CN105732881A - Waterborne epoxy/polyacrylate composite emulsion and preparation method thereof - Google Patents
Waterborne epoxy/polyacrylate composite emulsion and preparation method thereof Download PDFInfo
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- 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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- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- 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
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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Abstract
The invention discloses waterborne epoxy/polyacrylate composite emulsion and a preparation method thereof, and belongs to the field of high polymer materials. The preparation method comprises the following steps: dissolving a monomer containing vinyl into bisphenol A epoxy resin in a mass ratio of (92:8)-(40:60); in the presence of a solution of an emulsifier and a co-emulsifier, emulsifying by using a high-pressure homogenizer, a high-shearing homogenizer, an emulsification grinding machine, a cam rotor pump, a re-circulation type emulsifier, a vacuum homogenizer or a dispersed emulsification homogenizer, and initiating fine emulsion polymerization by using a redox initiator, thereby obtaining the waterborne epoxy/polyacrylate composite emulsion. The waterborne epoxy/polyacrylate composite emulsion can be stored for more than or equal to one year, various auxiliaries and anti-corrosion pigment and packing can be compounded by taking the emulsion as a main filming substance, then varnish and colored paint can be prepared, a high-property metal anti-corrosion coating can be prepared by using a waterborne epoxy curing agent, and the salt mist resistant time of a substrate can be greater than or equal to 2000 hours when the thickness of a steel plate coating of the substrate is about 70mu m.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of water-base epoxy/poly acrylate composite emulsion and preparation method thereof.
Technical background
Epoxy resin, with the tack of its excellence, heat stability, chemical-resistant, insulating properties and mechanical strength etc., is widely used in paint field.Conventional epoxy resin great majority are sticky liquid or solid, for non-water-soluble, are dissolved only in the organic solvents such as aromatic hydrocarbons, ketone and alcohols.Along with VOC (VOC) is discharged quantitative limitation by people, the application in paint field of the solvent type epoxy resin is restricted.Aqueous epoxy resins is using water as disperse medium, and VOC emission amount is very low, and safety improves a lot, so aqueous epoxy resins becomes the research direction that people are new.
Water-borne modification of epoxy resin method has direct emulsion process, phase inversion and self-emulsification.These three kinds of methods have many research reports, have successfully prepared aqueous epoxy emulsion.Direct emulsion process technique is simple, but the emulsion particle diameter obtained is relatively big, and poor stability, such as US Patent No. 4,247,439.The aqueous epoxy resin emulsion stability obtained by chemical method is also relatively better.Terminal groups modification method in chemical method, is using epoxide group as reactive group, thus introducing water miscible polar group, such as patent CN1451701 and US Patent No. 4,289,811 etc..Epoxide group is consumed, thus affecting the degree of cross linking of final coating.Graft Method is to be grafted on epoxy main chains by aqueous group, and course of reaction is complicated, uncontrollable, and grafting degree is low, US Patent No. 4,579,888, US2,068,967 etc..Current water corrosion-resistant epoxy paint is little thus to result in film compactness relatively solvent-borne type poor due to the degree of cross linking, thus have impact on every antiseptic property.
Summary of the invention
Problem for aqueous epoxy resins film compactness, the present invention have employed the method for mini-emulsion polymerization and be prepared for water-base epoxy/poly acrylate composite emulsion, this kind of method remains most epoxide group, it is ensured that degree of cross linking during film forming, and forms the film of densification.Being added with of co-emulsifier is beneficial to raising emulsion intercalation method；The emulsifier system of anion and nonionic compound, it is ensured that the shelf-stability of emulsion and resistance to Ca2+Stability；The addition of reducing agent in initiator so that system gel fraction in course of reaction is substantially reduced；The use of high pressure homogenizer, high-shear homogenizing machine, emulsifying grinder, lobed rotor pump, recirculation type mulser, vacuum homogeneous emulsifying machine or dispersion and emulsion homogenizer greatly reduces the particle diameter of pre-emulsion, it is ensured that stability during reaction；React under relatively low reaction temperature, reduce the open loop rate of epoxide group, it is ensured that major part epoxide group is retained in emulsion.Thus the water-based anticorrosive paint obtained by complex emulsions has the advantages such as the adhesive force of excellence, excellent salt fog resistance, excellent anti-corrosive properties, good hardness and good impact resistance.
A kind of water-base epoxy/poly acrylate composite emulsion provided by the present invention and preparation method thereof, it is characterized in that, so that the monomer containing vinyl is dissolved in bisphenol A type epoxy resin, the mass ratio of the monomer containing vinyl and epoxy resin is 92:8 to 40:60, monomer containing vinyl accounts for the 40-92% of the monomer containing vinyl and epoxy resin total amount, through high pressure homogenizer under emulsifying agent and co-emulsifier solution exist, high-shear homogenizing machine, emulsifying grinder, lobed rotor pump, recirculation type mulser, after vacuum homogeneous emulsifying machine or dispersion and emulsion homogenizer emulsifying, mini-emulsion polymerization is caused with redox initiator, obtain water-base epoxy/poly acrylate composite emulsion, solid content is 20% to 50%.
The preparation method of a kind of water-base epoxy/poly acrylate composite emulsion provided by the present invention is as follows:
1) in reactor A, add emulsifying agent, co-emulsifier and deionized water, after stirring, prepare mixing liquid；
2) in reactor B, add the monomer containing vinyl, fully dissolve after epoxy resin is added, after stirring, obtain another kind of mixing liquid；
3) under agitation, the liquid in reactor B is dropped to gradually in reactor A, after mixing, obtain preliminary pre-emulsion；Then preliminary pre-emulsion is added to carrying out pre-emulsification in high pressure homogenizer, high-shear homogenizing machine, emulsifying grinder, lobed rotor pump, recirculation type mulser, vacuum homogeneous emulsifying machine or dispersion and emulsion homogenizer, obtain pre-emulsion；
4) by step 3) part of pre-emulsion is under the constant temperature of 30 DEG C to 80 DEG C, think wherein dropping initiator and residue pre-emulsion initiation reaction, react after dropwising and carry out after 1h-6h cooling down, neutralize, filter, obtain water-base epoxy/poly acrylate composite emulsion.
Step 4) in a part be preferably 5%-30%.
Further, the monomer containing vinyl refers to the mixture of one or more kinds in methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, N-Hexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, n-butyl acrylate, Isobutyl 2-propenoate, ethyl acrylate, n-octyl, Isooctyl acrylate monomer, isobornyl acrylate, acrylic acid, methacrylic acid, styrene.Preferred acrylic acid, methacrylic acid both acids are not used alone.
Further, bisphenol A type epoxy resin is one or more the mixture in E-01, E-03, E-06, E-12, E-14, E-20, E-31, E-35, E-42, E-44, E-51, E-55.
Further, emulsifying agent is allyloxy NPE ammonium sulfate, allyloxy decyl polyoxyethylene ether ammonium sulfate, allyloxy nonyl phenol propanol polyoxyethylene ether ammonium sulfate, allyloxy fatty alcohol-polyoxyethylene ether, allyloxy propyl alkyl alcohol polyethers, 2-Sulfosuccinic acid decyl polyoxyethylene ether-ester disodium, N-(1, 2-dicarboxyethyl) N-octadecyl sulphosuccinamate four sodium, sulfosuccinate derivatives, NPE, OPEO, fatty alcohol-polyoxyethylene ether carboxylic acid sodium, epoxy ethane-epoxy propane block copolymer, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, dodecyl sodium sulfate, sodium lauryl sulphate, alkyl phenoxyl polyether thiourea hydrochlorate, one or more mixture in acrylamido sodium isopropyl xanthate.
Further, co-emulsifier is one or more the mixture in dodecane, hexadecane, capryl alcohol, nonyl alcohol, decanol, lauryl alcohol, tetradecyl alchohol, hexadecanol.
nullFurther，Redox initiator systems is Ammonium persulfate ./BRUGGOLITEFF6M、Potassium peroxydisulfate/BRUGGOLITEFF6M、Sodium peroxydisulfate/BRUGGOLITEFF6M、Ammonium persulfate ./BRUGGOLITEE01、Potassium peroxydisulfate/BRUGGOLITEE01、Sodium peroxydisulfate/BRUGGOLITEE01、Ammonium persulfate ./BRUGGOLITETP1328、Potassium peroxydisulfate/BRUGGOLITETP1328、Sodium peroxydisulfate/BRUGGOLITETP1328、Ammonium persulfate ./BRUGGOLITETP1351、Potassium peroxydisulfate/BRUGGOLITETP1351、Sodium peroxydisulfate/BRUGGOLITETP1351、Ammonium persulfate ./BRUGGOLITETP1352、Potassium peroxydisulfate/BRUGGOLITETP1352、Sodium peroxydisulfate/BRUGGOLITETP1352、Ammonium persulfate ./sodium sulfite、Potassium peroxydisulfate/sodium sulfite、Sodium peroxydisulfate/sodium sulfite、Potassium peroxydisulfate/ferrous chloride、Ammonium persulfate ./ferrous chloride、Sodium peroxydisulfate/ferrous chloride、Hydrogen peroxide/ferrous chloride、Dibenzoyl peroxide/aniline、T-butyl hydroperoxide/sodium formaldehyde sulphoxylate、One or more mixture in different phenylpropyl alcohol hydrogen peroxide/sodium formaldehyde sulphoxylate.
The application of the water-base epoxy/poly acrylate composite emulsion prepared by the present invention, it is characterized in that: being used for preparing water paint, prepared varnish paint component A is made up of the component of following weight portion: water-base epoxy/poly acrylate composite emulsion 100 parts adds levelling agent 0.3～0.6 part, defoamer 0.1～1 part, corrosion inhibiter 0.1～0.2 part, coalescents 4～6 parts, thickening agent 0.1～0.5 part；B component is that the aqueous epoxy curing agent such as HGF-100 of commercially available modified aromatic amine, component A and B component mix use according to the ratio 1:0.8 to 1:1.2 of epoxide equivalent and active hydrogen equivalent weight.
The application of the water-base epoxy/poly acrylate composite emulsion prepared by the present invention, it is characterized in that: being used for preparing water paint, prepared color paint coating component A is made up of the component of following weight portion: water-base epoxy/poly acrylate composite emulsion 60～70 parts, 8～10 parts of Talcum, Muscovitum iron oxide red 10～15 parts, zinc phosphate 10～13 parts, levelling agent 0.3～0.6 part, wetting dispersing agent 0.3～0.6 part, defoamer 0.1～1 part, corrosion inhibiter 0.1～0.2 part, coalescents 4～6 parts, thickening agent 0.1～0.5 part；B component is the aqueous epoxy curing agent such as HGF-100 of commercially available modified aromatic amine.Component A and B component mix use according to the ratio 1:0.8 to 1:1.2 of epoxide equivalent and active hydrogen equivalent weight.
Water-base epoxy/poly acrylate composite emulsion solid content is 20%-50%.
Emulsion prepared by the present invention can store placement more than 1 year.With this emulsion for main film forming matter, composite various auxiliary agent, and anticorrosive pigment/filler prepares varnish and colored paint, uses aqueous epoxy curing agent to solidify to obtain high-performance metal anticorrosive paint, when base material be steel plate coating thickness is about 70 μm, its salt-fog resistant time is up to more than 2000h.
Detailed description of the invention
Following example are further illustrating the present invention, rather than restriction the scope of the present invention.
Embodiment 1
Reactor A adds 0.1kg NPE, 0.2kg allyloxy nonyl phenol propanol polyoxyethylene ether ammonium sulfate, 0.4kg hexadecane and the mixing of 20kg deionized water, after stirring, obtains mixing liquid.Reactor B adds 4kg butyl acrylate, 10.8kg methyl methacrylate, 0.2kg acrylic acid, fully dissolves after 6.5kg epoxy resin E-44 is added, after stirring, obtain another kind of mixing liquid.Under agitation, the liquid in reactor B is dropped to gradually in reactor A, after mixing, obtain preliminary pre-emulsion.Preliminary pre-emulsion is added to high pressure homogenizer, under the homogenization pressure of 80MPa, carries out pre-emulsification, obtain pre-emulsion.0.2kg Ammonium persulfate. is dissolved in 3kg deionized water, stirs.0.08kgBRUGGOLITEFF6M is dissolved in 3kg deionized water, stirs.Partial monosomy pre-emulsion is added in reactor C, under the constant temperature of 60 DEG C, dropping initiator solution and residual monomer pre-emulsion initiation reaction respectively, carry out after reaction 3h cooling down, neutralize, filter, obtain water-base epoxy/poly acrylate composite emulsion.
Embodiment 2
The 6.5kg epoxy resin E-44 added in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replaces with 6.5kgE-51, and other are identical with embodiment 1.
Embodiment 3
The 6.5kg epoxy resin E-44 added in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replaces with 6.5kgE-20, and other are identical with embodiment 1.
Embodiment 4
The 6.5kg epoxy resin E-44 added in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replaces with 6.5kgE-06, and other are identical with embodiment 1.
Embodiment 5
6.5kgE-44,4kg butyl acrylate, the 10.8kg methyl methacrylate that add in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion change 1.7kgE-44,5.3kg butyl acrylate, 14.3kg methyl methacrylate into, and other are identical with embodiment 1.
Embodiment 6
6.5kgE-44,4kg butyl acrylate, the 10.8kg methyl methacrylate that add in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion change 3.2kgE-44,4.9kg butyl acrylate, 13.2kg methyl methacrylate into, and other are identical with embodiment 1.
Embodiment 7
6.5kgE-44,4kg butyl acrylate, the 10.8kg methyl methacrylate that add in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion change 9.6kgE-44,3.2kg butyl acrylate, 8.6kg methyl methacrylate into, and other are identical with embodiment 1.
Embodiment 8
6.5kgE-44,4kg butyl acrylate, the 10.8kg methyl methacrylate that add in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion change 12.8kgE-44,2.3kg butyl acrylate, 6.2kg methyl methacrylate into, and other are identical with embodiment 1.
Embodiment 9
The 0.1kg NPE added in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replaces with 0.1kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, and other are identical with embodiment 1.
Embodiment 10
The 0.1kg NPE, the 0.2kg allyloxy nonyl phenol propanol polyoxyethylene ether ammonium sulfate that add in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replace with 0.3kg OPEO, and other are identical with embodiment 1.
Embodiment 11
The 0.1kg NPE, the 0.2kg allyloxy nonyl phenol propanol polyoxyethylene ether ammonium sulfate that add in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replace with 0.2kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, allyloxy nonyl phenol propanol polyoxyethylene ether ammonium sulfate, and other are identical with embodiment 1.
Embodiment 12
The 0.1kg NPE, the 0.2kg allyloxy nonyl phenol propanol polyoxyethylene ether ammonium sulfate that add in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replace with 0.2kg disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, 0.1kg allyloxy fatty alcohol-polyoxyethylene ether, and other are identical with embodiment 1.
Embodiment 13
The 0.08kgBRUGGOLITEFF6M added in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replaces with 0.08kg sodium sulfite, and other are identical with embodiment 1.
Embodiment 14
The 0.2kg Ammonium persulfate., the 0.08kgBRUGGOLITEFF6M that add in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replace with 0.2kg t-butyl hydroperoxide, 0.08kg sodium formaldehyde sulphoxylate, and other are identical with embodiment 1.
Comparative example 15
The 0.2kg Ammonium persulfate., the 0.08kgBRUGGOLITEFF6M that add in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replace with 0.2kg dibenzoyl peroxide, 0.08kg aniline, and other are identical with embodiment 1.
Embodiment 16
The 10.8kg methyl methacrylate added in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replaces with 10.8kg styrene, and other are identical with embodiment 1.
Embodiment 17
The 0.2kg acrylic acid added in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replaces with 0.2kg methacrylic acid, and other are identical with embodiment 1.
Embodiment 18
The 0.4kg hexadecane added in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion replaces with 0.4kg hexadecanol, and other are identical with embodiment 1.
Embodiment 19
The homogenization pressure 80MPa carrying out the pre-emulsified high pressure homogenizer of monomer in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion changes 20MPa into, and other are identical with embodiment 1.
Embodiment 20
The homogenization pressure 80MPa carrying out the pre-emulsified high pressure homogenizer of monomer in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion changes 40MPa into, and other are identical with embodiment 1.
Embodiment 21
The homogenization pressure 80MPa carrying out the pre-emulsified high pressure homogenizer of monomer in the preparation method of present embodiment water-base epoxy/poly acrylate composite emulsion changes 60MPa into, and other are identical with embodiment 1.
Embodiment 22
The pre-emulsified high pressure homogenizer of monomer that carries out in the preparation method of embodiment water-base epoxy/poly acrylate composite emulsion replaces with homogenizer, and stir speed (S.S.) is 2000r min-1, mixing time is 20min, and other are identical with embodiment 1.
Embodiment 23
The pre-emulsified high pressure homogenizer of monomer that carries out in the preparation method of embodiment water-base epoxy/poly acrylate composite emulsion replaces with homogenizer, and stir speed (S.S.) is 4000r min-1, mixing time is 20min, and other are identical with embodiment 1.
Embodiment 24
The pre-emulsified high pressure homogenizer of monomer that carries out in the preparation method of embodiment water-base epoxy/poly acrylate composite emulsion replaces with high-shear homogenizing machine, and stir speed (S.S.) is 2000r min-1, mixing time is 30min, and other are identical with embodiment 1.
Embodiment 25
The pre-emulsified high pressure homogenizer of monomer that carries out in the preparation method of embodiment water-base epoxy/poly acrylate composite emulsion replaces with emulsifying grinder, and stir speed (S.S.) is 3000r min-1, mixing time is 20min, and other are identical with embodiment 1.
Embodiment 26
The pre-emulsified high pressure homogenizer of monomer that carries out in the preparation method of embodiment water-base epoxy/poly acrylate composite emulsion replaces with lobed rotor pump, and stir speed (S.S.) is 400r min-1, mixing time is 20min, and other are identical with embodiment 1.
Embodiment 27
The pre-emulsified high pressure homogenizer of monomer that carries out in the preparation method of embodiment water-base epoxy/poly acrylate composite emulsion replaces with recirculation type mulser, and stir speed (S.S.) is 100r min-1, mixing time is 20min, and other are identical with embodiment 1.
Embodiment 28
The pre-emulsified high pressure homogenizer of monomer that carries out in the preparation method of embodiment water-base epoxy/poly acrylate composite emulsion replaces with vacuum homogeneous emulsifying machine, and stir speed (S.S.) is 2000r min-1, mixing time is 20min, and other are identical with embodiment 1.
Embodiment 29
The pre-emulsified high pressure homogenizer of monomer that carries out in the preparation method of embodiment water-base epoxy/poly acrylate composite emulsion replaces with dispersion and emulsion homogenizer, and frequency is 50Hz, and mixing time is 20min, and other are identical with embodiment 1.
Embodiment 30
Water varnish coating: under high velocity agitation, by 0.4gBYK333,0.1gBYK012,0.1gNaNO2, 4gDPNB and 0.2gBYK425 add to gained 100g complex emulsions in embodiment 1, obtain final required varnish paint component A.12gB component HGF-100 is mixed with the component A prepared, after stirring, prepares varnish.
Embodiment 31
Water varnish coating: under high velocity agitation, by 0.4gBYK333,0.1gBYK012,0.1gNaNO2, 4gDPNB and 0.2gBYK425 add to gained 100g complex emulsions in embodiment 7, obtain final required varnish paint component A.18gB component HGF-100 is mixed with the component A prepared, after stirring, prepares varnish.
Embodiment 32
Water varnish coating: under high velocity agitation, by 0.4gBYK333,0.1gBYK012,0.1gNaNO2, 4gDPNB and 0.2gBYK425 add to gained 100g complex emulsions in embodiment 8, obtain final required varnish paint component A.24gB component HGF-100 is mixed with the component A prepared, after stirring, prepares varnish.
Embodiment 33
Water colour paint coating: under high velocity agitation, by 14g Talcum, 20g Muscovitum iron oxide red, 17g zinc phosphate, 0.6gBYK190,0.6gBYK333,0.7gBYK012,0.2gNaNO2, 6.4gDPNB and 0.3gBYK425 add to the 90g emulsion of gained in above-described embodiment 1, obtain final required color paint coating component A.10gB component HGF-100 is mixed with the component A prepared, after stirring, prepares colored paint.
Embodiment 34
Water colour paint coating: under high velocity agitation, by 14g Talcum, 20g Muscovitum iron oxide red, 17g zinc phosphate, 0.6gBYK190,0.6gBYK333,0.7gBYK012,0.2gNaNO2, 6.4gDPNB and 0.3gBYK425 add to the 90g emulsion of gained in above-described embodiment 7, obtain final required color paint coating component A.10gB component HGF-100 is mixed with the component A prepared, after stirring, prepares colored paint.
Embodiment 35
Water colour paint coating: under high velocity agitation, by 14g Talcum, 20g Muscovitum iron oxide red, 17g zinc phosphate, 0.6gBYK190,0.6gBYK333,0.7gBYK012,0.2gNaNO2, 6.4gDPNB and 0.3gBYK425 add to the 90g emulsion of gained in above-described embodiment 8, obtain final required color paint coating component A.10gB component HGF-100 is mixed with the component A prepared, after stirring, prepares colored paint.
Water-base epoxy obtained by embodiment 1～29/poly acrylate composite emulsion performance is as shown in table 1.
Table 1 embodiment test result
Water paint varnish obtained by embodiment 30～35 and colored paint, obtain the perishable metal anti-corrosive paint of high-performance after overcuring, when coating layer thickness is about 70 μm, and its key technical indexes, the i.e. Corrosion Protection of coating and mechanical property, as shown in table 2.The hardness of paint film presses GB/T6739-2006, adopts QHQ pencil hardness instrument to measure.The adhesive force of paint film presses GB9286-1998, adopts cross-hatching to measure；The resistance to impact of paint film presses GB/T1732-1993, adopts QJL shock machine to measure；The salt spray resistance of paint film is pressed GB/T1771-1991 and is measured, and varnish use is complete, and paint film is tested, and colored paint is tested after scratching；The resistance to water of paint film is pressed GB/T1733-1993 and is measured；The resistant to liquid medium of paint film is pressed GB/T9274-1988 and is measured.
The properties of table 2 varnish and colored paint coating
Claims (10)
1. the preparation method of water-base epoxy/poly acrylate composite emulsion, it is characterized in that, so that the monomer containing vinyl is dissolved in bisphenol A type epoxy resin, the mass ratio of the monomer containing vinyl and epoxy resin is 92:8 to 40:60, under emulsifying agent and co-emulsifier solution exist after high pressure homogenizer, high-shear homogenizing machine, emulsifying grinder, lobed rotor pump, recirculation type mulser, vacuum homogeneous emulsifying machine or dispersion and emulsion homogenizer emulsifying, cause mini-emulsion polymerization with redox initiator, obtain water-base epoxy/poly acrylate composite emulsion.
2. the preparation method of a kind of water-base epoxy/poly acrylate composite emulsion described in claim 1, it is characterised in that specifically include following steps further:
1) in reactor A, add emulsifying agent, co-emulsifier and deionized water, after stirring, prepare mixing liquid；
2) in reactor B, add the monomer containing vinyl, fully dissolve after epoxy resin is added, after stirring, obtain another kind of mixing liquid；
3) under agitation, the liquid in reactor B is dropped to gradually in reactor A, after mixing, obtain preliminary pre-emulsion；Then preliminary pre-emulsion is added to carrying out pre-emulsification in high pressure homogenizer, high-shear homogenizing machine, emulsifying grinder, lobed rotor pump, recirculation type mulser, vacuum homogeneous emulsifying machine or dispersion and emulsion homogenizer, obtain pre-emulsion；
4) by step 3) part of pre-emulsion is under the constant temperature of 30 DEG C to 80 DEG C, think wherein dropping redox initiator and residue pre-emulsion initiation reaction, react after dropwising and carry out after 1h-6h cooling down, neutralize, filter, obtain water-base epoxy/poly acrylate composite emulsion.
3. the preparation method of a kind of water-base epoxy/poly acrylate composite emulsion described in claim 1 or 2, it is characterised in that step 4) in a part be 5%-30%.
4. the preparation method of a kind of water-base epoxy/poly acrylate composite emulsion described in claim 1, it is characterized in that, monomer containing vinyl refers to methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, N-Hexyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, n-butyl acrylate, Isobutyl 2-propenoate, ethyl acrylate, n-octyl, Isooctyl acrylate monomer, isobornyl acrylate, acrylic acid, methacrylic acid, the mixture of one or more kinds in styrene.
5. the preparation method of a kind of water-base epoxy/poly acrylate composite emulsion described in claim 1, it is characterized in that, bisphenol A type epoxy resin is one or more the mixture in E-01, E-03, E-06, E-12, E-14, E-20, E-31, E-35, E-42, E-44, E-51, E-55.
null6. the preparation method of a kind of water-base epoxy/poly acrylate composite emulsion described in claim 1，It is characterized in that，Emulsifying agent is allyloxy NPE ammonium sulfate、Allyloxy decyl polyoxyethylene ether ammonium sulfate、Allyloxy nonyl phenol propanol polyoxyethylene ether ammonium sulfate、Allyloxy fatty alcohol-polyoxyethylene ether、Allyloxy propyl alkyl alcohol polyethers、2-Sulfosuccinic acid decyl polyoxyethylene ether-ester disodium、N-(1，2-dicarboxyethyl) N-octadecyl sulphosuccinamate four sodium、Sulfosuccinate derivatives、NPE、OPEO、Fatty alcohol-polyoxyethylene ether carboxylic acid sodium、Epoxy ethane-epoxy propane block copolymer、Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate、Dodecyl sodium sulfate、Sodium lauryl sulphate、Alkyl phenoxyl polyether thiourea hydrochlorate、One or more mixture in acrylamido sodium isopropyl xanthate.
7. the preparation method of a kind of water-base epoxy/poly acrylate composite emulsion described in claim 1, it is characterized in that, co-emulsifier is one or more the mixture in dodecane, hexadecane, capryl alcohol, nonyl alcohol, decanol, lauryl alcohol, tetradecyl alchohol, hexadecanol.
null8. the preparation method of a kind of water-base epoxy/poly acrylate composite emulsion described in claim 1，It is characterized in that，Redox initiator systems is Ammonium persulfate ./BRUGGOLITEFF6M、Potassium peroxydisulfate/BRUGGOLITEFF6M、Sodium peroxydisulfate/BRUGGOLITEFF6M、Ammonium persulfate ./BRUGGOLITEE01、Potassium peroxydisulfate/BRUGGOLITEE01、Sodium peroxydisulfate/BRUGGOLITEE01、Ammonium persulfate ./BRUGGOLITETP1328、Potassium peroxydisulfate/BRUGGOLITETP1328、Sodium peroxydisulfate/BRUGGOLITETP1328、Ammonium persulfate ./BRUGGOLITETP1351、Potassium peroxydisulfate/BRUGGOLITETP1351、Sodium peroxydisulfate/BRUGGOLITETP1351、Ammonium persulfate ./BRUGGOLITETP1352、Potassium peroxydisulfate/BRUGGOLITETP1352、Sodium peroxydisulfate/BRUGGOLITETP1352、Ammonium persulfate ./sodium sulfite、Potassium peroxydisulfate/sodium sulfite、Sodium peroxydisulfate/sodium sulfite、Potassium peroxydisulfate/ferrous chloride、Ammonium persulfate ./ferrous chloride、Sodium peroxydisulfate/ferrous chloride、Hydrogen peroxide/ferrous chloride、Dibenzoyl peroxide/aniline、T-butyl hydroperoxide/sodium formaldehyde sulphoxylate、One or more mixture in different phenylpropyl alcohol hydrogen peroxide/sodium formaldehyde sulphoxylate.
9. water-base epoxy/poly acrylate composite emulsion that the method described in any one of claim 1-8 prepares.
10. the application of water-base epoxy/poly acrylate composite emulsion prepared by the method described in any one of claim 1-8, it is characterized in that: being used for preparing water paint, prepared varnish paint component A is made up of the component of following weight portion: water-base epoxy/poly acrylate composite emulsion 100 parts adds levelling agent 0.3～0.6 part, defoamer 0.1～1 part, corrosion inhibiter 0.1～0.2 part, coalescents 4～6 parts, thickening agent 0.1～0.5 part；B component is the aqueous epoxy curing agent of modified aromatic amine；Component A and B component mix use according to the ratio 1:0.8 to 1:1.2 of epoxide equivalent and active hydrogen equivalent weight.
Or it being used for preparing water paint, prepared color paint coating component A is made up of the component of following weight portion: water-base epoxy/poly acrylate composite emulsion 60～70 parts, 8～10 parts of Talcum, Muscovitum iron oxide red 10～15 parts, zinc phosphate 10～13 parts, levelling agent 0.3～0.6 part, wetting dispersing agent 0.3～0.6 part, defoamer 0.1～1 part, corrosion inhibiter 0.1～0.2 part, coalescents 4～6 parts, thickening agent 0.1～0.5 part；B component is the aqueous epoxy curing agent of modified aromatic amine；Component A and B component mix use according to the ratio 1:0.8 to 1:1.2 of epoxide equivalent and active hydrogen equivalent weight；
The solid content of water-base epoxy/poly acrylate composite emulsion is 20%-50%.
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