CN115058170A - Modified phenolic epoxy emulsion and preparation method and application thereof - Google Patents
Modified phenolic epoxy emulsion and preparation method and application thereof Download PDFInfo
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- CN115058170A CN115058170A CN202210697456.2A CN202210697456A CN115058170A CN 115058170 A CN115058170 A CN 115058170A CN 202210697456 A CN202210697456 A CN 202210697456A CN 115058170 A CN115058170 A CN 115058170A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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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
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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
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of phenolic epoxy emulsion preparation, and particularly discloses a modified phenolic epoxy emulsion and a preparation method and application thereof. The invention discloses a modified phenolic epoxy emulsion which comprises the following components in parts by mass: 20-80 parts of epoxy compound, 5-20 parts of polyether amine, 2-30 parts of rubber, 1-6 parts of organic solvent and 20-60 parts of water; the preparation method disclosed by the invention comprises the steps of heating an epoxy compound, adding polyetheramine, and reacting for 2-8 hours to obtain the hydrophilic modified novolac epoxy resin with emulsifying capacity. And adding rubber, performing heat preservation reaction for 1-2 hours, cooling to 50-80 ℃, and adding water under a high-speed stirring state to prepare the modified phenolic epoxy emulsion. The preparation method is simple, and the obtained modified novolac epoxy emulsion has the flexibility of rubber and the heat resistance of novolac epoxy at the same time, and can be used for water-based insulating paint and pipeline anticorrosion water-based paint.
Description
Technical Field
The invention relates to the technical field of phenolic epoxy emulsion preparation, in particular to a modified phenolic epoxy emulsion and a preparation method and application thereof.
Background
The novolac epoxy resin is a multifunctional epoxy resin, has the performances of both the novolac resin and the epoxy resin, increases the rigidity of molecular chain segments of cured epoxy resin due to the increase of the functionality and the introduction of a rigid benzene ring structure, improves the heat resistance of the epoxy resin, can form a network structure with high crosslinking density after curing, and has high strength and excellent heat resistance.
The aqueous epoxy resin refers to a dispersion system in which an epoxy resin is dispersed in water in the form of fine particles or droplets. The commercially available waterborne epoxy resin mainly comprises bisphenol A type epoxy resin, and the phenolic type waterborne epoxy resin is less, mainly because the phenolic epoxy resin has stronger hydrophobicity, and the waterborne phenolic epoxy emulsion prepared by adopting the preparation method of the waterborne bisphenol A type epoxy resin has poor stability and is easy to delaminate and settle. Although many studies claim that a certain method for preparing bisphenol a type aqueous epoxy emulsions is also suitable for preparing aqueous novolac epoxy emulsions, we have found in experiments that this simple correspondence does not exist.
Because the epoxy functionality of the novolac epoxy resin is high, the internal stress is large when the novolac epoxy resin is cured into a film, and the film is brittle and has poor impact resistance. In order to overcome the defects of the epoxy resin and fully exert the excellent performance of the epoxy resin, the epoxy resin is blended and toughened by using rubber elastomers or nano particles in a solvent-based system. However, in an aqueous system, a delicate structural design is required to stably disperse these tougheners having high hydrophobicity in water.
Therefore, how to provide a modified novolac epoxy emulsion, a preparation method and an application thereof, and improving the impact resistance, flexibility and stability of the modified novolac epoxy emulsion are difficult problems to be solved in the field.
Disclosure of Invention
In view of the above, the invention provides a modified novolac epoxy emulsion, and a preparation method and an application thereof, so as to solve the problems that the existing bisphenol a epoxy resin preparation method is not suitable for preparing a water-based novolac epoxy emulsion, and the preparation of the water-based novolac epoxy emulsion in the prior art is less researched.
In order to achieve the purpose, the invention adopts the following technical scheme:
the modified phenolic epoxy emulsion is prepared from the following raw materials in parts by mass: 20-80 parts of epoxy compound, 3-20 parts of polyether amine, 2-30 parts of rubber, 1-6 parts of organic solvent and 20-60 parts of water.
Preferably, the epoxy compound includes a novolac type epoxy resin and/or a polyphenol type epoxy compound.
Preferably, the epoxy functionality of the epoxy compound is more than or equal to 2, and the epoxy equivalent is 170-220 g/eq.
Preferably, the novolac-type epoxy resin includes phenol-type novolac epoxy resin and/or cresol-type epoxy resin;
the polyphenolic epoxy compound comprises triphenolmethanetriglycidyl ether.
Preferably, the active hydrogen equivalent of the polyether amine is 150-1500 g/eq, and the amino functionality is 2-3.
Preferably, the rubber comprises one or more of vulcanized rubber, hydroxyl-terminated rubber, carboxyl-terminated rubber, epoxy-terminated rubber and mercapto-terminated rubber.
Preferably, the organic solvent comprises one or more of ethylene glycol monomethyl ether, propylene glycol methyl ether, dioxane, n-butanol, acetone or butanone.
The invention also aims to provide a preparation method of the modified phenolic epoxy emulsion, which comprises the following steps:
1) mixing the epoxy compound with the polyetheramine, and reacting to obtain polyetheramine modified novolac epoxy resin;
2) mixing the polyether amine modified phenolic epoxy resin with rubber, and reacting to obtain an intermediate product;
3) and mixing the intermediate product with an organic solvent, cooling, and then mixing with water to obtain the modified phenolic epoxy emulsion.
Preferably, the reaction temperature in the step 1) is 100-120 ℃, and the reaction time is 2-8 h;
in the step 2), the reaction temperature is 100-120 ℃, and the reaction time is 2-4 h;
and 3) reducing the temperature to 50-80 ℃.
The invention further aims to provide application of the modified phenolic epoxy emulsion in the field of pipeline corrosion prevention or the field of water-based insulating paint.
The invention adopts a hydrophilic polyether amine structure to modify a phenolic epoxy compound to obtain modified phenolic epoxy with a structure similar to an emulsifier, and then rubber components with reactive end groups react with the modified phenolic epoxy to obtain a prepolymer simultaneously containing hydrophilic ends and hydrophobic ends, wherein the structure of the prepolymer is similar to a macromolecular surfactant, and the prepolymer can be self-emulsified and can also be used for emulsifying rubber which is not grafted. After water is added into the prepolymer for phase inversion, the hydrophobic chains of the rubber and the novolac epoxy resin are effectively wrapped in the latex particles by the hydrophilic chains of the polyether amine, so that the stable rubber modified novolac epoxy emulsion is formed.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1. the modified novolac epoxy emulsion disclosed by the invention simultaneously contains a novolac epoxy component with excellent heat resistance and a rubber component with excellent flexibility, and when the modified novolac epoxy emulsion is used as a film forming material, the rubber component can effectively improve the crack extension of a novolac epoxy resin cured material, and can be used in the application fields of having certain requirements on heat resistance, good flexibility of a film and crack resistance, such as aqueous insulating paint.
2. When the modified novolac epoxy emulsion disclosed by the invention is cured, the rubber soft segment, the novolac epoxy and the curing agent are mutually interpenetrated to form a network structure, so that the flexibility, the water resistance, the chemical medium resistance and the salt water resistance of a paint film are effectively improved, and the modified novolac epoxy emulsion can also be used in the fields of pipeline corrosion prevention and metal corrosion prevention by matching with a proper curing agent.
3. The preparation method of the aqueous rubber modified phenolic epoxy emulsion is simple, the storage stability of the emulsion is excellent, and the emulsion is suitable for industrial production.
4. The aqueous rubber modified phenolic epoxy emulsion obtained by the invention has high bonding strength, can improve the impact strength of the surface of a coating film, is matched with a proper epoxy curing agent, and can be suitable for the field of floor coatings.
Detailed Description
The invention provides a modified phenolic epoxy emulsion which is prepared from the following raw materials in parts by mass: 20-80 parts of epoxy compound, 3-20 parts of polyether amine, 2-30 parts of rubber, 1-6 parts of organic solvent and 20-60 parts of water; preferably 30-60 parts of epoxy compound, 5-15 parts of polyether amine, 5-20 parts of rubber, 2-5 parts of organic solvent and 30-50 parts of water, and further preferably 50 parts of epoxy compound, 10 parts of polyether amine, 15 parts of rubber, 4 parts of organic solvent and 40 parts of water.
In the present invention, the epoxy compound includes a novolac type epoxy resin and/or a polyphenol type epoxy compound.
In the invention, the epoxy functionality of the epoxy compound is more than or equal to 2, preferably 3-5, and more preferably 4; the epoxy equivalent is 170 to 220g/eq, preferably 180 to 200g/eq, and more preferably 190 g/eq.
In the present invention, the novolac-type epoxy resin includes phenol-type novolac epoxy resin and/or cresol-type epoxy resin;
the polyphenolic epoxy compound comprises triphenolmethanetriglycidyl ether.
In the invention, the equivalent weight of active hydrogen of the polyether amine is 150-1500 g/eq, preferably 500-1200 g/eq, and more preferably 1000 g/eq; the amino functionality is 2 to 3, preferably 2.2 to 2.8, and more preferably 2.5.
In the invention, the polyether amine is preferably polyether amine containing polyethylene glycol long chain, and the average molecular weight is preferably not less than 1000, more preferably 1200-1500, and more preferably 1300.
In the invention, the rubber comprises one or more of vulcanized rubber, hydroxyl-terminated rubber, carboxyl-terminated rubber, epoxy-terminated rubber and mercapto-terminated rubber.
In the invention, the organic solvent comprises one or more of ethylene glycol monomethyl ether, propylene glycol methyl ether, dioxane, n-butanol, acetone or butanone.
In the invention, the solid content of the modified phenolic epoxy emulsion is 40-55%, preferably 42-50%, and further preferably 48%; the average particle size of the modified novolac epoxy emulsion is 200-500 nm, preferably 300-400 nm, and more preferably 350 nm.
The invention also provides a preparation method of the modified phenolic epoxy emulsion, which comprises the following steps:
1) mixing the epoxy compound with the polyetheramine, and reacting to obtain polyetheramine modified novolac epoxy resin;
2) mixing the polyether amine modified phenolic epoxy resin with rubber, and reacting to obtain an intermediate product;
3) and mixing the intermediate product with an organic solvent, cooling, and then mixing with water to obtain the modified phenolic epoxy emulsion.
In the invention, before the epoxy compound and the polyether amine are mixed, the epoxy compound is liquefied and viscosity is reduced, wherein the liquefaction and viscosity reduction temperature is 80-90 ℃, preferably 82-88 ℃, and further preferably 85 ℃.
In the invention, the reaction temperature in the step 1) is 100-120 ℃, preferably 105-115 ℃, and more preferably 110 ℃; the reaction time is 2-8 h, preferably 4-6 h, and more preferably 5 h.
In the invention, the reaction temperature in the step 2) is 100-120 ℃, preferably 105-115 ℃, and more preferably 110 ℃; the reaction time is 2-4 h, preferably 2.5-3.5 h, and more preferably 3 h.
In the invention, the temperature of the cooling operation in the step 3) is reduced to 50-80 ℃, preferably 60-70 ℃, and more preferably 65 ℃.
In the invention, the mixing in the step 3) is preferably stirring mixing, and the stirring speed is 2500-4000 rpm, preferably 2800-3500 rpm, and more preferably 3000 rpm; the stirring time is 12-20 min, preferably 15-18 min, and more preferably 16 min.
The invention also provides application of the modified phenolic epoxy emulsion in the field of pipeline corrosion prevention or the field of water-based insulating paint.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 30g of novolac epoxy resin (epoxy equivalent is 195g/eq, epoxy functionality is 3) into a 500ml reaction kettle provided with a stirring device and a thermometer, heating the novolac epoxy resin to 85 ℃, completing liquefaction and viscosity reduction, adding 6.5g of polyetheramine (M2070, Hensman; active hydrogen equivalent is 1040g/eq, amino functionality is 2), heating to 110 ℃, and carrying out heat preservation reaction for 6 hours. Then 6g of vulcanized rubber (Shandong Shawei New Material Co., Ltd., No. 7865) is added, the mixture is stirred for 2h (the temperature is kept at 110 ℃), 5g of propylene glycol methyl ether is added, the temperature is reduced to 65 ℃, 35g of deionized water is slowly added within 15min under the condition of high-speed stirring (3000rpm) for emulsification, and the modified novolac epoxy emulsion is obtained, wherein the solid content of the modified novolac epoxy emulsion is 53%, the average particle size of the modified novolac epoxy emulsion is 400nm, and the emulsion is milky and blue.
Example 2
Adding 40g of novolac epoxy resin (epoxy equivalent is 195g/eq, epoxy functionality is 3) into a 500ml reaction kettle provided with a stirring device and a thermometer, heating the novolac epoxy resin to 82 ℃, adding 5.6g of polyetheramine (M3080, Hensman; active hydrogen equivalent is 1500g/eq, amino functionality is 2), heating to 110 ℃, and carrying out heat preservation reaction for 6 hours. Then 10g of hydroxyl-terminated polybutadiene (trade name HTPB of the Letian handicraft article Co., Jining City) is added and stirred for 2h (the temperature is kept at 110 ℃), 6g of dioxane is added and cooled to 80 ℃, and 40g of deionized water is slowly added within 12min under the condition of high-speed stirring (4000rpm) for emulsification to obtain the modified novolac epoxy emulsion, wherein the solid content of the modified novolac epoxy emulsion is 50%, the average particle size of the modified novolac epoxy emulsion is 450nm, and the emulsion is milky blue.
Example 3
50g of triphenol methane triglycidyl ether (epoxy equivalent is 210g/eq, epoxy functionality is 3) is added into a 500ml reaction kettle provided with a stirring device and a thermometer, the temperature of the novolac epoxy resin is heated to 80 ℃, 10g of polyether amine (La Na Bai medicine chemical Co., Ltd., brand No. D-2000; active hydrogen equivalent is 600g/eq, amino functionality is 2) is added, the temperature is raised to 100 ℃, and the reaction is kept for 8 hours. Then 8g of epoxy-terminated polybutadiene (Jiangsu chemical (Shanghai) Co., Ltd., EPOLEAD PB 4700) is added and stirred for 4h (the temperature is kept at 100 ℃), 6g of acetone is added and cooled to 65 ℃, 40g of deionized water is slowly added within 15min under the condition of high-speed stirring (3000rpm) for emulsification, so that the modified novolac epoxy emulsion is obtained, the solid content of the modified novolac epoxy emulsion is 53%, the average particle size of the modified novolac epoxy emulsion is 380nm, and the emulsion is milky and blue.
Example 4
Adding 20g of novolac epoxy resin (epoxy equivalent is 185g/eq, epoxy functionality is 3.5) into a 500ml reaction kettle with a stirring device and a thermometer, heating the novolac epoxy resin to 90 ℃, adding 7g of polyetheramine (La Na Bai pharmaceutical chemical Co., Ltd., trade name ED-600; active hydrogen equivalent is 150g/eq, amino functionality is 3), heating to 110 ℃, and carrying out heat preservation reaction for 6 hours. Then adding 2g of carboxyl-terminated polybutadiene liquid rubber (CTPB, product number CTPB, Kagaku chemical technology Co., Ltd., Shandong) and stirring for 2h (keeping the temperature at 110 ℃), adding 2g of propylene glycol methyl ether, cooling to 65 ℃, and slowly adding 25g of deionized water for emulsification within 20min under the condition of high-speed stirring (2500rpm) to obtain the modified novolac epoxy emulsion, wherein the solid content of the modified novolac epoxy emulsion is 50%, the average particle size of the modified novolac epoxy emulsion is 420nm, and the emulsion is milky blue.
Example 5
Adding 80g of novolac epoxy resin (the epoxy equivalent is 190g/eq, the epoxy functionality is 2.7) into a 500ml reaction kettle provided with a stirring device and a thermometer, heating the novolac epoxy resin to 85 ℃, adding 20g of polyetheramine (Jining Hongming chemical reagent Co., Ltd., brand ED-900; active hydrogen equivalent is 250g/eq, the amino functionality is 2), heating to 120 ℃, and carrying out heat preservation reaction for 3 hours. Then 30g of polysulfide rubber (JLY-121, Wuhan Carnous science and technology Co., Ltd.) is added, the mixture is stirred for 2h (the temperature is kept at 120 ℃), 5g of n-butyl alcohol is added, the temperature is reduced to 50 ℃, 50g of deionized water is slowly added within 15min under the condition of high-speed stirring (3000rpm) for emulsification, the modified novolac epoxy emulsion is obtained, the solid content is 53 percent, the average particle size is about 430nm, and the emulsion is milky and blue.
Experimental example 1
TABLE 1 ingredient table for component A
Respectively preparing a component A from the modified novolac epoxy emulsion prepared in the embodiments 1 to 5 according to the following table 1, and mixing the component A with an AQUAC-3126 epoxy curing agent (Jiangsu Fuqisen) diluted by 1:1 propylene glycol methyl ether in an epoxy-amine hydrogen molar ratio of 1: 0.65 of paint preparation, spraying the paint on a polished tin plate and a polished cold-rolled steel plate to prepare a paint film, standing and leveling the constructed paint film for 15min, and then placing the paint film in an oven at 80 ℃ for curing for 2 h. The test pieces were left for 24 hours and then subjected to the performance test, and the test results are shown in Table 2.
TABLE 2 Properties of cured films of modified Novolac epoxy emulsion with AQUAC-3126 epoxy hardener (Jiangsu Fuqisen)
It can be seen from table 2 that the cured film formed by the modified phenolic epoxy emulsion prepared by the invention and the epoxy curing agent has high hardness, good flexibility, and good impact resistance and acid and alkali corrosion resistance.
Experimental example 2
Component A was prepared according to Table 1, with AQUAC-3126 epoxy curing agent (Jiangsu Fuqisen) diluted with propylene glycol methyl ether 1:1 and 1:1, and then mixed at an epoxy to amine hydrogen molar ratio of 1: 0.65 of paint preparation, spraying the paint on a polished tin plate to prepare a paint film, standing and leveling the constructed paint film for 15min, and then placing the paint film in an oven at 80 ℃ for curing for 2 h. Cured films of 35 μm, 45 μm, 55 μm, 75 μm and 85 μm were obtained in this order, and after standing for 24 hours, performance tests were performed on the cured films of different thicknesses, and the test results are shown in table 3.
TABLE 3 detection results of properties of cured films of different film thicknesses
From Table 3, it can be seen that the cured coating still exhibits excellent adhesion and impact resistance with increasing film thickness of the cured film, the film thickness has less influence on hardness, and the flexibility is maintained well when the film thickness reaches 85 μm.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The modified phenolic epoxy emulsion is characterized by being prepared from the following raw materials in parts by mass: 20-80 parts of epoxy compound, 3-20 parts of polyether amine, 2-30 parts of rubber, 1-6 parts of organic solvent and 20-60 parts of water.
2. The modified novolac epoxy emulsion of claim 1, wherein the epoxy compound comprises novolac epoxy resin and/or polyphenol epoxy compound.
3. The modified novolac epoxy emulsion of claim 2, wherein the epoxy functionality of the epoxy compound is not less than 2, and the epoxy equivalent weight is 170-220 g/eq.
4. The modified novolak epoxy emulsion according to claim 2 or 3, wherein said novolak epoxy resin comprises a phenol novolak epoxy resin and/or a cresol novolak epoxy resin;
the polyphenolic epoxy compound comprises triphenolmethanetriglycidyl ether.
5. The modified novolac epoxy emulsion according to any one of claims 1-3, wherein the polyether amine has an active hydrogen equivalent weight of 150-1500 g/eq and an amine functionality of 2-3.
6. The modified phenolic epoxy emulsion of claim 5, wherein the rubber comprises one or more of vulcanized rubber, hydroxyl-terminated rubber, carboxyl-terminated rubber, epoxy-terminated rubber and mercapto-terminated rubber.
7. The modified phenolic epoxy emulsion of claim 6, wherein the organic solvent comprises one or more of ethylene glycol monomethyl ether, propylene glycol methyl ether, dioxane, n-butanol, acetone or butanone.
8. The preparation method of the modified phenolic epoxy emulsion as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
1) mixing the epoxy compound with the polyetheramine, and reacting to obtain polyetheramine modified novolac epoxy resin;
2) mixing the polyether amine modified phenolic epoxy resin with rubber, and reacting to obtain an intermediate product;
3) and mixing the intermediate product with an organic solvent, cooling, and then mixing with water to obtain the modified phenolic epoxy emulsion.
9. The preparation method of the modified phenolic epoxy emulsion as claimed in claim 8, wherein the reaction temperature in the step 1) is 100-120 ℃, and the reaction time is 2-8 h;
in the step 2), the reaction temperature is 100-120 ℃, and the reaction time is 2-4 h;
and 3) reducing the temperature to 50-80 ℃.
10. The application of the modified phenolic epoxy emulsion of any one of claims 1 to 7 in the field of pipeline corrosion prevention or the field of water-based insulating paint.
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| CN101899196A (en) * | 2010-07-29 | 2010-12-01 | 华南理工大学 | Water-borne phenolic epoxy resin emulsion and preparation method thereof |
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| CN102337072A (en) * | 2010-07-16 | 2012-02-01 | 比亚迪股份有限公司 | Paint as well as preparation method and use method thereof |
| CN102432830A (en) * | 2011-08-02 | 2012-05-02 | 华南理工大学 | Water-based epoxy resin curing agent emulsion and preparation method thereof |
| CN112898733A (en) * | 2019-12-03 | 2021-06-04 | 南通星辰合成材料有限公司 | Water-based polyphenol epoxy emulsion and preparation method thereof |
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2022
- 2022-06-20 CN CN202210697456.2A patent/CN115058170A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102337072A (en) * | 2010-07-16 | 2012-02-01 | 比亚迪股份有限公司 | Paint as well as preparation method and use method thereof |
| CN101899196A (en) * | 2010-07-29 | 2010-12-01 | 华南理工大学 | Water-borne phenolic epoxy resin emulsion and preparation method thereof |
| CN101955589A (en) * | 2010-08-31 | 2011-01-26 | 上海三瑞化学有限公司 | Diluent-free self-emulsifying waterborne epoxy resin emulsion and preparation method thereof |
| CN102432830A (en) * | 2011-08-02 | 2012-05-02 | 华南理工大学 | Water-based epoxy resin curing agent emulsion and preparation method thereof |
| CN112898733A (en) * | 2019-12-03 | 2021-06-04 | 南通星辰合成材料有限公司 | Water-based polyphenol epoxy emulsion and preparation method thereof |
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