CN116640416A - Water-based epoxy emulsion, preparation method and application thereof, and modified water-based epoxy paint - Google Patents
Water-based epoxy emulsion, preparation method and application thereof, and modified water-based epoxy paint Download PDFInfo
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- CN116640416A CN116640416A CN202310798171.2A CN202310798171A CN116640416A CN 116640416 A CN116640416 A CN 116640416A CN 202310798171 A CN202310798171 A CN 202310798171A CN 116640416 A CN116640416 A CN 116640416A
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- emulsifier
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- aqueous epoxy
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 189
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000000839 emulsion Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003973 paint Substances 0.000 title claims description 32
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 108
- 239000003822 epoxy resin Substances 0.000 claims abstract description 50
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 49
- 238000002156 mixing Methods 0.000 claims description 44
- 239000011259 mixed solution Substances 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000010008 shearing Methods 0.000 claims description 16
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 15
- 239000002562 thickening agent Substances 0.000 claims description 15
- 239000000080 wetting agent Substances 0.000 claims description 15
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 229920006334 epoxy coating Polymers 0.000 abstract description 18
- 239000007788 liquid Substances 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 12
- 239000012752 auxiliary agent Substances 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000010998 test method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 238000007385 chemical modification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920006313 waterborne resin Polymers 0.000 description 3
- 239000013035 waterborne resin Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 glycidyl ester Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
Classifications
-
- 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
- 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
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of waterborne epoxy coating, and in particular relates to a waterborne epoxy emulsion, a preparation method and application thereof, and a modified waterborne epoxy coating. The preparation raw materials of the aqueous epoxy emulsion provided by the invention comprise: an epoxy resin, a first emulsifier, a second emulsifier and water; the first emulsifier is an aqueous epoxy emulsifier with an epoxy equivalent weight of >1000 g/eq; the second emulsifier is an aqueous epoxy emulsifier with an epoxy equivalent weight of <5000 g/eq. The small molecular emulsifier in the aqueous epoxy emulsion prepared by adopting the composite emulsifier can fill gaps among macromolecular liquid drops, the obtained emulsion has smaller particle size, regular shape and good stability, the modified aqueous epoxy coating prepared by the emulsion has compact film formation, excellent flexibility, strength, impact resistance, water resistance and corrosion resistance, the requirement of an aqueous epoxy coating system on dispersion auxiliary agents such as a dispersing agent is reduced, and the auxiliary agent cost is saved.
Description
Technical Field
The invention belongs to the technical field of waterborne epoxy coating, and in particular relates to a waterborne epoxy emulsion, a preparation method and application thereof, and a modified waterborne epoxy coating.
Background
The epoxy resin has the advantages of strong adhesive force, good chemical resistance and the like due to the special molecular structure, and is widely applied to the field of paint. The traditional epoxy resin coating has the defects of high solvent content, environmental pollution caused by solvent volatilization, harm to human health, environmental protection and convenience in construction, so that the water-based epoxy coating becomes a research hot spot at present. The water-soluble epoxy resin is a stable dispersed emulsion formed by dispersing the epoxy resin in water in some way, in the form of droplets or particles, with water as a continuous phase. The aqueous epoxy resin has the characteristics of low price, easy storage, good environmental protection, easy cleaning and the like, and has strong adhesive force, good wear resistance, excellent electrical insulation performance, and excellent corrosion resistance and chemical resistance on the aspect of service performance.
The conventional emulsification methods for preparing the water-based epoxy resin are a chemical modification method, a reverse rotation method and a mechanical method. The chemical modification method is also called as self-emulsifying method, and mainly utilizes active groups in the epoxy resin, such as hydrogen and secondary hydroxyl on methine, and the like, to introduce hydrophilic groups into the molecular skeleton of the epoxy resin by a chemical modification method, so that the epoxy resin has hydrophilic property, thereby obtaining the waterborne epoxy resin with similar surfactant property, and improving the water dispersion property of the waterborne epoxy resin. The reverse inversion method refers to the transformation of the continuous phase of an emulsion from an oil-in-water form to an aqueous-in-oil form by the interconversion of the continuous phase in a multicomponent system under specific conditions. The mechanical method is mainly that the epoxy resin is directly ground into small particles by mechanical means such as a colloid mill or a ball mill, then a certain amount of emulsifying agent and water are added, the epoxy resin and emulsifying agent particles are uniformly dispersed in aqueous solution under the mechanical stirring action, and then the aqueous solution is heated to a certain temperature, so that the uniform epoxy resin emulsion is formed. However, the water-based epoxy paint is brittle and has weaker corrosion resistance than solvent-based epoxy paint, so that the water-based epoxy paint is also required to be modified to obtain the composite paint with excellent mechanical property and corrosion resistance.
The waterborne epoxy coating consists of multiple components such as waterborne resin, filler, curing agent and the like, the performance of the waterborne resin serving as a main body of the coating determines the final performance of the coating, and how to prepare the waterborne resin with higher stability and high strength is a key factor for solving the problem of weak functionality of the waterborne epoxy coating. However, the emulsion of the water-based epoxy resin prepared by the traditional method has larger particle size, irregular particle morphology, poor stability and easy demulsification phenomenon to influence the film forming performance.
Disclosure of Invention
In view of the above, the invention aims to provide a water-based epoxy emulsion, a preparation method and application thereof, and a modified water-based epoxy coating.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a water-based epoxy emulsion, which comprises the following raw materials: an epoxy resin, a first emulsifier, a second emulsifier and water;
the first emulsifier is an aqueous epoxy emulsifier with an epoxy equivalent weight of >1000 g/eq;
the second emulsifier is an aqueous epoxy emulsifier with an epoxy equivalent weight of <5000 g/eq.
Preferably, the solid content of the aqueous epoxy emulsion is 50-75%.
Preferably, the mass ratio of the first emulsifier to the epoxy resin is 0.09-0.15:1.
Preferably, the epoxy equivalent ratio of the second emulsifier to the first emulsifier is < 1:4; the mass ratio of the second emulsifier to the first emulsifier is 1 (2-4).
The invention provides a preparation method of the aqueous epoxy emulsion, which comprises the following steps:
first mixing a first emulsifier and epoxy resin under the condition of heating and stirring to obtain a premix;
mixing the pre-mixed solution with a second emulsifier to obtain a pre-emulsified mixed solution;
and adding water into the pre-emulsified mixed solution, and performing a shearing induction phase inversion process to obtain the aqueous epoxy emulsion.
Preferably, the heating temperature is 40-90 ℃; the stirring speed is 800-1400 r/min.
Preferably, the second mixing is performed under stirring; the stirring rotating speed is 1200-1600 r/min.
Preferably, the water consumption for adding water is 1/3-2/3 of the mass of the pre-emulsified mixed liquid; the water adding time is 60-120 min; the rotating speed of the shearing is 1200-1800 r/min.
The invention provides application of the aqueous epoxy emulsion prepared by the technical scheme or the preparation method of the aqueous epoxy emulsion in aqueous epoxy paint.
The invention provides a modified water-based epoxy paint, which comprises the following raw materials: the paint comprises water-based epoxy emulsion, water, a defoaming agent, pigment and filler, a leveling agent, a wetting agent, a thickening agent and a flash rust inhibitor;
the aqueous epoxy emulsion is the aqueous epoxy emulsion prepared by the technical scheme or the preparation method.
The invention provides a water-based epoxy emulsion, which comprises the following raw materials: an epoxy resin, a first emulsifier, a second emulsifier and water; the first emulsifier is an aqueous epoxy emulsifier with an epoxy equivalent weight of >1000 g/eq; the second emulsifier is an aqueous epoxy emulsifier with an epoxy equivalent weight of <5000 g/eq. The small molecular emulsifier and the macromolecular emulsifier can fill gaps among macromolecular liquid drops, bear uniform stress on resin molecules, are mutually contained, reduce molecular agglomeration so as to reduce emulsion particle size, and the obtained emulsion has smaller particle size, regular shape and good stability, and the modified waterborne epoxy coating prepared by the modified waterborne epoxy coating has compact film formation, excellent flexibility, strength, impact resistance, water resistance and corrosion resistance, reduces the requirement of a waterborne epoxy coating system on dispersion auxiliary agents such as dispersing auxiliary agents and the like, and saves the cost of the auxiliary agents.
Detailed Description
The invention provides a water-based epoxy emulsion, which comprises the following raw materials: an epoxy resin, a first emulsifier, a second emulsifier and water;
the first emulsifier is an aqueous epoxy emulsifier with an epoxy equivalent weight of >1000 g/eq;
the second emulsifier is an aqueous epoxy emulsifier with an epoxy equivalent weight of <5000 g/eq.
The present invention is not limited to the specific source of the raw materials used, and may be commercially available products known to those skilled in the art, unless otherwise specified.
The preparation raw materials of the aqueous epoxy emulsion provided by the invention comprise epoxy resin. In the present invention, the epoxy equivalent of the epoxy resin is preferably 180 to 700g/eq, more preferably 200 to 650g/eq; the epoxy resin preferably includes one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin, and glycidyl amine type epoxy resin, more preferably bisphenol a type epoxy resin or bisphenol F type epoxy resin.
The preparation raw materials of the aqueous epoxy emulsion provided by the invention comprise a first emulsifier. In the present invention, the first emulsifier is an aqueous epoxy emulsifier having an epoxy equivalent weight of >1000g/eq, preferably 1500-25000 g/eq; the mass ratio of the first emulsifier to the epoxy resin is preferably 0.09-0.15:1, more preferably 0.12-0.14:1; the aqueous epoxy emulsifier is preferably a nonionic emulsifier.
The preparation raw materials of the aqueous epoxy emulsion provided by the invention comprise a second emulsifier. In the invention, the second emulsifier is an aqueous epoxy emulsifier with an epoxy equivalent weight of <5000g/eq, preferably 100-900 g/eq; the epoxy equivalent ratio of the second emulsifier to the first emulsifier is preferably less than 1:4, more preferably 1 (7-15); the mass ratio of the second emulsifier to the first emulsifier is preferably 1 (2-4), more preferably 1 (2-3).
The preparation raw materials of the aqueous epoxy emulsion provided by the invention comprise water. In the present invention, the water is preferably deionized water; the mass ratio of the epoxy resin to water is preferably (1 to 3): 1, more preferably (1 to 2): 1.
In the present invention, the solid content of the aqueous epoxy emulsion is preferably 50 to 75%, more preferably 55 to 70%.
The small molecular emulsifier in the aqueous epoxy emulsion prepared by adopting the composite emulsifier can fill gaps among macromolecular liquid drops, so that the aqueous epoxy emulsion has good stability.
The invention also provides a preparation method of the aqueous epoxy emulsion, which comprises the following steps:
first mixing a first emulsifier and epoxy resin under the condition of heating and stirring to obtain a premix;
mixing the pre-mixed solution with a second emulsifier to obtain a pre-emulsified mixed solution;
and adding water into the pre-emulsified mixed solution, and performing a shearing induction phase inversion process to obtain the aqueous epoxy emulsion.
The invention mixes the first emulsifier and the epoxy resin under the condition of heating and stirring to obtain the premix.
In the present invention, the heating temperature is preferably 40 to 90 ℃, more preferably 50 to 80 ℃; the rotation speed of stirring is preferably 800-1400 r/min, more preferably 900-1100 r/min; the time of the first mixing is preferably 10 to 30 minutes, more preferably 15 to 20 minutes.
After the pre-mixed solution is obtained, the pre-mixed solution is mixed with a second emulsifier for the second time to obtain a pre-emulsified mixed solution.
In the present invention, the temperature of the second mixing is preferably 40 to 90 ℃, more preferably 50 to 80 ℃; the second mixing is preferably carried out under stirring; the rotation speed of stirring is preferably 1200-1600 r/min, more preferably 1400-1600 r/min; the second mixing time is preferably 5 to 30 minutes, more preferably 10 to 20 minutes.
After the pre-emulsified mixed solution is obtained, the water-based epoxy emulsion is obtained by adding water into the pre-emulsified mixed solution and then performing a shearing induction phase inversion process.
In the present invention, the temperature of the pre-emulsified mixture is preferably 40 to 90 ℃, more preferably 50 to 80 ℃ when water is added; the water consumption for adding water is 1/3-2/3 of the mass of the pre-emulsified mixed liquid, and more preferably 1/3-1/2; the time for adding water is preferably 60-120 min, more preferably 80-100 min; the rotating speed of shearing is preferably 1200-1800 r/min, more preferably 1600-1700 r/min; the water addition rate is preferably 90 to 110mL/min, more preferably 100mL/min. Under the action of strong shearing force, the water drops are gradually fused to become a continuous phase, and finally the phase inversion process is completed, so that the stable aqueous epoxy emulsion with small particle size of dispersed phase particles is obtained.
The invention provides application of the aqueous epoxy emulsion prepared by the technical scheme or the preparation method of the aqueous epoxy emulsion in aqueous epoxy paint.
The invention provides a modified water-based epoxy paint, which comprises the following raw materials: the paint comprises water-based epoxy emulsion, water, a defoaming agent, pigment and filler, a leveling agent, a wetting agent, a thickening agent and a flash rust inhibitor;
the aqueous epoxy emulsion is the aqueous epoxy emulsion prepared by the technical scheme or the preparation method.
In the present invention, the pigment filler preferably includes a pigment and an extender filler; the pigment is preferably added according to the use chromaticity requirement, and has no influence on the resin performance; the physical filler preferably comprises one or more of powdered calcium carbonate, talcum powder, powdered aluminum silicate, powdered calcium sulfate, barite powder, silicon dioxide, mica powder and powdered calcium silicate, more preferably talcum powder, barite powder or mica powder. The invention has no special limitation on the types of the defoamer, the flatting agent, the wetting agent, the thickening agent and the flash rust inhibitor, and can be adjusted according to the product requirement and the cost.
In the invention, the mass ratio of the water to the aqueous epoxy emulsion is preferably 1 (4-5), more preferably 1:5; the mass ratio of the aqueous epoxy emulsion to the physical filler is preferably 10 (1-4), more preferably 10 (1-3); the mass of the defoamer is preferably 0.5% of the mass of the aqueous epoxy emulsion. The amount of the defoaming agent, leveling agent, wetting agent, thickener and flash rust inhibitor used in the present invention is not particularly limited, and any of those known in the art may be used.
In the present invention, the solid content of the modified aqueous epoxy paint is preferably 70 to 90%, more preferably 80 to 85%.
The modified aqueous epoxy coating prepared by the aqueous epoxy emulsion provided by the invention has compact film formation, excellent flexibility, strength, impact resistance, water resistance and corrosion resistance, reduces the requirement of an aqueous epoxy coating system on a dispersion-assisting auxiliary agent, and saves the auxiliary agent cost.
The invention provides a preparation method of the modified waterborne epoxy coating, which comprises the following steps:
mixing the aqueous epoxy emulsion, water, a defoaming agent, pigment and filler, a leveling agent, a wetting agent, a thickening agent and an anti-flash rust agent, and filtering to obtain the modified aqueous epoxy coating.
In the present invention, the mixing is preferably: and adding water and a defoaming agent into the aqueous epoxy emulsion for first stirring, adding pigment and filler for first dispersion, and finally adding a leveling agent, a wetting agent, a thickening agent and an anti-flash rust agent for second stirring.
In the present invention, the rotation speed of the first stirring is preferably 400 to 800r/min, more preferably 500 to 800r/min; the time of the first stirring is preferably 10 to 30min, more preferably 15 to 20min; the rotation speed of the first dispersion is preferably 600-800 r/min, more preferably 600-700 r/min; the time of the first dispersion is preferably 5 to 30 minutes, more preferably 10 to 20 minutes; the rotation speed of the second stirring is preferably 600-1600 r/min, more preferably 1500-1600 r/min; the second stirring time is preferably 10 to 20 minutes, more preferably 10 to 15 minutes.
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing a first emulsifier (aqueous epoxy emulsifier with the epoxy equivalent of 6535 g/eq) and bisphenol A epoxy resin (semisolid epoxy resin with the epoxy equivalent of 329 g/eq) at the temperature of 60 ℃ according to the mass ratio of 12:100, and stirring for 15min at the speed of 1200r/min to obtain a premix;
mixing the pre-mixed solution and a second emulsifier (an aqueous epoxy emulsifier with the epoxy equivalent of 892 g/eq) at the temperature of 60 ℃, wherein the mass ratio of the first emulsifier to the second emulsifier is 3:1, and stirring for 15min at 1500r/min to obtain a pre-emulsified mixed solution;
and slowly adding deionized water into the pre-emulsified mixed liquid at the speed of 100mL/min for 80min at the temperature of 60 ℃, and simultaneously shearing at the speed of 1600r/min, wherein the water adding amount is 1/2 of the mass of the pre-emulsified mixed liquid, so as to obtain the aqueous epoxy emulsion.
Example 2
Mixing a first emulsifier (aqueous epoxy emulsifier with epoxy equivalent of 15395 g/eq) and bisphenol A epoxy resin (solid epoxy resin with epoxy equivalent of 637 g/eq) at 60 ℃ in a mass ratio of 12:100, and stirring for 20min at 1200r/min to obtain a premix;
mixing the pre-mixed solution and a second emulsifier (aqueous epoxy emulsifier with the epoxy equivalent of 2937 g/eq) at the temperature of 80 ℃, wherein the mass ratio of the first emulsifier to the second emulsifier is 2:1, and stirring for 10min at 1500r/min to obtain a pre-emulsified mixed solution;
and slowly adding deionized water into the pre-emulsified mixed liquid at the speed of 90mL/min for 120min at the temperature of 80 ℃, and simultaneously shearing at the speed of 1600r/min, wherein the water adding amount is 2/3 of the mass of the pre-emulsified mixed liquid, so as to obtain the aqueous epoxy emulsion.
Example 3
Mixing a first emulsifier (an aqueous epoxy emulsifier with an epoxy equivalent of 12785 g/eq) and bisphenol A epoxy resin (a solid epoxy resin with an epoxy equivalent of 423 g/eq) at a mass ratio of 15:100 at 75 ℃, and stirring for 20min at 1200r/min to obtain a premix;
mixing the pre-mixed solution and a second emulsifier (aqueous epoxy emulsifier with the epoxy equivalent of 1023 g/eq) at the temperature of 75 ℃, wherein the mass ratio of the first emulsifier to the second emulsifier is 3:1, and stirring for 10min at 1500r/min to obtain a pre-emulsified mixed solution;
and slowly adding deionized water into the pre-emulsified mixed liquid at the speed of 90mL/min for 90min at the temperature of 75 ℃, and simultaneously shearing at the speed of 1600r/min, wherein the water adding amount is 1/2 of the mass of the pre-emulsified mixed liquid, so as to obtain the aqueous epoxy emulsion.
Example 4
Mixing a first emulsifier (aqueous epoxy emulsifier with an epoxy equivalent of 2935 g/eq) and bisphenol F type epoxy resin (solid epoxy resin with an epoxy equivalent of 213 g/eq) at a mass ratio of 9:100 at 50 ℃, and stirring for 15min at 800r/min to obtain a premix;
mixing the pre-mixed solution and a second emulsifier (aqueous epoxy emulsifier with the epoxy equivalent of 409 g/eq) at 50 ℃, wherein the mass ratio of the first emulsifier to the second emulsifier is 3:1, and stirring for 10min at 1200r/min to obtain a pre-emulsified mixed solution;
and slowly adding deionized water into the pre-emulsified mixed liquid at the speed of 110mL/min for 60min at the temperature of 50 ℃, and simultaneously shearing at the speed of 1200r/min, wherein the water adding amount is 1/3 of the mass of the pre-emulsified mixed liquid, so as to obtain the aqueous epoxy emulsion.
Example 5
Mixing a first emulsifier (aqueous epoxy emulsifier with epoxy equivalent of 1537 g/eq) and bisphenol F type epoxy resin (solid epoxy resin with epoxy equivalent of 185.2 g/eq) at 40 ℃ in a mass ratio of 12:100, and stirring for 15min at 800r/min to obtain a premix;
mixing the pre-mixed solution and a second emulsifier (aqueous epoxy emulsifier with the epoxy equivalent of 219 g/eq) at the temperature of 40 ℃, wherein the mass ratio of the first emulsifier to the second emulsifier is 3:1, and stirring for 10min at 1200r/min to obtain a pre-emulsified mixed solution;
and slowly adding deionized water into the pre-emulsified mixed liquid at the speed of 100mL/min for 60min at the temperature of 40 ℃, and simultaneously shearing at the speed of 1400r/min, wherein the water adding amount is 1/2 of the mass of the pre-emulsified mixed liquid, so as to obtain the aqueous epoxy emulsion.
Example 6
Mixing a first emulsifier (an aqueous epoxy emulsifier with an epoxy equivalent of 24735 g/eq) and bisphenol F type epoxy resin (a solid epoxy resin with an epoxy equivalent of 689 g/eq) at a mass ratio of 12:100 at 85 ℃, and stirring for 30min at 1400r/min to obtain a premix;
mixing the pre-mixed solution and a second emulsifier (aqueous epoxy emulsifier with the epoxy equivalent of 1354 g/eq) at the temperature of 60 ℃, wherein the mass ratio of the first emulsifier to the second emulsifier is 3:1, and stirring for 20min at 1500r/min to obtain a pre-emulsified mixed solution;
and slowly adding deionized water into the pre-emulsified mixed liquid at the speed of 90mL/min for 120min at the temperature of 60 ℃, and simultaneously shearing at the speed of 1600r/min, wherein the water adding amount is 2/3 of the mass of the pre-emulsified mixed liquid, so as to obtain the aqueous epoxy emulsion.
Comparative example 1
Mixing a first emulsifier (an aqueous epoxy emulsifier with an epoxy equivalent of 17535 g/eq) and bisphenol A epoxy resin (a solid epoxy resin with an epoxy equivalent of 632 g/eq) at a mass ratio of 15:100 at 85 ℃, and stirring for 30min at 1400r/min to obtain a premix;
and slowly adding deionized water into the pre-mixed solution at the speed of 90mL/min for 120min at the temperature of 85 ℃, and simultaneously shearing at the speed of 1600r/min, wherein the water adding amount is 2/3 of the mass of the pre-emulsified mixed solution, so as to obtain the aqueous epoxy emulsion.
Comparative example 2
Mixing a first emulsifier (an aqueous epoxy emulsifier with an epoxy equivalent of 2375 g/eq) and bisphenol F type epoxy resin (a solid epoxy resin with an epoxy equivalent of 196 g/eq) at a mass ratio of 15:100 at 40 ℃, and stirring for 15min at 1200r/min to obtain a premix;
and slowly adding deionized water into the pre-mixed solution at the speed of 110mL/min for 120min at the temperature of 40 ℃, and simultaneously shearing at the speed of 1600r/min, wherein the water adding amount is 1/2 of the mass of the pre-emulsified mixed solution, so as to obtain the aqueous epoxy emulsion.
Application example 1
Adding water (the mass ratio of the water-based epoxy powder to the water-based epoxy emulsion is 1:5) and a defoaming agent (accounting for 0.5% of the mass of the water-based epoxy emulsion) into the water-based epoxy emulsion prepared in the example 1, stirring for 10min at 600r/min, adding physical filler (specific type is barite powder accounting for 10% of the mass of the water-based epoxy emulsion) after fully mixing, fully mixing for 15min at 800r/min, adding a flatting agent, a wetting agent, a thickening agent and a flash rust inhibitor, and stirring for 10min at 600r/min to obtain the modified water-based epoxy paint.
Application example 2
Adding water (the mass ratio of the water-based epoxy powder to the water-based epoxy emulsion is 1:5) and a defoaming agent (accounting for 0.5% of the mass of the water-based epoxy emulsion) into the water-based epoxy emulsion prepared in the example 2, stirring for 10min at 600r/min, adding physical filler (specific type is barite powder accounting for 10% of the mass of the water-based epoxy emulsion) after fully mixing, fully mixing for 15min at 800r/min, adding a flatting agent, a wetting agent, a thickening agent and a flash rust inhibitor, and stirring for 10min at 600r/min to obtain the modified water-based epoxy paint.
Application example 3
Adding water (the mass ratio of the water-based epoxy powder to the water-based epoxy emulsion is 1:5) and a defoaming agent (accounting for 0.5% of the mass of the water-based epoxy emulsion) into the water-based epoxy emulsion prepared in the example 3, stirring for 10min at 600r/min, adding physical filler (specific type is barite powder accounting for 10% of the mass of the water-based epoxy emulsion) after fully mixing, fully mixing for 15min at 800r/min, adding a flatting agent, a wetting agent, a thickening agent and a flash rust inhibitor, and stirring for 10min at 600r/min to obtain the modified water-based epoxy paint.
Application example 4
Adding water (the mass ratio of the water-based epoxy powder to the water-based epoxy emulsion is 1:5) and a defoaming agent (accounting for 0.5% of the mass of the water-based epoxy emulsion) into the water-based epoxy emulsion prepared in the example 4, stirring for 10min at 600r/min, adding physical filler (the specific type is barite powder accounting for 10% of the mass of the water-based epoxy emulsion) after fully mixing, fully mixing for 15min at 800r/min, adding a flatting agent, a wetting agent, a thickening agent and a flash rust inhibitor, and stirring for 10min at 600r/min to obtain the modified water-based epoxy paint.
Application example 5
Adding water (the mass ratio of the water-based epoxy powder to the water-based epoxy emulsion is 1:5) and a defoaming agent (accounting for 0.5% of the mass of the water-based epoxy emulsion) into the water-based epoxy emulsion prepared in the example 5, stirring for 10min at 600r/min, adding physical filler (specific type is barite powder accounting for 10% of the mass of the water-based epoxy emulsion) after fully mixing, fully mixing for 15min at 800r/min, adding a flatting agent, a wetting agent, a thickening agent and a flash rust inhibitor, and stirring for 10min at 600r/min to obtain the modified water-based epoxy paint.
Application example 6
Adding water (the mass ratio of the water-based epoxy powder to the water-based epoxy emulsion is 1:5) and a defoaming agent (accounting for 0.5% of the mass of the water-based epoxy emulsion) into the water-based epoxy emulsion prepared in the example 6, stirring for 10min at 600r/min, adding physical filler (specific type is barite powder accounting for 10% of the mass of the water-based epoxy emulsion) after fully mixing, fully mixing for 15min at 800r/min, adding a flatting agent, a wetting agent, a thickening agent and a flash rust inhibitor, and stirring for 10min at 600r/min to obtain the modified water-based epoxy paint.
Comparative application example 1
Adding water (the mass ratio of the water-based epoxy powder to the water-based epoxy emulsion is 1:5) and a defoaming agent (accounting for 0.5% of the mass of the water-based epoxy emulsion) into the water-based epoxy emulsion prepared in comparative example 1, stirring for 10min at 600r/min, adding physical filler (specific type is barite powder accounting for 10% of the mass of the water-based epoxy emulsion) after fully mixing, fully mixing for 15min at 800r/min, adding a flatting agent, a wetting agent, a thickening agent and a flash rust inhibitor, and stirring for 10min at 600r/min to obtain the modified water-based epoxy paint.
Comparative application example 2
Adding water (the mass ratio of the water-based epoxy powder to the water-based epoxy emulsion is 1:5) and a defoaming agent (accounting for 0.5% of the mass of the water-based epoxy emulsion) into the water-based epoxy emulsion prepared in comparative example 2, stirring for 10min at 600r/min, adding physical filler (specific type is barite powder accounting for 10% of the mass of the water-based epoxy emulsion) after fully mixing, fully mixing for 15min at 800r/min, adding a flatting agent, a wetting agent, a thickening agent and a flash rust inhibitor, and stirring for 10min at 600r/min to obtain the modified water-based epoxy paint.
Performance testing
(1) The performance of the aqueous epoxy emulsions prepared in examples 1 to 6 and comparative examples 1 to 2 was tested, and the results are shown in Table 1.
Table 1 data for emulsions of examples 1-6 and comparative examples 1-2
As can be seen from Table 1, the aqueous epoxy emulsion prepared in the examples of the present invention has lower rotational viscosity, emulsion average particle diameter and D than those of the comparative examples 80 The particle size has higher centrifugal stability.
(2) The modified aqueous epoxy coating and the aqueous epoxy curing agent prepared in application examples 1-6 and comparative application examples 1-2 are mixed, a base material is treated according to the BG/T9271 standard, the coating is coated on the surface of standard tin plate, the coating is subjected to leveling for 30min, low-temperature baking for 15min at 40 ℃ and high-temperature baking for 30min at 70 ℃, after curing for 7d, the relevant properties of the paint film are tested, the pencil hardness test method is referred to the GB/T6739-1996 film hardness pencil test method, the flexibility test method is referred to the GB/T1731-2020 paint film and putty film flexibility test method, the impact resistance test method is referred to the GB/T1732-2020 paint film impact resistance test method, the water resistance test method is referred to the GB/T1733-1993 paint film measurement method, the salt spray resistance test method is referred to the GB/T1771-1991 paint and the neutral salt spray resistance test method of the varnish, and the test results are shown in Table 2.
TABLE 2 paint film Properties of application examples 1 to 6 and comparative application examples 1 to 2
As can be seen from Table 2, the water-based epoxy paint obtained by the preparation method provided by the invention has the characteristics of compact film formation and strong structure, the water resistance and the corrosion resistance are obviously improved, and in terms of cost, the cost of the auxiliary agent can be greatly saved due to the improvement of the preparation method.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, according to which one can obtain other embodiments without inventiveness, these embodiments are all within the scope of the invention.
Claims (10)
1. The aqueous epoxy emulsion is characterized by comprising the following preparation raw materials: an epoxy resin, a first emulsifier, a second emulsifier and water;
the first emulsifier is an aqueous epoxy emulsifier with an epoxy equivalent weight of >1000 g/eq;
the second emulsifier is an aqueous epoxy emulsifier with an epoxy equivalent weight of <5000 g/eq.
2. The aqueous epoxy emulsion of claim 1, wherein the aqueous epoxy emulsion has a solids content of 50 to 75%.
3. The aqueous epoxy emulsion of claim 1, wherein the mass ratio of the first emulsifier to the epoxy resin is 0.09-0.15:1.
4. The aqueous epoxy emulsion of claim 1 or 2, wherein the epoxy equivalent ratio of the second emulsifier to the first emulsifier is < 1:4;
the mass ratio of the second emulsifier to the first emulsifier is 1 (2-4).
5. The method for preparing the aqueous epoxy emulsion according to any one of claims 1 to 4, comprising the steps of:
first mixing a first emulsifier and epoxy resin under the condition of heating and stirring to obtain a premix;
mixing the pre-mixed solution with a second emulsifier to obtain a pre-emulsified mixed solution;
and adding water into the pre-emulsified mixed solution, and performing a shearing induction phase inversion process to obtain the aqueous epoxy emulsion.
6. The method according to claim 5, wherein the heating temperature is 40 to 90 ℃; the stirring speed is 800-1400 r/min.
7. The method according to claim 5, wherein the second mixing is performed under stirring; the stirring rotating speed is 1200-1600 r/min.
8. The preparation method according to claim 5, wherein the water amount for adding water is 1/3 to 2/3 of the mass of the pre-emulsified mixture; the water adding time is 60-120 min; the rotating speed of the shearing is 1200-1800 r/min.
9. Use of the aqueous epoxy emulsion according to any one of claims 1 to 4 or the aqueous epoxy emulsion prepared by the preparation method according to any one of claims 5 to 8 in aqueous epoxy paint.
10. The modified water-based epoxy paint is characterized in that the preparation raw materials comprise: the paint comprises water-based epoxy emulsion, water, a defoaming agent, pigment and filler, a leveling agent, a wetting agent, a thickening agent and a flash rust inhibitor;
the aqueous epoxy emulsion is the aqueous epoxy emulsion prepared by the preparation method of any one of claims 1 to 4 or 5 to 8.
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| CN202310798171.2A CN116640416A (en) | 2023-06-29 | 2023-06-29 | Water-based epoxy emulsion, preparation method and application thereof, and modified water-based epoxy paint |
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