amino group.
In some embodiments, the method of making specifically comprises: mixing N, N, N ', N' -tetramethyl-1, 6-hexanediamine, bisphenol A epoxy resin and organic solvent, and heating from room temperature to reaction temperature at a heating rate of 1-2 deg.C/min to perform the reaction.
Preferably, the reaction time is 2-5 h.
In some embodiments, the method of making specifically comprises: after the reaction is finished, removing the solvent in the obtained reaction mixture, and adjusting the pH value of the reaction mixture to 6.5-7.
Wherein the solvent in the reaction mixture can be removed by rotary evaporation or the like.
in some embodiments, the method of making specifically comprises: and adjusting the pH value of the reaction mixture to 6.5-7 by adopting weak acid.
Further, the weak acid includes any one or a combination of two or more of acetic acid, phosphoric acid, citric acid, malic acid, and benzoic acid, but is not limited thereto.
Preferably, the weak acid is any one or a combination of two or more of acetic acid, citric acid and malic acid.
In some embodiments, the molar ratio of the N, N, N ', N' -tetramethyl-1, 6-hexanediamine to the bisphenol A epoxy resin is from 1: 2.0 to 1: 3.0.
preferably, the molar ratio of the N, N, N ', N' -tetramethyl-1, 6-hexanediamine to the bisphenol A epoxy resin is 1: 2.5-1: 3.0.
In some embodiments, the bisphenol a type epoxy resin includes any one or a combination of two or more of E20, E44, E51, and novolac epoxy resin, and is not limited thereto.
Further, the bisphenol a type epoxy resin may be a combination of a novolac epoxy resin and E20.
Further, the mass ratio of the novolac epoxy resin to the E20 is 1: 1-1: 2.
In some embodiments, the solvent includes an organic solvent including any one or a combination of two or more of acetone, ethyl acetate, ethylene glycol ethyl ether acetate, cyclohexanone, ethanol, n-butanol, and n-hexane, and is not limited thereto.
further, the solvent is a mixed solvent of acetone and ethyl acetate.
wherein the dosage ratio of the acetone to the 97% ethyl acetate is preferably 1: 1-1: 2.
in some more specific embodiments, the method for preparing the modified epoxy resin emulsion specifically comprises: firstly, putting N, N, N ', N' -tetramethyl-1, 6-hexamethylene diamine and bisphenol A epoxy resin into a reaction container (such as a three-neck flask), adding an organic solvent, slowly heating to the reaction temperature for reaction, discharging the solvent in an obtained reaction mixed system in a rotary evaporation mode and the like after the reaction is finished, then adjusting the pH value of the mixed system to 6.5-7 by weak acid, adding deionized water after the reaction is completed, and stirring to obtain viscosity, thereby preparing the modified epoxy resin emulsion with the solid content of 60% -85%.
correspondingly, the embodiment of the invention also provides a modified epoxy resin emulsion, which is prepared by any preparation method of the modified epoxy resin emulsion.
In some embodiments, the modified epoxy resin emulsion has a viscosity of 250 to 350 cp.
Preferably, the viscosity of the modified epoxy resin emulsion is 300-350 cp.
The modified epoxy resin emulsion provided by the invention has good stability, can be placed for a long time without deterioration, has small influence on the environment, is easy to dissolve and disperse in the preparation process of the coating, and is simple and convenient in preparation method.
Correspondingly, the embodiment of the invention also provides a conductive coating, which comprises the modified epoxy resin emulsion, conductive pigment and filler, an auxiliary agent, a solvent and a curing agent.
In some embodiments, the conductive coating comprises, by mass, 15% to 25% of the modified epoxy resin emulsion, 40% to 60% of the conductive pigment, filler and auxiliary agent, and the balance comprising a solvent and an epoxy curing agent.
Correspondingly, the embodiment of the invention also provides a method for preparing the conductive coating, which comprises the following steps:
Fully dissolving the modified epoxy resin emulsion by using a solvent to form a solution, sequentially adding a conductive pigment filler and an auxiliary agent into the solution, and fully mixing to form slurry;
And grinding the slurry, filtering by using a screen of 800-1200 meshes, and mixing the filtered slurry with an epoxy curing agent to obtain the conductive coating.
In some more specific embodiments, the method of preparing the conductive coating comprises the steps of:
(1) Fully dissolving the modified epoxy resin emulsion by using a solvent, sequentially adding the conductive pigment, filler and auxiliary agent into the solution, and stirring for 1h at the speed of 1500r/min by using a high-speed stirrer;
(2) Grinding the slurry obtained in the step (1) and zirconium beads in a grinding machine for 12 hours, then filtering by using a screen with 800-1200 meshes, and stirring at the rotating speed of 1500r/min for 0.5 hour;
(3) And (3) adding a proper amount of epoxy curing agent into the slurry filtered and stirred in the step (2), and uniformly stirring to obtain the conductive coating.
Further, in the step (2), the mass ratio of the slurry to the zirconium beads is 1: 1.
When the conductive coating is prepared, the modified epoxy resin emulsion is used as a film forming substance, the dispersibility of the conductive coating on pigments and fillers is excellent, the modified epoxy resin emulsion is high in crosslinking degree and compact in network structure, the functional effect of the pigments and fillers is outstanding, and the problems that the pigments and fillers are not uniformly dispersed and are seriously settled when the traditional epoxy resin is used as the film forming substance are solved.
Correspondingly, the embodiment of the invention also provides the application of the modified epoxy resin emulsion or the conductive coating in a grounding grid. For example, the embodiment of the invention also provides the application of the conductive coating as an anticorrosion coating of a grounding grid.
When the conductive coating is applied to a functional coating of a power grid grounding grid, the conductive coating has lasting conductive performance, can improve the bonding strength of a paint film and a base material, and slows down or prevents the damage of a metal matrix, so that the conductive coating can be widely applied to the protection of grounding grid metal under different working conditions.
The technical solution of the present invention will be described in further detail below with reference to examples. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1:
0.5mol of mixed resin of novolac epoxy and E20 with the mass ratio of 1: 1 and 0.5mol of mixed solvent of acetone and ethyl acetate with the mass ratio of 1: 1 are added into a three-neck flask, wherein a thermometer, a condenser tube and a dropping funnel are respectively arranged in the three-neck flask. Adding 0.25mol of N, N, N ', N' -tetramethyl-1, 6-hexanediamine, slowly heating to 50 ℃ at the heating speed of 2 ℃/min, carrying out constant-temperature continuous reaction for 2.5h, and then discharging the solvent in the system in a rotary evaporation mode. And finally, adjusting the pH value to 6.5-7 by using acetic acid, adding deionized water after the reaction is completed, stirring until the viscosity is 300cp, and preparing the modified epoxy resin emulsion with the solid content of 65-75%.
The conductive coating applied to the grounding grid is prepared by taking the modified epoxy resin emulsion as a film forming substance, and the preparation process comprises the following steps:
And (2) taking a proper amount of solvent to fully dissolve the modified epoxy resin emulsion, wherein the mass ratio of the solvent to the modified epoxy resin emulsion is 3: 1, then sequentially adding 30-45 parts of conductive pigment and filler and 12-18 parts of auxiliary agent into the solution, and stirring for 1 hour at 1500r/min by using a high-speed stirrer. The obtained slurry and zirconium beads are ground for 12 hours in a grinding machine according to the mass ratio of 1: 1, then filtered by a screen with 800-1200 meshes, and stirred for 0.5 hour at the rotating speed of 1500 r/min. And (3) adding a proper amount of epoxy curing agent into the prepared slurry, and uniformly stirring to obtain the conductive coating.
Example 2:
0.5mol of mixed resin of novolac epoxy and E20 with the mass ratio of 1: 1.5 and 0.5mol of mixed solvent of acetone and ethyl acetate with the mass ratio of 1: 1.5 are added into a three-mouth flask, wherein the three-mouth flask is respectively provided with a thermometer, a condenser and a dropping funnel. Adding 0.25mol of N, N, N ', N' -tetramethyl-1, 6-hexanediamine, slowly heating to 60 ℃ at the heating speed of 2 ℃/min, carrying out constant-temperature continuous reaction for 3h, and then discharging the solvent in the system in a rotary evaporation mode. And finally, adjusting the pH value to 6.5-7 by using acetic acid, adding a certain amount of deionized water after the reaction is completed, and stirring until the viscosity is 270cp, thereby preparing the modified epoxy resin emulsion with the solid content of 60-70%.
The conductive paint was prepared in the same manner as in example 1.
Example 3:
mixing 1.5mol of the mixture with the mass ratio of 1: the mixed resin of 2-novolac epoxy and E20 and 0.5mol of a mixed solvent of acetone and ethyl acetate in a mass ratio of 1: 2 are added into a three-neck flask, wherein a thermometer, a condenser tube and a dropping funnel are respectively arranged in the three-neck flask. Adding 0.5mol of N, N, N ', N' -tetramethyl-1, 6-hexanediamine, slowly heating to 55 ℃ at the heating speed of 1 ℃/min, carrying out constant-temperature continuous reaction for 4h, and then discharging the solvent in the system in a rotary evaporation mode. And finally, adjusting the pH value to 6.5-7 by using acetic acid, adding a certain amount of deionized water after the reaction is completed, and stirring until the viscosity is 330cp, thereby preparing the modified epoxy resin emulsion with the solid content of 75-85%.
The conductive paint was prepared in the same manner as in example 1.
Example 4:
1mol of mixed resin of epoxy E51 and E20 in a mass ratio of 1: 1 and 0.5mol of mixed solvent of n-butanol and ethyl acetate in a mass ratio of 1: 1.5 are added into a three-neck flask, wherein a thermometer, a condensation tube and a dropping funnel are respectively arranged in the three-neck flask. Adding 0.5mol of N, N, N ', N' -tetramethyl-1, 6-hexanediamine, slowly heating to 70 ℃ at the heating speed of 1.5 ℃/min, carrying out constant-temperature continuous reaction for 4.5h, and then discharging the solvent in the system in a rotary evaporation mode. And finally, adjusting the pH value to 6.5-7 by using malic acid, adding a certain amount of deionized water after the reaction is completed, and stirring until the viscosity is 310cp, thereby preparing the modified epoxy resin emulsion with the solid content of 60-70%.
the conductive paint was prepared in the same manner as in example 1.
Example 5:
0.75mol of a mixed resin of epoxy E44 and E20 in a mass ratio of 1: 2.5 and 0.5mol of a mixed solvent of cyclohexanone and ethanol in a mass ratio of 1: 1.3 are added into a three-necked flask, wherein a thermometer, a condenser and a dropping funnel are respectively arranged in the three-necked flask. Adding 0.25mol of N, N, N ', N' -tetramethyl-1, 6-hexanediamine, slowly heating to 65 ℃ at the heating speed of 1.6 ℃/min, carrying out constant-temperature continuous reaction for 3.5h, and then discharging the solvent in the system in a rotary evaporation mode. And finally, adjusting the pH value to 6.5-7 by using acetic acid, adding a certain amount of deionized water after the reaction is completed, and stirring until the viscosity is 290cp, thereby preparing the modified epoxy resin emulsion with the solid content of 65-75%.
The conductive paint was prepared in the same manner as in example 1.
example 6:
0.5mol of mixed resin of epoxy E51 and E44 with the mass ratio of 1: 1.5 and 0.5mol of mixed solvent of ethyl acetate and n-butanol with the mass ratio of 1: 2 are added into a three-mouth flask which is respectively provided with a thermometer, a condenser and a dropping funnel. Adding 0.25mol of N, N, N ', N' -tetramethyl-1, 6-hexanediamine, slowly heating to 68 ℃ at the heating speed of 1.2 ℃/min, carrying out constant-temperature continuous reaction for 4.5h, and then discharging the solvent in the system in a rotary evaporation mode. And finally, adjusting the pH value to 6.5-7 by using acetic acid, adding a certain amount of deionized water after the reaction is completed, and stirring until the viscosity is 350cp, thereby preparing the modified epoxy resin emulsion with the solid content of 65-80%.
The conductive paint was prepared in the same manner as in example 1.
Example 7:
0.5mol of mixed resin of novolac epoxy and E20 with the mass ratio of 1: 2 and 0.5mol of mixed solvent of acetone and ethanol with the mass ratio of 1: 2 are added into a three-mouth flask, wherein a thermometer, a condenser tube and a dropping funnel are respectively arranged in the three-mouth flask. Adding 0.25mol of N, N, N ', N' -tetramethyl-1, 6-hexanediamine, slowly heating to 60 ℃ at the heating speed of 2 ℃/min, carrying out constant-temperature continuous reaction for 3.6h, and then discharging the solvent in the system in a rotary evaporation mode. And finally, adjusting the pH value to 6.5-7 by using citric acid, adding a certain amount of deionized water after complete reaction, and stirring until the viscosity is 350cp, thereby preparing the modified epoxy resin emulsion with the solid content of 60-70%.
The conductive paint was prepared in the same manner as in example 1.
Example 8:
0.5mol of mixed resin of novolac epoxy and E20 in a mass ratio of 1: 1 and 1mol of mixed solvent of acetone and cyclohexanone in a mass ratio of 1: 2 are added into a three-neck flask, wherein the three-neck flask is respectively provided with a thermometer, a condenser and a dropping funnel. Adding 0.25mol of N, N, N ', N' -tetramethyl-1, 6-hexanediamine, slowly heating to 50 ℃ at the heating speed of 1 ℃/min, carrying out constant-temperature continuous reaction for 3h, and then discharging the solvent in the system in a rotary evaporation mode. And finally, adjusting the pH value to 6.5-7 by using acetic acid, adding a certain amount of deionized water after the reaction is completed, stirring until the viscosity is 320cp, and preparing the modified epoxy resin emulsion with the solid content of 75-85%.
The conductive paint was prepared in the same manner as in example 1.
Example 9:
0.75mol of mixed resin of novolac epoxy and E51 with the mass ratio of 1: 2 and 0.5mol of mixed solvent of acetone and ethyl acetate with the mass ratio of 1: 1.5 are added into a three-neck flask, wherein a thermometer, a condenser tube and a dropping funnel are respectively arranged in the three-neck flask. Adding 0.25mol of N, N, N ', N' -tetramethyl-1, 6-hexanediamine, slowly heating to 60 ℃ at the heating speed of 2 ℃/min, carrying out constant-temperature continuous reaction for 3h, and then discharging the solvent in the system in a rotary evaporation mode. And finally, adjusting the pH value to 6.5-7 by using malic acid, adding a certain amount of deionized water after the reaction is completed, and stirring until the viscosity is 250cp, thereby preparing the modified epoxy resin emulsion with the solid content of 60-75%.
The conductive paint was prepared in the same manner as in example 1.
Example 10:
0.5mol of mixed resin of novolac epoxy and E20 with the mass ratio of 1: 2.5 and 0.5mol of mixed solvent of acetone and ethyl acetate with the mass ratio of 1: 2 are added into a three-neck flask, wherein a thermometer, a condenser tube and a dropping funnel are respectively arranged in the three-neck flask. Adding 0.25mol of N, N, N ', N' -tetramethyl-1, 6-hexanediamine, slowly heating to 70 ℃ at the heating speed of 2 ℃/min, carrying out constant-temperature continuous reaction for 5h, and then discharging the solvent in the system in a rotary evaporation mode. And finally, adjusting the pH value to 6.5-7 by using acetic acid, adding a certain amount of deionized water after the reaction is completed, and stirring until the viscosity is 350cp, thereby preparing the modified epoxy resin emulsion with the solid content of 65-70%.
the conductive paint was prepared in the same manner as in example 1.
the modified epoxy resin emulsions of examples 1 to 10 were subjected to various property tests, and the test results are shown in Table 1; the conductive coatings prepared in examples 1 to 10 were subjected to the relevant property tests, and the test results are shown in table 2.
TABLE 1 detection of various properties of modified epoxy resin emulsions
| group of | appearance of the emulsion | Mechanical stability | Compatibility | average particle diameter | Solid content |
| 1 | Is transparent | emulsion breaking and flocculation preventing emulsion | Light transmission | 50nm | 68.9％ |
| 2 | Is transparent | Emulsion breaking and flocculation preventing emulsion | Light transmission | 69nm | 63.1％ |
| 3 | is transparent | Emulsion breaking and flocculation preventing emulsion | slightly transparent | 87nm | 76.2％ |
| 4 | Semi-transparent | Emulsion breaking and flocculation preventing emulsion | Slightly transparent | 59nm | 60.5％ |
| 5 | Is transparent | Emulsion breaking and flocculation preventing emulsion | Light transmission | 73nm | 74.3％ |
| 6 | Is transparent | Emulsion breaking and flocculation preventing emulsion | Light transmission | 85nm | 68.7％ |
| 7 | Is transparent | Emulsion breaking and flocculation preventing emulsion | Light transmission | 61nm | 66.1％ |
| 8 | Is transparent | Emulsion breaking and flocculation preventing emulsion | Slightly transparent | 102nm | 84.8％ |
| 9 | Semi-transparent | Emulsion breaking and flocculation preventing emulsion | Slightly transparent | 103nm | 72.9％ |
| 10 | Semi-transparent | Emulsion breaking and flocculation preventing emulsion | Slightly transparent | 127nm | 67.2％ |
| Is commercially available | is slightly transparent | Emulsion breaking and flocculation preventing emulsion | Difference in light transmission | 158nm | 64％ |
TABLE 2 conductive coating-related Performance test
Compared with commercially available epoxy emulsions and corresponding conductive coatings, the modified epoxy resin emulsion and the conductive coating obtained in the embodiments 1-10 have better stability after being modified, the particle size is greatly reduced, the specific surface area is greatly increased, the modified epoxy resin emulsion and the conductive coating are better compatible with pigments, fillers and additives, and the formed film is more uniform. The network structure of the epoxy resin is more compact through modification, and aggressive ions such as chloride ions, sulfate ions and the like are blocked, so that the service life of the metal matrix is greatly prolonged. Meanwhile, the modified epoxy resin has excellent conductivity in the preparation process of the coating, and mainly the energy band structure is changed by the connection of amino and hydroxyl groups.
In addition, the inventor also carries out corresponding experiments by using other raw materials and other process conditions listed above instead of various raw materials and corresponding process conditions in the examples 1 to 10, and the contents to be verified are similar to the products in the examples 1 to 10. Therefore, the contents of the verification of the respective examples are not described herein, and the excellent points of the present invention will be described only by examples 1 to 10 as representative examples.
It should be understood that the above describes only some embodiments of the present invention and that various other changes and modifications may be affected therein by one of ordinary skill in the related art without departing from the scope or spirit of the invention.
Claims (10)
1. A preparation method of modified epoxy resin emulsion is characterized by comprising the following steps:
Heating a mixed reaction system containing N, N, N' -tetramethyl-1, 6-hexanediamine, bisphenol A type epoxy resin and an organic solvent to 50-70 ℃, reacting for more than 2 hours, adjusting the pH value of the obtained reaction mixture to 6.5-7, and adding water to obtain the modified epoxy resin emulsion.
2. The method according to claim 1, comprising:
Mixing N, N, N' -tetramethyl-1, 6-hexanediamine, bisphenol A epoxy resin and organic solvent, and heating from room temperature to reaction temperature at a heating rate of 1-2 deg.C/min to perform the reaction.
3. The production method according to claim 1 or 2, characterized in that: the reaction time is 2-5 h.
4. the method according to claim 1, comprising: after the reaction is finished, removing the solvent in the obtained reaction mixture, and adjusting the pH value of the reaction mixture to 6.5-7.
5. the method according to claim 1, comprising: adjusting the pH value of the reaction mixture to 6.5-7 by adopting weak acid; preferably, the weak acid comprises any one or a combination of two or more of acetic acid, phosphoric acid, citric acid, malic acid and benzoic acid.
6. the method of claim 1, wherein: the molar ratio of the N, N, N' -tetramethyl-1, 6-hexanediamine to the bisphenol A epoxy resin is 1: 2.0-1: 3.0;
And/or the bisphenol A epoxy resin comprises any one or the combination of more than two of E20, E44, E51 and phenolic epoxy resin; preferably, the bisphenol A epoxy resin comprises phenolic epoxy resin and E20 in a mass ratio of 1: 1-1: 2.5;
And/or the organic solvent comprises any one or the combination of more than two of acetone, ethyl acetate, ethylene glycol ethyl ether acetate, cyclohexanone, ethanol, n-butyl alcohol and n-hexane; preferably, the solvent comprises acetone and ethyl acetate in a mass ratio of 1: 1-1: 2;
And/or the viscosity of the modified epoxy resin emulsion is 250-350 cp.
7. A modified epoxy resin emulsion prepared by the preparation method of any one of claims 1 to 6.
8. A conductive coating, characterized by comprising the modified epoxy resin emulsion of claim 7, a conductive pigment, a filler, an auxiliary agent, a solvent and an epoxy curing agent; preferably, the conductive coating comprises, by mass, 15 to 25 wt% of the modified epoxy resin emulsion and 40 to 60 wt% of the conductive pigment filler, and the balance of the conductive coating comprises an auxiliary agent, a solvent and an epoxy curing agent.
9. The method for preparing the conductive paint according to claim 8, comprising:
Fully dissolving the modified epoxy resin emulsion by using a solvent to form a solution, sequentially adding a conductive pigment filler and an auxiliary agent into the solution, and fully mixing to form slurry;
And grinding the slurry, filtering by using a screen of 800-1200 meshes, and mixing the filtered slurry with an epoxy curing agent to obtain the conductive coating.
10. Use of the modified epoxy resin emulsion of claim 7 or the conductive coating of claim 9 in a grounding grid.
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| CN113480747A (en) * | 2021-07-02 | 2021-10-08 | 江南大学 | Preparation and application of epoxy acrylate microsphere emulsion |
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