CN107746450A - A kind of waterborne epoxy modified acrylic ester emulsion and preparation method and application - Google Patents
A kind of waterborne epoxy modified acrylic ester emulsion and preparation method and application Download PDFInfo
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- CN107746450A CN107746450A CN201710841991.XA CN201710841991A CN107746450A CN 107746450 A CN107746450 A CN 107746450A CN 201710841991 A CN201710841991 A CN 201710841991A CN 107746450 A CN107746450 A CN 107746450A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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Abstract
The invention discloses a kind of waterborne epoxy modified acrylic ester emulsion and preparation method and application, belong to polymeric material field, its emulsion is made up of the shell of polyacrylate and the stratum nucleare of epoxy resin, and the mass ratio of epoxy resin and institute's polyacrylate is 1:1~1:19, the solid content of emulsion is 40~50%.Liquid epoxies is dissolved in (methyl) acrylate monomer, in the presence of composite emulsifying system after high speed is scattered, emulsion polymerization is triggered with initiator, obtains waterborne epoxy modified acrylic ester emulsion.Using this emulsion and aqueous amine epoxy hardener as film forming matter, compound various auxiliary agents, coating prepared by anticorrosive pigment/filler, the multiple cross-linked structure that can be formed in its film between acrylate, epoxy resin and curing agent, thus there is excellent antiseptic property, when thickness reaches 40 μm, salt fog resistance is up to more than 500h.
Description
Technical field
The invention belongs to polymeric material field, is related to a kind of waterborne epoxy modified acrylic ester emulsion and preparation method thereof
With application.
Background technology
Epoxy resin has fabulous adhesive force, excellent chemical-resistant, heat endurance in metal surface, thus in anti-corrosion
Paint field is widely used.But the problems such as outdoor weathe resistance is poor, and film fragility is big be present in epoxy coating, and acrylic acid
Esters coating can just solve these problems.So the research for waterborne epoxy modified acrylic ester emulsion is increasingly becoming people
The focus paid close attention to.
The preparation method of waterborne epoxy modified acrylic ester emulsion is first using acrylic ester monomer epoxy resin at present
Dissolve and emulsify, then carry out emulsion polymerization, the existing many research reports of such a method, but acrylic ester monomer and asphalt mixtures modified by epoxy resin
Lack effective crosslinking between fat.
The content of the invention
Lack effective crosslinking between (methyl) acrylicacidandesters class monomer and epoxy resin in the prior art to overcome
The defects of, the present invention provides a kind of waterborne epoxy modified acrylic ester emulsion and preparation method and application, water-based with gained
Not only antiseptic property is good for coating prepared by epoxy modification acrylate emulsion, and is free of VOC, safety collar
Protect.
To realize object above, the present invention provides a kind of waterborne epoxy modified acrylic ester emulsion, and the emulsion is by poly- third
The mass ratio of the shell of olefin(e) acid ester and the stratum nucleare composition of epoxy resin, the epoxy resin and the polyacrylate is 1:1~
1:19, the solid content of the emulsion is 40~50%.
A kind of preparation method of waterborne epoxy modified acrylic ester emulsion, is comprised the technical steps that：
(1) (methyl) acrylicacidandesters class monomer is added in monomer kettle, stirs lower addition liquid epoxies, dissolving
Afterwards, mix monomer is obtained, wherein the mass ratio of the liquid epoxies and the monomer of (methyl) acrylicacidandesters class is 1:1
~1:19；
(2) deionized water and first step compound emulsifying agent are added in emulsifying kettle, emulsifier solution is obtained after stirring；
(3) under agitation, the mix monomer in monomer kettle is added into the emulsifying kettle, scattered 30min is obtained at a high speed
To pre-emulsion；
(4) deionized water, second step compound emulsifying agent, initiator and part pre-emulsion are added in a kettle, 75~
At 80 DEG C, 10~30min is reacted, remaining pre-emulsion is then added dropwise in 1~3h, after being added dropwise, be incubated 1~3h, it is cold
But described waterborne epoxy modified acrylic ester emulsion, is filtrated to get, the part pre-emulsion accounts for the matter of the pre-emulsion
Measure the 3~10% of percentage.
Specifically, the mass ratio of the liquid epoxies and (methyl) acrylic monomers is 1:2.5~1:4.
Specifically, described liquid epoxies is epoxy resin E44, epoxy resin E51, epoxy resin E55 one kind
Or two or more blending epoxy.
Specifically, described first step compound emulsifying agent and second step compound emulsifying agent are by anionic emulsifier and non-
Ionic emulsifying agent forms, the mass ratio of nonionic emulsifier and anionic emulsifier in the first step compound emulsifying agent
For 4:1~1:2, the mass ratio of nonionic emulsifier and anionic emulsifier is 1 in the second step compound emulsifying agent:1
~1:10 anionic emulsifier are lauryl sodium sulfate, neopelex, ethoxylated alkyl ammonium sulfate
Salt, alkyl phenol ethoxylates ammonium sulfate, tridecyl alcohol polyethers sodium sulphate, fatty alcohol (ether) phosphate ammonium salt, butanedioic acid nonyl phenolic ester
Sodium sulfonate, sodium dioctyl sulfosuccinate, sulfosuccinic acid alkyl alcohol ether ester sodium salt, vinylsulfonate or 1- propenyloxy groups
2- hydroxypropanesulfonic acid sodium；The nonionic emulsifier is NPE, OPEO, secondary alkyl
Alcohol ether, the polyethers of ethylene oxide propylene oxide block or tridecyl alcohol b-oxide.
Specifically, the first step compound emulsifying agent forms compound emulsifying agent gross mass plus second step compound emulsifying agent,
The compound emulsifying agent gross mass is 1 with the solid masses ratio in the waterborne epoxy modified acrylic ester emulsion:100~5:
100。
Specifically, described initiator is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, one kind of TBHP
Or two or more mixture.
Specifically, described (methyl) acrylicacidandesters class monomer is methacrylic acid, methacrylate-based monomer, third
Olefin(e) acid, acrylic ester monomer, styrene, the acrylate monomer containing epoxide group, acrylonitrile it is one or more kinds of
Mixture, the acrylate monomer containing epoxide group are glycidyl acrylate or GMA.
Specifically, prepared waterborne epoxy modified acrylic ester emulsion needs the aqueous epoxy curing agent with modified amine
Be used cooperatively, epoxide equivalent in waterborne epoxy modified acrylic ester emulsion and in the aqueous epoxy curing agent of modified amine it is active
The ratio of hydrogen equivalent is 1:0.5~1:1.2.
Specifically, the water-base epoxy of the epoxide equivalent in the waterborne epoxy modified acrylic ester emulsion and modified amine is consolidated
The ratio of active hydrogen equivalent weight is 1 in agent:0.7~1:0.9.
The beneficial effects of the invention are as follows：The waterborne epoxy modified acrylic ester emulsion of technical solution of the present invention is by (methyl)
The shell of acrylate and the stratum nucleare composition of liquid epoxies.First waterborne epoxy modified acrylic ester emulsion polymerization it
Before, (methyl) acrylate monomer serves as the solvent of liquid epoxies, with waterborne epoxy modified acrylic ester emulsion polymerization
Completion, (methyl) acrylate polymer formed act as the emulsifying agent of liquid epoxies, the product so obtained
Solvent, cosolvent are not needed not only, nor need substantial amounts of emulsifying agent.In addition, the waterborne epoxy modified propylene of the present invention
Acid esters emulsion be (introduce epoxide group in methacrylate shell, in the presence of the epoxy hardener of modified amine,
Multiple cross-linked structure is formed between stratum nucleare, shell and curing agent, thus uses the waterborne epoxy modified acrylic ester emulsion system of gained
Standby anticorrosive paint has excellent water resistance, salt fog resistance, chemical-resistant and high mechanical strength.
Embodiment
The present invention is described further with reference to embodiments, but is not limited to this.Each embodiment raw materials remove
It is commercially available industrial goods to be otherwise noted outer, is commercially available, following 0.2gBYK-025 aqueous defoamers, 0.3gBYK-
346 organic silicon surfactants and 1.5gBYK-190 dispersants are bought from BYK companies.
Embodiment 1
132Kg methyl methacrylates, 94Kg Isooctyl acrylate monomers, 22Kg acrylonitrile, 11Kg first are added in monomer kettle
Base glycidyl acrylate, 6.8Kg methacrylic acids, then add liquid 66Kg epoxy resin E51 and fully dissolve, stirring is equal
It is even to obtain mix monomer.Added in emulsifying kettle 110Kg deionized waters, 1.6Kg sulfosuccinic acid alkyl alcohol ethers ester sodium salt,
2.2Kg tridecyl alcohol b-oxides are well mixed.Under the high-speed stirred of the tooth-like emulsifying kettle of disk, by the mixing list in monomer kettle
Body is slowly added dropwise into emulsifying kettle, is disperseed 30min at a high speed with the tooth-like emulsifying kettle of disk, is obtained 445.6Kg pre-emulsions.In reactor
Middle addition 220Kg deionized waters, 0.8Kg sulfosuccinic acid alkyl alcohol ethers ester sodium salt, 0.6Kg tridecyl alcohol b-oxides, will
1.0Kg ammonium persulfates are dissolved in 20Kg deionized waters and added in reactor, add 20Kg pre-emulsions, stir simultaneously
75 DEG C of heating, the remaining pre-emulsions of 425.6Kg are added dropwise in 2h, cools after insulation reaction 1h, filtering and discharging, that is, obtains this hair
Bright waterborne epoxy modified acrylic ester emulsion.
Embodiment 2
33Kg methyl methacrylates, 24Kg Isooctyl acrylate monomers, 6Kg acrylonitrile, 3Kg methyl-props are added in monomer kettle
Olefin(e) acid ethylene oxidic ester, 2Kg methacrylic acids, then add liquid 66Kg epoxy resin E51 and fully dissolve, be uniformly mixing to obtain
Mix monomer.40Kg deionized waters, 1.6Kg sulfosuccinic acid alkyl alcohol ethers ester sodium salt, 0.8Kg tridecanes are added in emulsifying kettle
Base alcohol b-oxide is well mixed.Under the high-speed stirred of the tooth-like emulsifying kettle of disk, the mix monomer in monomer kettle is slowly added dropwise
Into emulsifying kettle, disperse 30min at a high speed with the tooth-like emulsifying kettle of disk, obtain 150Kg pre-emulsions.70Kg is added in a kettle to go
Ionized water, 0.6Kg sulfosuccinic acid alkyl alcohol ethers ester sodium salt, 0.6Kg：Tridecyl alcohol b-oxide, sulfuric acid is introduced through by 1.0Kg
Ammonium is dissolved in 7Kg deionized waters and added in reactor, adds 7Kg pre-emulsions, stirs and heats up 75 DEG C, in 2h
The remaining pre-emulsions of interior dropwise addition 143Kg, cooling, filtering and discharging after insulation reaction 1h, that is, the water-base epoxy for obtaining the present invention change
Property acrylic acid ester emulsion.
Embodiment 3
132Kg methyl methacrylates, 94Kg Isooctyl acrylate monomers, 22Kg acrylonitrile, 11Kg first are added in monomer kettle
Base glycidyl acrylate, 6.8Kg methacrylic acids, then add liquid 14Kg epoxy resin E51 and fully dissolve, stirring is equal
It is even to obtain mix monomer.20Kg deionized waters, 1.6Kg sulfosuccinic acid alkyl alcohol ethers ester sodium salt, 6.4Kg are added in emulsifying kettle
Tridecyl alcohol b-oxide is well mixed.Under the high-speed stirred of the tooth-like emulsifying kettle of disk, the mix monomer in monomer kettle is delayed
Slowly it is added dropwise in emulsifying kettle, disperses 30min at a high speed with the tooth-like emulsifying kettle of disk, obtain 90Kg pre-emulsions.Add in a kettle
30Kg deionized waters, 6Kg sulfosuccinic acid alkyl alcohol ethers ester sodium salt, 0.6Kg tridecyl alcohol b-oxides, by 1.0Kg over cures
Sour ammonium is dissolved in 3Kg deionized waters and added in reactor, adds 4Kg pre-emulsions, stirs and heats up 75 DEG C,
The remaining pre-emulsions of 86Kg are added dropwise in 2h, cool after insulation reaction 1h, filtering and discharging, that is, the water-base epoxy for obtaining the present invention changes
Property acrylic acid ester emulsion.
Embodiment 4
Substituted in the preparation method of the waterborne epoxy modified acrylic ester emulsion of present embodiment with 66Kg epoxy resin E44
66Kg epoxy resin E51, it is other same as Example 1.
Embodiment 5
In the preparation method of the waterborne epoxy modified acrylic ester emulsion of present embodiment with 89Kg methyl methacrylates,
70Kg Isooctyl acrylate monomers, that 133Kg epoxy resin E51 substitutes 132Kg methyl methacrylates, 94Kg acrylic acid respectively is different pungent
Ester, 66Kg epoxy resin E51, it is other same as Example 1.
Embodiment 6
1.6Kg dodecyl sulphates are used in the preparation method of the waterborne epoxy modified acrylic ester emulsion of present embodiment
Sodium, 2.2Kg OPEOs replace 1.6Kg sulfosuccinic acid alkyl alcohol ethers ester sodium salt, 2.2Kg tridecyl alcohol respectively
B-oxide；0.8Kg sulfosuccinic acid alkane is substituted respectively with 0.8Kg lauryl sodium sulfate, 0.6Kg OPEOs
Base alcohol ether ester sodium salt, 0.6Kg tridecyl alcohol b-oxides, it is other same as Example 1.
Embodiment 7
Substituted in the preparation method of the waterborne epoxy modified acrylic ester emulsion of present embodiment with 1.0Kg potassium peroxydisulfates
1.0Kg ammonium persulfates, it is other same as Example 1.
Embodiment 8
The application of waterborne epoxy modified acrylic ester emulsion prepared by the present embodiment 1
The preparation of water-based iron oxide red paint：By 48g water, 0.2gBYK-025 aqueous defoamers, 0.3gBYK-346 organosilyl surfaces
Activating agent, 1.5gBYK-190 dispersants, 2.4gTexanol ((2,2,4- trimethyl -1,3- pentanediol mono isobutyrate)), 30g
Iron oxide red, 7.5g talcum powder, 33g natives sulfate of barium, 40g trbasic zinc phosphates, 9.5g mica powders are well mixed and to be ground to fineness small
In 60 μm, the 280g emulsions of the gained of above-described embodiment 1 are then added, obtain water-based iron oxide red paint component A.30gBanco901 is changed
Property amine epoxy hardener be well mixed to obtain component B with 30g deionized waters, component A and component B are mixed, stirred i.e.
Obtain water-based iron oxide red paint.
Embodiment 9
The application of waterborne epoxy modified acrylic ester emulsion prepared by the present embodiment 4
The preparation of water-based iron oxide red paint：By 48g water, 0.2gBYK-025 aqueous defoamers, 0.3gBYK-346 organosilyl surfaces
Activating agent, 1.5gBYK-190 dispersants, 2.4gTexanol ((2,2,4- trimethyl -1,3- pentanediol mono isobutyrate)), 30g
Iron oxide red, 7.5g talcum powder, 33g natives sulfate of barium, 40g trbasic zinc phosphates, 9.5g mica powders are well mixed and to be ground to fineness small
In 60 μm, the 283.7g emulsions of the gained of above-described embodiment 2 are then added, obtain water-based iron oxide red paint component A.Will
26.3gBanco901 modified amines epoxy hardener is well mixed to obtain component B with 26.3g deionized waters, by component A and component
B mixing, stirring obtains the red paint of aqueous iron.
Embodiment 10
The application of waterborne epoxy modified acrylic ester emulsion prepared by the present embodiment 5
The preparation of water-based iron oxide red paint：By 48g water, 0.2gBYK-025 aqueous defoamers, 0.3gBYK-346 organosilyl surfaces
Activating agent, 1.5gBYK-190 dispersants, 2.4gTexanol ((2,2,4- trimethyl -1,3- pentanediol mono isobutyrate)), 30g
Iron oxide red, 7.5g talcum powder, 33g natives sulfate of barium, 40g trbasic zinc phosphates, 9.5g mica powders are well mixed and to be ground to fineness small
In 60 μm, the 255g emulsions of the gained of above-described embodiment 3 are then added, obtain water-based iron oxide red paint component A.55gBanco901 is changed
Property amine epoxy hardener be well mixed to obtain component B with 55g deionized waters, component A and component B are mixed, stirred i.e.
Obtain water-based iron oxide red paint.
Embodiment Isosorbide-5-Nitrae, the waterborne epoxy modified acrylic emulsion property test result prepared by 5,6,7 are shown in Table 1.In table 1
Solid part method as defined in GB/T1725-2007 standards tested；Gel fraction represents to collect produced by during experiment
All condensation products, after being cleaned with distilled water, be dried to constant weight and be designated as W1, gel fraction=W1/W2*100%, wherein W2 for breast
Liquid gross mass；Heat-storage method as defined in GB/T6753.3-1986 standards in table 1 is tested.
The embodiment Isosorbide-5-Nitrae of table 1, the waterborne epoxy modified acrylic emulsion property test result prepared by 5,6,7
| Solid part (120 DEG C/2h) | Gel fraction/% | Heat-storage (50 DEG C, 7d) | |
| Embodiment 1 | 48.3% | 0.08 | Pass through |
| Embodiment 4 | 47.8% | 0.28 | Pass through |
| Embodiment 5 | 48.2% | 0.14 | Pass through |
| Embodiment 6 | 47.9% | 0.22 | Pass through |
| Embodiment 7 | 47.5% | 0.16 | Pass through |
Water-based iron oxide red paint prepared by embodiment 8~10, spraying 1, it is 40 μm or so to control coating thickness of dry film, 50
Its performance is tested after being conserved 1 day under the conditions of DEG C, the performance test results are shown in Table 2.Paint film adhesion presses GB/T 9286-1998 standards
Defined method is tested；Paint film salt fog resistance method as defined in GB/T 1771-1991 standards is tested；Paint film is resistance to
The water-based method as defined in GB/T 1733-1993 standards is tested；Paint film resistant to liquid medium is marked by GB/T 9274-1988
Method is tested as defined in standard；
As shown in Table 1, the waterborne epoxy modified acrylic emulsion prepared according to technical solution of the present invention, product gel fraction
Low, excellent storage stability can be with industrialized production.
Table 2 prepares the performance test of water-based iron oxide red paint using the gained waterborne epoxy modified acrylic emulsion of embodiment 8~10
| Adhesive force/level | Salt spray resistance/h | Water resistance/h | Resistance to salt water/h | Chemicals-resistant/h | |
| Embodiment 8 | 0 | ＞ 500 | ＞ 240 | ＞ 240 | ＞ 240 |
| Embodiment 9 | 0 | ＞ 500 | ＞ 240 | ＞ 240 | ＞ 240 |
| Embodiment 10 | 0 | ＞ 500 | ＞ 240 | ＞ 240 | ＞ 240 |
From the testing result of table 2, the water-based iron oxide red paint prepared using waterborne epoxy modified acrylic emulsion of the present invention,
When thickness reaches 40 μm, salt fog resistance has excellent antiseptic property, metal surface can played very well up to more than 500h
Protective effect.
Claims (10)
- A kind of 1. waterborne epoxy modified acrylic ester emulsion, it is characterised in that：The emulsion by polyacrylate shell and ring The mass ratio of the stratum nucleare composition of oxygen tree fat, the epoxy resin and the polyacrylate is 1:1~1:19, the emulsion contains Gu amount is 40~50%.
- 2. the preparation method of waterborne epoxy modified acrylic ester emulsion according to claim 1, is comprised the technical steps that：(1) (methyl) acrylicacidandesters class monomer is added in monomer kettle, lower addition liquid epoxies is stirred, after dissolving, obtains To mix monomer, wherein the mass ratio of the liquid epoxies and the monomer of (methyl) acrylicacidandesters class is 1:1~1: 19；(2) deionized water and first step compound emulsifying agent are added in emulsifying kettle, emulsifier solution is obtained after stirring；(3) under agitation, the mix monomer in monomer kettle is added into the emulsifying kettle, scattered 30min is obtained pre- at a high speed Emulsion；(4) deionized water, second step compound emulsifying agent, initiator and part pre-emulsion are added in a kettle, at 75~80 DEG C Under, 10~30min is reacted, remaining pre-emulsion is then added dropwise in 1~3h, after being added dropwise, is incubated 1~3h, cooling, mistake Filter obtains described waterborne epoxy modified acrylic ester emulsion, and the part pre-emulsion accounts for the quality percentage of the pre-emulsion Several 3~10%.
- 3. the preparation method of the waterborne epoxy modified acrylic ester emulsion according to right 2, it is characterised in that：The Breakup of Liquid Ring The mass ratio of oxygen tree fat and (methyl) acrylic monomers is 1:2.5~1:4.
- 4. the preparation method of the waterborne epoxy modified acrylic ester emulsion according to right 2, it is characterised in that：Described liquid Epoxy resin is epoxy resin E44, epoxy resin E51, epoxy resin E55 one or more kinds of blending epoxies.
- 5. the preparation method of the waterborne epoxy modified acrylic ester emulsion according to right 2, it is characterised in that：Described first Walk compound emulsifying agent and second step compound emulsifying agent to form by anionic emulsifier and nonionic emulsifier, described first It is 4 to walk the mass ratio of nonionic emulsifier and anionic emulsifier in compound emulsifying agent:1~1:2, the second step is compound The mass ratio of nonionic emulsifier and anionic emulsifier is 1 in emulsifying agent:1~1:10, the anionic emulsifier For lauryl sodium sulfate, neopelex, ethoxylated alkyl ammonium sulfate salt, alkyl phenol ethoxylates ammonium sulfate Salt, tridecyl alcohol polyethers sodium sulphate, fatty alcohol (ether) phosphate ammonium salt, butanedioic acid nonyl phenolic ester sodium sulfonate, butanedioic acid dioctyl ester sulphur Sour sodium, sulfosuccinic acid alkyl alcohol ether ester sodium salt, vinylsulfonate or 1- propenyloxy group 2- hydroxypropanesulfonic acid sodium；It is described non- Ionic emulsifying agent is that NPE, OPEO, secondary alkyl alcohol ether, ethylene oxide propylene oxide are embedding The polyethers or tridecyl alcohol b-oxide of section.
- 6. the preparation method of the waterborne epoxy modified acrylic ester emulsion according to right 2, it is characterised in that：The first step Compound emulsifying agent plus second step compound emulsifying agent composition compound emulsifying agent gross mass, the compound emulsifying agent gross mass with it is described Solid masses ratio in waterborne epoxy modified acrylic ester emulsion is 1:100~5:100.
- 7. the preparation method of the waterborne epoxy modified acrylic ester emulsion according to right 2, it is characterised in that：Described initiation Agent is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, one or more kinds of mixtures of TBHP.
- 8. the preparation method of the waterborne epoxy modified acrylic ester emulsion according to right 2, it is characterised in that：(methyl) The monomer of acrylicacidandesters class is methacrylic acid, methacrylate-based monomer, acrylic acid, acrylic ester monomer, benzene Ethene, the acrylate monomer containing epoxide group, one or more kinds of mixtures of acrylonitrile, it is described containing epoxide group Acrylate monomer is glycidyl acrylate or GMA.
- 9. the application of waterborne epoxy modified acrylic ester emulsion according to claim 1, it is characterised in that：The water-based ring Oxygen modified acrylate emulsion is used cooperatively with aqueous amine epoxy hardener, the ring in waterborne epoxy modified acrylic ester emulsion The ratio of active hydrogen equivalent weight is 1 in oxygen equivalent and aqueous amine epoxy hardener:0.5~1:1.2.
- 10. the application of waterborne epoxy modified acrylic ester emulsion according to claim 9, it is characterised in that：It is described water-based The ratio of active hydrogen equivalent weight is 1 in epoxide equivalent and aqueous amine epoxy hardener in epoxy modification acrylate emulsion:0.7~ 1:0.9。
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| CN201710841991.XA CN107746450A (en) | 2017-09-18 | 2017-09-18 | A kind of waterborne epoxy modified acrylic ester emulsion and preparation method and application |
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| CN109180878A (en) * | 2018-09-26 | 2019-01-11 | 陕西科技大学 | A kind of acrylic acid ester emulsion and its synthetic method of epoxy resin modification |
| CN109401690A (en) * | 2018-10-29 | 2019-03-01 | 无锡海特斯帝高分子材料有限公司 | A kind of waterborne epoxy modified acrylic ester medical pressure sensitive adhesive and preparation method thereof |
| CN110746840A (en) * | 2019-10-08 | 2020-02-04 | 苏州扬子江新型材料股份有限公司 | Heat shield color steel plate |
| CN111019281A (en) * | 2019-12-19 | 2020-04-17 | 上海贝塔建筑科技有限公司 | Acrylate epoxy resin hybrid emulsion, preparation method and application thereof, and artificial colored sand using acrylate epoxy resin hybrid emulsion |
| CN111978486A (en) * | 2020-08-20 | 2020-11-24 | 濮阳展辰新材料有限公司 | Polyacrylate emulsion and preparation method thereof |
| CN113307947A (en) * | 2021-05-24 | 2021-08-27 | 濮阳展辰新材料有限公司 | Acrylate emulsion and preparation method thereof |
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| CN103755890A (en) * | 2014-01-21 | 2014-04-30 | 山东圣光化工集团有限公司 | Method for preparing special epoxy modified polyacrylate emulsion for waterborne industrial paints |
| CN105732881A (en) * | 2016-05-16 | 2016-07-06 | 北京化工大学 | Waterborne epoxy/polyacrylate composite emulsion and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109180878A (en) * | 2018-09-26 | 2019-01-11 | 陕西科技大学 | A kind of acrylic acid ester emulsion and its synthetic method of epoxy resin modification |
| CN109401690A (en) * | 2018-10-29 | 2019-03-01 | 无锡海特斯帝高分子材料有限公司 | A kind of waterborne epoxy modified acrylic ester medical pressure sensitive adhesive and preparation method thereof |
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| CN110746840A (en) * | 2019-10-08 | 2020-02-04 | 苏州扬子江新型材料股份有限公司 | Heat shield color steel plate |
| CN110746840B (en) * | 2019-10-08 | 2021-08-24 | 苏州扬子江新型材料股份有限公司 | Heat shield color steel plate |
| CN111019281A (en) * | 2019-12-19 | 2020-04-17 | 上海贝塔建筑科技有限公司 | Acrylate epoxy resin hybrid emulsion, preparation method and application thereof, and artificial colored sand using acrylate epoxy resin hybrid emulsion |
| CN111019281B (en) * | 2019-12-19 | 2021-12-10 | 上海贝塔建筑科技有限公司 | Acrylate epoxy resin hybrid emulsion, preparation method and application thereof, and artificial colored sand using acrylate epoxy resin hybrid emulsion |
| CN111978486A (en) * | 2020-08-20 | 2020-11-24 | 濮阳展辰新材料有限公司 | Polyacrylate emulsion and preparation method thereof |
| CN111978486B (en) * | 2020-08-20 | 2024-02-27 | 濮阳展辰新材料有限公司 | Polyacrylate emulsion and preparation method thereof |
| CN113307947A (en) * | 2021-05-24 | 2021-08-27 | 濮阳展辰新材料有限公司 | Acrylate emulsion and preparation method thereof |
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