CN104559682B - A kind of water-based epoxy acrylic self demixing emulsion protected for concrete surface - Google Patents
A kind of water-based epoxy acrylic self demixing emulsion protected for concrete surface Download PDFInfo
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- 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
- 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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Abstract
The invention provides a kind of water-based epoxy acrylic self demixing emulsion protected for concrete surface and preparation method thereof.The present invention utilizes RAFT mini-emulsion polymerization methods, prepares epoxy-acrylate emulsion, this method have effectively achieved the control of epoxy monomer addition.Epoxy emulsion, epoxy-acrylate emulsion, acrylic emulsion, various auxiliary agents etc. are configured to the concrete protectant of self demixing, coating process is simplified, the excellent adhesive force of epoxy and the ageing-resistant advantage of acrylic acid are played to greatest extent.
Description
Technical field
The present invention relates to a kind of preparation side for the aqueous epoxy-acrylic self demixing emulsion protected for concrete surface
Method.
Background technology
Concrete under arms during, be faced with the erosion of many extraneous hazardous mediums, especially carbon dioxide and chlorine from
Son.Problem of Cracking is generally asking of facing in engineering caused by the steel bar corrosion expansion as caused by carbon dioxide and Chloride Attack
Topic, seriously reduces the durability and service life of concrete.The frequent bearing temperature change in outer surface, the current punching of concrete
Brush, alternation of wetting and drying, Frozen-thawed cycled etc. are acted on, thus constantly weathering, degrade, be carbonized, progressively aggravate with the passage of time, final danger
And the safety of engineering structure.
Solving the method for the problem at present mainly includes three below aspect：1, in concrete preparation process, strengthen matter
Amount control, it is to avoid because the concrete density that raw material reason is caused declines, the especially generation of cracking phenomena；2, concrete
After pouring, strengthen maintenance measure, it is ensured that cement being capable of abundant aquation, the compactness of increase concrete, so as to lift concrete sheet
The ability of body resistant to carbon dioxide and Chloride Attack；3, during concrete military service, protective layer is applied, so as to reduce titanium dioxide
The erosion of carbon and chlorion.Concrete surface coating protection method is the method for economical and efficient the most, but conventional surface protection is applied
There are many deficiencies in anti-carbonation, durability, anti-salt corrosion etc. in layer.
The method of current emulsion coating protective layer reduction carbon dioxide and Chloride Attack is all to brush a kind of emulsion, for example
CN201210431578.3 discloses a kind of without the concrete protection emulsion obtained using soap emulsion polymerization.Individual layer emulsion paint film is very
Hardly possible integrates cost and performance.
Existing self demixing technology is applied in solvent type coating, and for example CN103525284A is disclosed
It is a kind of with N, N- dimethyl acetamides and dimethylbenzene are solvent ocean heavy antisepsis epoxy-fluorine-containing self stratifying coating.And it is aqueous from
The design of intermediate layer emulsion is the ratio of conventional emulsion polymerizations, epoxy monomer or resin in layering emulsion（0-10%）It is relatively low.
The content of the invention
In order to solve in existing concrete protection or the problem of the good individual layer paint film of performance is costly, and tack is good
Self demixing paint film the problem of cause environmental pollution using solvent, the invention provides a kind of water protected for concrete surface
Property epoxy-acrylic self demixing emulsion and preparation method thereof.
The present invention utilizes RAFT mini-emulsion polymerization methods, prepares epoxy-acrylic emulsion, this method is effectively realized
The control of epoxy monomer addition.Emulsification is obtained into epoxy emulsion, epoxy-acrylic emulsion, acrylic emulsion, various auxiliary agents
Etc. the concrete protectant for being configured to self demixing, coating process is simplified, the excellent adhesive force of epoxy is played to greatest extent
With the ageing-resistant advantage of acrylic acid.
Aqueous epoxy-acrylic self demixing emulsion of the present invention is made up of following components by following percentage by weights：
Epoxy emulsion 10-50%,
Epoxy-acrylic emulsion 1-10%,
Acrylic emulsion 6-40%,
Curing agent 0-6%,
PH conditioning agent 0.5-3%,
Coalescents 0-6%,
Plasticizer 0-6%,
Defoamer 0-6%,
Levelling agent 0-6%,
Water surplus；
The solid content of the aqueous epoxy-acrylic self demixing emulsion is not less than 20wt%；
The acrylic emulsion is through emulsion polymerization by esters of acrylic acid or methyl acrylic ester and other olefinic type monomers
The water dispersion emulsion of formation, commercially available, the MFT of resin is not less than 10 DEG C in emulsion, and solid content is not less than 45%.
The curing agent is in the polyamine such as ethylenediamine, diethylenetriamine, polyethylene polyamine, phenylenediamine, m-xylene diamine
More than one arbitrary proportion mixture.
The pH value conditioning agent is selected from 2-amino-2-methyl-1-propanol（AMP95）Or ammoniacal liquor.
The coalescents are alcohol ester 12, butyl glycol ether, propylene glycol monomethyl ether, propandiol butyl ether, propane diols phenylate, two
The mixture of one or more of ethylene glycol monoethyl ether and dipropylene glycol methyl ether arbitrary proportion.
The plasticizer is dibutyl phthalate.
The defoamer is C7-C22 higher alcohols, more than one arbitrary proportions of polyethers and organic silicon defoamer
Mixture.
The levelling agent is more than one any ratios of silicone levelling agent, acrylic compounds levelling agent and fluorine class levelling agent
The mixture of example.
The epoxy emulsion is prepared by following methods：
At 60-90 DEG C, deionized water is added dropwise under 200-600rpm stirring conditions in the mixture of epoxy resin and emulsifying agent
Obtain epoxy emulsion.
The epoxy resin is bisphenol A type epoxy resin：One kind in E51, E44, E42, E54, E35, E31, E20, E12
Or it is two or more mixed with arbitrary proportion, the emulsifying agent used in the epoxy emulsion be anion nonionic emulsifier compounding obtain
's.Between emulsifying agent/bisphenol A type epoxy resin=8-10%, HLB=13-15.
The epoxy-acrylic emulsion by epoxy monomer with（Methyl）Acrylic acid（Ester）And/or styrene is carefully newborn through RAFT
Liquid polymerization is made, epoxy monomer with（Methyl）Acrylic acid（Ester）And/or the mass ratio of styrene is 3:7-7:3.
If use simultaneously（Methyl）Acrylic acid（Ester）And styrene,（Methyl）Acrylic acid（Ester）/ styrene>1：1.
The specific preparation process of the epoxy-acrylic emulsion is：
1）In addition to above-mentioned polymerized monomer, chain-transferring agent, initiator, emulsifying agent, assistant for emulsifying agent and water are also added, is gathered relatively
Close the quality of monomer, chain-transferring agent, initiator, emulsifying agent, the amount of assistant for emulsifying agent and water be respectively 0.5-4%, 0.3-0.6%,
1.5-3 %、1-3%、2.3-5.7；
2）After above-mentioned each component stirring and emulsifying, ultrasonic disperse 5-15min obtains adding after miniemulsion, deoxygenation 15-30min
Heat obtains the epoxy-acrylic emulsion to 70-85 DEG C of reaction 1h-3h.
The solid content of the epoxy-acrylic emulsion is 15-30wt%.
Described epoxy monomer, selected from allyl glycidyl（AGE）, glycidyl acrylate（GA）And methyl
Glycidyl acrylate（GMA）One or both of more than.
It is described（Methyl）Propylene（Acid）Ester monomer is methacrylic acid, methyl methacrylate, EMA, first
One kind in base 2-ethyl hexyl acrylate, butyl methacrylate, acrylic acid, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate or
Plant or the mixing of two or more arbitrary proportions.
Described chain-transferring agent be 2- (dodecyl trithiocarbonate) -2- methacrylic acids, S-1- dodecyls -
One kind in S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate.
Initiator used is one kind in potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate.
Emulsifying agent used is anion or anion nonionic compound emulsifier, assistant for emulsifying agent are hexadecane.
The preparation method of aqueous epoxy-acrylic self demixing concrete protectant of the present invention, its preparation method is：Will
Above-mentioned each component is well mixed and obtains the aqueous epoxy-acrylic self demixing concrete protectant.
Relative to traditional protective materials, the advantages of the present invention are：MOLECULE DESIGN and component it is reasonable
It is transported to, introduces self demixing technology and obtain gradient coating.It is automatic to base layer motion in emulsion drying and forming-film process epoxy resin, increase
Plus with the adhesive force of concrete surface so as to improving agent on crack resistance of concrete carbonization, anti-salt corrosion and impermeability.And acrylic resin to
Top layer motion compensate for the characteristics of epoxy resin is not weather-proof, the connection of the compatibility and its paint film of epoxy resin and acrylic resin
Property improve by the epoxy-acrylic resin in intermediate layer.Emulsion applications newest RAFT mini-emulsion polymerizations in intermediate layer obtain epoxy
The controllable epoxy-acrylic emulsion of ratio.Compared with prior art, the advantage of epoxy and acrylic resin had not only been combined but also had simplified
Construction technology, and with cost advantage.
Embodiment
For a better understanding of the present invention, present disclosure is further described with reference to embodiment, but this
The content of invention is not limited to the scope of embodiment statement.
In each embodiment, number of freezing and thawing, concrete carbonization degree and chloride permeability depth are produced according to building industry industry
Product standard JG/T335-2011《Film-forming type coating is used in concrete structure protection》It is required that determining.It is number of freezing and thawing, mixed in each embodiment
Solidifying soil carbonizing degree and chloride permeability depth are according to building industry industry product standard JG/T335-2011《Concrete structure is prevented
Shield uses film-forming type coating》It is required that determining.The acrylic emulsion said in another following embodiment is from the purchase of Xi Ka Co., Ltds
Model sikagard 550 emulsion.
Embodiment 1
1）The preparation of epoxy-acrylic emulsion：Use 25 ethyl acrylates, 5g 2-Propenoic acid, 2-methyl-, octyl esters, 15g allyl glycidyls
Glyceride（AGE), 2.4g 2- (dodecyl trithiocarbonate) -2- methacrylic acids（DDMAT）, 0.58g potassium peroxydisulfates
（KPS）, 1g dodecyl sodium sulfates（SDS）, 1g hexadecanes, 100g deionized waters mixing 100rmp stirring and emulsifyings after ultrasonic disperse
5-15min is obtained under miniemulsion, stirring condition, and 75 DEG C of reaction 2h are heated to after logical deoxygenation 15-30min and obtain terminal epoxy-the third
Olefin(e) acid emulsion.
2）The preparation of epoxy emulsion：Under stirring condition, by 25g bisphenol A epoxide resins E51,25g bisphenol A epoxide resin
E31,3.0g polyoxyethylene (20) sorbitan mono-laurate（Tween20）, 1.5g sorbitan monostearates
（Span60）, the mixture of 0.5g dodecyl sodium sulfates is heated to 80 DEG C, and 61g deionized waters are slowly added drop-wise into mixed epoxy mixes
Epoxy emulsion is obtained in compound.Stirring 1h obtains terminal epoxy emulsion.
3）The preparation of aqueous epoxy-acrylic self demixing emulsion：28g epoxy emulsions, 1g epoxy-acrylic emulsions；6g third
Olefin(e) acid emulsion, 1g curing agent ethylene diamines, 0.5g PH conditioning agents AMP95,1g coalescents alcohol ester 12,1g plasticizer neighbour's benzene two
Formic acid dibutyl ester, 1g defoamer n-octyl alcohols, 1g fluorine carbon levelling agents, 59.5g deionized waters compound obtaining water-base epoxy-propylene
Sour self demixing emulsion.It is 15% to test its solid content.The freeze thawing more than 500 times is met without peeling, without foaming phenomena, 28d carbon is reduced
Change degree 90%, chloride permeability depth 90%.
Embodiment 2
1）The preparation of epoxy-acrylic emulsion：With 35g butyl methacrylate, 15g allyl glycidyls
（AGE), 2.4g 2- (dodecyl trithiocarbonate) -2- methacrylic acids（DDMAT）, 0.58g potassium peroxydisulfates（KPS）,
1g dodecyl sodium sulfates（SDS）, 1g hexadecanes, 100g deionized waters mixing 100rmp stirring and emulsifyings after ultrasonic disperse 5-
15min is obtained under miniemulsion, stirring condition, and 75 DEG C of reaction 2h are heated to after logical deoxygenation 15-30min and obtain terminal epoxy-propylene
Yogurt liquid.
2）The preparation of epoxy emulsion：Under stirring condition, by 25g bisphenol A epoxide resins E51,25g bisphenol A epoxide resin
E18,3.0g polyoxyethylene (20) sorbitan mono-laurate（Tween20）, 1.5g sorbitan monostearates
（Span60）, the mixture of 0.5g dodecyl sodium sulfates is heated to 80 DEG C, and 61g deionized waters are slowly added drop-wise into mixed epoxy mixes
Epoxy emulsion is obtained in compound.Stirring 1h obtains terminal epoxy emulsion.
3）The preparation of aqueous epoxy-acrylic self demixing emulsion：22g epoxy emulsions, 1g epoxy-acrylic emulsions；10g third
Olefin(e) acid emulsion；1g curing agent ethylene diamines, 0.5g PH conditioning agents AMP95,1g coalescents alcohol ester 12,1g plasticizer neighbour's benzene two
Formic acid dibutyl ester, 1g defoamer n-octyl alcohols, 1g fluorine carbon levelling agents, 61.5g deionized waters compound obtaining water-base epoxy-propylene
Sour self demixing emulsion.It is 15% to test its solid content.The freeze thawing more than 600 times is met without peeling, without foaming phenomena, 28d carbon is reduced
Change degree 94%, chloride permeability depth 91%.
Embodiment 3
1）The preparation of epoxy-acrylic emulsion：With 20g methyl methacrylate, 5g butyl acrylates, 15g acrylic acid
Ethylene oxidic ester（GA）, 1.2g S-1- dodecyls-S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate（TTC）,
0.29g potassium peroxydisulfates（KPS）, 1g dodecyl sodium sulfates（SDS）, 1g hexadecanes, 100g deionized waters mixing 100rmp stirring
Ultrasonic disperse 5-15min is obtained under miniemulsion, stirring condition after emulsification, and 85 DEG C of reaction 2h are heated to after logical deoxygenation 15-30min and are obtained
To terminal epoxy-acrylic emulsion.
2）The preparation of epoxy emulsion：Under stirring condition, by 25g bisphenol A epoxide resins E44,25g bisphenol A epoxide resin
E21,3.5g polyoxyethylene (40) sorbitan mono-laurate（Tween40）, 1g sorbitan monostearates
（Span20）, the mixture of 0.5g dodecyl sodium sulfates is heated to 80 DEG C, and 61g deionized waters are slowly added drop-wise into mixed epoxy mixes
Epoxy emulsion is obtained in compound.Stirring 1h obtains terminal epoxy emulsion.
3）The preparation of aqueous epoxy-acrylic self demixing emulsion：30g epoxy emulsions, 3g epoxy-acrylic emulsions, 12g third
Olefin(e) acid emulsion, 1g curing agent ethylene diamines, 0.5g PH conditioning agents AMP95,1g coalescents alcohol ester 12,1g plasticizer neighbour's benzene two
Formic acid dibutyl ester, 1g defoamer n-octyl alcohols, 1g fluorine carbon levelling agents, 49.5g deionized waters compound obtaining water-base epoxy-propylene
Sour self demixing emulsion.It is 20% to test its solid content.The freeze thawing more than 600 times is met without peeling, without foaming phenomena, 28d carbon is reduced
Change degree 93%, chloride permeability depth 92%.
Embodiment 4
1）The preparation of epoxy-acrylic emulsion：With 5g styrene, 10g butyl acrylates, 35g glycidyls
Ester（GA）, 1.2g S-1- dodecyls-S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate（TTC）, 0.29g over cures
Sour potassium（KPS）, 1g dodecyl sodium sulfates（SDS）, 1g hexadecanes, 100g deionized waters mixing 100rmp stirring and emulsifyings after ultrasound
Scattered 5-15min is obtained under miniemulsion, stirring condition, and 85 DEG C of reaction 2h are heated to after logical deoxygenation 15-30min and obtain terminal ring
Oxygen-acrylic emulsion.
2）The preparation of epoxy emulsion：Under stirring condition, by 25g bisphenol A epoxide resins E31,25g bisphenol A epoxide resin
E44,3.5g polyoxyethylene (40) sorbitan mono-laurate（Tween40）, 1g sorbitan monostearates
（Span20）, the mixture of 0.5g dodecyl sodium sulfates is heated to 80 DEG C, and 61g deionized waters are slowly added drop-wise into mixed epoxy mixes
Epoxy emulsion is obtained in compound.Stirring 1h obtains terminal epoxy emulsion.
3）The preparation of aqueous epoxy-acrylic self demixing emulsion：10g epoxy emulsions, 10g epoxy-acrylic emulsions, 41g
Acrylic emulsion, 1g curing agent ethylene diamines, 0.5g PH conditioning agents AMP95,1g coalescents alcohol ester 12,1g plasticizer neighbour's benzene
Dibutyl carboxylic acid, 1g defoamer n-octyl alcohols, 1g fluorine carbon levelling agents, 45.5g deionized waters compound obtaining water-base epoxy-the third
Olefin(e) acid self demixing emulsion.It is 25% to test its solid content.The freeze thawing more than 600 times is met without peeling, without foaming phenomena, 28d is reduced
Carbonizing degree 96%, chloride permeability depth 94%.
Embodiment 5
1）The preparation of epoxy-acrylic emulsion：With 10g EMA, 5g 2-ethyl hexyl acrylates, 35g methyl-props
Olefin(e) acid ethylene oxidic ester（GMA), 1.2g S-1- dodecyls-S '-(a, a '-dimethyl-a "-acetic acid) trithiocarbonate
（TTC）, 0.29g potassium peroxydisulfates（KPS）, 1g dodecyl sodium sulfates（SDS）, 1g hexadecanes, 100g deionized waters mixing
Ultrasonic disperse 5-15min is obtained under miniemulsion, stirring condition after 100rmp stirring and emulsifyings, and 85 are heated to after logical deoxygenation 15-30min
DEG C reaction 2h obtain terminal epoxy-acrylic emulsion.
2）The preparation of epoxy emulsion：Under stirring condition, 50g bisphenol A epoxide resins E35,3.5g polyoxyethylene (40) is lost
Water sorbitan monolaurate（Tween40）, 1g sorbitan monostearates（Span20）, 0.5g dodecyl sodium sulfates
Mixture be heated to 80 DEG C, 61g deionized waters are slowly added drop-wise in mixed epoxy mixture and obtain epoxy emulsion.Stirring 1h is obtained
To terminal epoxy emulsion.
3）The preparation of aqueous epoxy-acrylic self demixing emulsion：50g epoxy emulsions, 10g epoxy-acrylic emulsions；11g
Acrylic emulsion, 1g curing agent ethylene diamines, 0.5g PH conditioning agents AMP95,1g coalescents alcohol ester 12,1g plasticizer neighbour's benzene
Dibutyl carboxylic acid, 1g defoamer n-octyl alcohols, 1g fluorine carbon levelling agents, 23.5g deionized waters compound obtaining water-base epoxy-the third
Olefin(e) acid self demixing emulsion.It is 30% to test its solid content.The freeze thawing more than 600 times is met without peeling, without foaming phenomena, 28d is reduced
Carbonizing degree 96%, chloride permeability depth 95%.
Comparative example 1：The acrylic emulsion coated on the thin slice of alloy in one layer of embodiment 5 obtains acrylic acid coatings.
Comparative example 2：The epoxy emulsion in one layer of embodiment 5 is coated on the thin slice of alloy, one layer is coated with after drying
Acrylic emulsion in embodiment 5, it is the two procedures coating that bottom acrylic acid is surface layer to obtain epoxy.
Application effect is detected：
Surveyed by QFZ types Coating adhesion test instrument and Britain easily high Elcometer drawing types adhesion-force tester
The epoxy-acrylic self demixing emulsion coating obtained by embodiment 1-5 and the adhesive force of comparative example 1 and comparative example 2 are tried, it is specific attached
Force data referring to table 1.
Table 1：The attachment force data of epoxy-acrylic self demixing emulsion
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 |
| Adhesive force | 1 | 1 | 1 | 1 | 1 | 3 | 1 |
| Adhesive force（MPa） | 4.0 a | 4.3a | 4.1 a | 4.6 a | 4.9 a | 1.2 | 3.1b |
Remarks：a：Destroyed between only whole coating and base material
b：In addition to being destroyed between coating and base material, also there is destruction between two kinds of coatings.
By the number in table 1 it has been found that testing obtained embodiment 1-5 middle rings by QFZ types Coating adhesion test instrument
The adhesive force of oxygen-acrylic acid self demixing emulsion coating suitable with the adhesive force of comparative example 2 is 1 grade.And acrylic emulsion coating
Adhesive force is 3 grades, far below epoxy-acrylic self demixing emulsion coating and the adhesive force of comparative example 2.Thereby determine that epoxy-the third
Olefin(e) acid self demixing emulsion there occurs directional migration in film forming procedure, and epoxy polymer is automatic during self demixing emulsion film forming
Migrated to lower floor, add the adhesive force of paint film and bottom plate.With drawing type adhesion-force tester quantitative test testing coating and base
The adhesion results of material show the adhesive force of embodiment 1-5 epoxy-acrylic self demixing all in more than 4.0MPa, next to that right
The adhesive force 3.1MPa of ratio 2, what it is to difference is that comparative example 1 only has 1.2MPa.Checking epoxy-acrylic self demixing emulsion exists again
Directional migration is there occurs in drying process.Not only adhesive force is less than embodiment 1-5 but also two layers of painting in drawing process to comparative example 2
Also destroyed between layer.Illustrate comparative example 2 compared with embodiment 1-5, the interlayer attachment of epoxy coating and acrylic acid coatings
Power is poor.And self demixing emulsion of this patent by the use of epoxy-acrylic emulsion as intermediate layer not only increases operating efficiency also
Substantially significantly improve the adhesive force between epoxy coating-acrylic acid coatings.
Claims (4)
1. a kind of aqueous epoxy-acrylic self demixing emulsion protected for concrete surface, it is characterised in that：By following components
Constituted by following percentage by weights：
The solid content of the aqueous epoxy-acrylic self demixing emulsion is not less than 20wt%；
The acrylic emulsion is to be formed by esters of acrylic acid or methyl acrylic ester and other olefinic type monomers through emulsion polymerization
Water dispersion emulsion, the MFT of resin is not less than 10 DEG C in emulsion, and solid content is not less than 45wt%；
The curing agent is one or more of ethylenediamine, diethylenetriamine, polyethylene polyamine, phenylenediamine, m-xylene diamine
Arbitrary proportion mixture；
The pH value regulator is selected from 2-amino-2-methyl-1-propanol (AMP95) or ammoniacal liquor；
The coalescents are alcohol ester 12, butyl glycol ether, propylene glycol monomethyl ether, propandiol butyl ether, propane diols phenylate, diethyl two
The mixture of one or more of alcohol list ether and dipropylene glycol methyl ether arbitrary proportion；
The plasticizer is dibutyl phthalate；
The defoamer is C7-C22 higher alcohols, the mixing of more than one arbitrary proportions of polyethers and organic silicon defoamer
Thing；
The levelling agent is silicone levelling agent, more than one arbitrary proportions of acrylic compounds levelling agent and fluorine class levelling agent
Mixture；
The epoxy-acrylic emulsion is made up of epoxy monomer with (methyl) acrylic acid (ester) through RAFT mini-emulsion polymerizations, epoxy
The mass ratio of monomer and (methyl) acrylic acid (ester) is 3:7-7:3；
Or, it is made up of epoxy monomer with (methyl) acrylic acid (ester) and styrene through RAFT mini-emulsion polymerizations, epoxy monomer：
The mass ratio of (methyl) acrylic acid (ester) and styrene is 3:7-7:3；
The specific preparation process of the epoxy-acrylic emulsion is：
1) in addition to above-mentioned polymerized monomer, chain-transferring agent, initiator, emulsifying agent, assistant for emulsifying agent and water, relative polymerization list be also added
The quality of body, chain-transferring agent, initiator, emulsifying agent, the amount of assistant for emulsifying agent and water be respectively 0.5-4%, 0.3-0.6%,
1.5-3%, 1-3%, 2.3-5.7%；
2) by after above-mentioned each component stirring and emulsifying, ultrasonic disperse 5-15min is heated to after obtaining miniemulsion, deoxygenation 15-30min
70-85 DEG C of reaction 1h-3h obtains the epoxy-acrylic emulsion；
The solid content of the epoxy-acrylic emulsion is 15-30wt%；
Described epoxy monomer is selected from allyl glycidyl (AGE), glycidyl acrylate (GA) and methacrylic acid
It is more than one or both of ethylene oxidic ester (GMA)；
(methyl) acrylic acid (ester) monomer is methacrylic acid, methyl methacrylate, EMA, methyl-prop
One kind or kind in olefin(e) acid monooctyl ester, butyl methacrylate, acrylic acid, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate or
Two or more arbitrary proportion mixing；
Described chain-transferring agent be 2- (dodecyl trithiocarbonate) -2- methacrylic acids, S-1- dodecyls-S '-(a,
A '-dimethyl-a "-acetic acid) one kind in trithiocarbonate；
Initiator used is one kind in potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate；
Emulsifying agent used is anion or anion nonionic compound emulsifier；Assistant for emulsifying agent is hexadecane.
2. the aqueous epoxy-acrylic self demixing emulsion according to claim 1 protected for concrete surface, its feature
It is,
The epoxy emulsion is prepared by following methods：
At 60-90 DEG C, deionized water is added dropwise under 200-600rpm stirring conditions and obtains for the mixture of epoxy resin and emulsifying agent
Epoxy emulsion；
The epoxy resin is bisphenol A type epoxy resin：One kind in E51, E44, E42, E54, E35, E31, E20, E12 or two
Mixed more than kind with arbitrary proportion；
Emulsifying agent used in the epoxy emulsion compounds what is obtained with nonionic emulsifier for anion emulsifier with arbitrary proportion,
Emulsifying agent accounts for the 8-10% of bisphenol A type epoxy resin quality, and HLB value is 13-15.
3. the aqueous epoxy-acrylic self demixing emulsion according to claim 1 protected for concrete surface, its feature
It is, if using (methyl) acrylic acid (ester) and styrene simultaneously, the mass ratio of (methyl) acrylic acid (ester) and styrene is more than
1：1.
4. it is used for the aqueous epoxy-acrylic self demixing breast that concrete surface is protected described in any one of claim 1-3
Liquid, it is characterised in that above-mentioned each component is well mixed and obtains the aqueous epoxy-acrylic self demixing emulsion.
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| CN105860889B (en) * | 2016-04-20 | 2018-01-16 | 黑龙江省科学院石油化学研究院 | A kind of water base Peelable shim adhesive and preparation method thereof |
| CN107022278B (en) * | 2017-04-27 | 2019-07-19 | 珠海富邦新材料科技有限公司 | Metal zip fastener Singapore frame water paint and the preparation method and application thereof |
| CN110408248A (en) * | 2019-09-09 | 2019-11-05 | 上海昱彩包装材料有限公司 | A kind of aqueous high-performance household electrical appliances coil coating of self demixing and preparation method thereof |
| CN110724436B (en) * | 2019-10-24 | 2021-07-27 | 厦门双瑞船舶涂料有限公司 | Epoxy grafted acrylate self-layering connecting paint and preparation method thereof |
| CN111073445B (en) * | 2019-11-26 | 2021-05-14 | 上海昭和高分子有限公司 | Water-based two-component paint with high impact resistance and application thereof |
| CN113789121A (en) * | 2021-09-06 | 2021-12-14 | 江苏科技大学 | Self-layering super-hydrophobic composite coating |
| CN115521684B (en) * | 2022-09-30 | 2023-12-29 | 山西米洞虐电子科技有限公司 | Petroleum storage tank inner wall anti-corrosion paint and preparation method thereof |
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| CN1500559A (en) * | 2002-11-08 | 2004-06-02 | 日本油漆株式会社 | Process for forming cured gradient coating film and multi-layered coating film containing the same |
| CN104046211A (en) * | 2013-04-25 | 2014-09-17 | 中国船舶重工集团公司第七二五研究所 | Epoxy modified acrylic resin gradient connection paint and preparation method thereof |
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| CN103773154A (en) * | 2012-10-15 | 2014-05-07 | 李翠平 | Water-based epoxy grafted acrylic ester concrete anticorrosive paint and preparation method thereof |
| CN102976652B (en) * | 2012-11-01 | 2014-06-18 | 江苏苏博特新材料股份有限公司 | Concrete maintenance agent having high water retention rate, and its preparation method |
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| CN104046211A (en) * | 2013-04-25 | 2014-09-17 | 中国船舶重工集团公司第七二五研究所 | Epoxy modified acrylic resin gradient connection paint and preparation method thereof |
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