CN110229573A - A kind of aqueous rusty anti-corrosive primer and preparation method thereof - Google Patents
A kind of aqueous rusty anti-corrosive primer and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to chemical anticorrosion paint fields, specifically disclose a kind of aqueous rusty anti-corrosive primer and preparation method thereof, the aqueous rusty anti-corrosive primer selects main base vinyl emulsion using vinyl emulsion, core-shell structure acrylic emulsion and phosphate modified acrylic emulsion as base-material first；Auxiliary base-material core-shell structure emulsion acrylic resin and phosphate modified acrylic emulsion are synthesized again；Aqueous rusty priming paint is mixed and made by the auxiliary agents such as base-material and rust transforming agent, antifreeze, wetting agent, defoaming agent of above-mentioned three kinds of lotions again.Obtained aqueous rusty anti-corrosive primer VOC content is low, safety and environmental protection, easy for construction, good with common antisepsis finishing paint matching, turns the primer for rusted steel that rust effect is good, adhesive force is strong, rust-proof life effect is long, is with a wide range of applications.
Description
Technical field
The present invention relates to chemical anticorrosion paint fields, and in particular to a kind of aqueous rusty anti-corrosive primer and preparation method thereof.
Background technique
The processing of ground is very big on the influence of the protective performance of coating, and the coating of general anticorrosive paint is to ground processing requirement ratio
Relatively stringent, derusting grade, which often requires that, reaches Sa2.5 or St3.When surface of bottom material corrosion is more serious, derusting need of work flower
Take very big manpower.In order to mitigate derusting workload, two approach are mainly taken.A kind of approach is applied using low prepared surface
Material, this kind of coating has usual viscosity lower, in favor of the infiltration to ground.Such as the epoxy primer of low prepared surface, allow bottom
The oxide skin of material residual adhesion-tight and old paint film；Another way is to brush rust conversion coating, and this kind of priming paint is usual
Using vinyl resins lotion as base-material, addition tannic acid etc. turns rust ingredient, is reacted with corrosion by loose porous rust using tannic acid
Layer is converted into comparatively dense passivating film, in addition the permeability resistance that polyvinyls coating is excellent, can reach prevent ground into
The purpose of one step corrosion.
Existing aqueous rusty priming paint is mostly rust transforming agent with tannic acid or the similar organic acid of other properties, with phosphoric acid,
Citric acid, tartaric acid etc. are inorganic or organic acid is auxiliary rust transforming agent, using vinylidene chloride lotion as base-material, using the agent that turns to become rusty to iron
The conversion of rust and the closure of vinylidene chloride lotion, obtaining can be in rust surface construction, the excellent paint film of rustless property.Its advantage exists
In can mitigate significantly pre-treatment derusting workload.The disadvantage is that paint can be reduced in corrosion non-uniform surface part organic acid residual
Film protective performance, vinylidene chloride polymer molecular weight is big, glass transition temperature is higher, relatively low to substrate adhesion.
Summary of the invention:
An object of the present invention is to provide a kind of aqueous rusty anti-corrosive primer, and VOC content is low, safety and environmental protection, construction
Convenient, good with common antisepsis finishing paint matching, turn rust effect is good, adhesive force is strong, rust-proof life effect length.
A kind of aqueous rusty anti-corrosive primer, is prepared from the following parts by weight of the components:
Preferably, the vinyl emulsion is acrylic acid modified vinylidene chloride lotion, and solid content is about 60%, such as Supreme Being
The PERMAX805 lotion of this graceful Haloflex202, Lu Borun；
The softened water (similarly hereinafter) is selected from deionized water or distilled water, conductivity < 20 μ s/cm；
The dispersing agent is non-ionic macromolecule dispersing agent, as OMG company Gen0451, profound new VXW6208 win wound
ZetaSperse179；
The wetting agent selects alkyl butynediols polyoxyethylene ether, as aerochemistry company SURFYNOLGA,
SURFYNOLTG,Dynol607；
The levelling agent selects or mixtures thereof fluorine carbon surfactant, organic silicon modified by polyether type auxiliary agent, such as moral
67 wetting agents of Byk348, Tao Shi of Guo Bike company, AJA company, the U.S. SFL-50；
The defoaming agent be selected from mineral oil, polyethers, organic siliconresin and its compound, such as NOPCO company SN1311,
1340,1370, NXZ, the BYK024 of BYK company, the 902W of Digao, this DF-677 of hamming；
The preservative is water-soluble isothiazolinone compound, such as chloro isothiazolinone, methylisothiazolinone
Or mixtures thereof, such as the KATHON LXE of Tao Shi, the PG520 of South Korea SK；
The mould inhibitor is or mixtures thereof benzoisothiazolinone, n-octyl-isothiazolin ketone, such as the SKANE of Tao Shi
The MA-21 of M-8, South Korea SK；
The neutralizer is selected from ammonium hydroxide, triethylamine, N, one of N- dimethylethanolamine, N-ethylmorpholine or it is a kind of with
On；
The pigment is selected from iron oxide red, iron oxide black, iron oxide yellow, rutile type titanium white, BGS phthalocyanine blue and carbon black
One or more；
The rust resisting pigment is selected from the one of trbasic zinc phosphate, modified zinc phosphate, composite phosphate, aluminium triphosphate and phosphomolybdic acid zinc
Kind or more than one；
The filler is selected from calcium carbonate, kaolin, mica powder or talcum powder；
The thickener is polyether-polyurethane type thickener, such as hamming this R-278,288 thickeners, and Qingdao is prosperous permanent poly-
821 thickeners of chemical industry, the 830W thickener of COATEX company；
Described turn of rust agent is the aqueous solution of organic acid；
The organic acid is selected from one kind of tannic acid, pyrogallic acid, tannin tannin extract, citric acid, tartaric acid and oxalic acid
Or more than one；
The rust resisting pigment use composite phosphate, can both react with corrosion layer by loose oxide be converted into densification it is organic
Hydrochlorate, and can react to form phosphatization passivating film with ground, significantly improve the antiseptic property of paint film；
The multifunctional assistant is 2-amino-2-methyl-1-propanol, such as the AMP-95 of Tao Shi；
The coalescing agent is alcohol ester 12 (2,2,4- trimethyl -1,3- pentanediol mono isobutyrate).
Preferably, the core-shell structure acrylic emulsion is prepared from the following parts by weight of the components:
It is first copolymerized with the mix monomer compared with high glass transition temperature, then acrylic acid and second compared with low Tg is added dropwise
Alkenes mix monomer further polymerize, and rear insulation reaction is added dropwise for a period of time, add reducing agent continue cause eliminate it is residual
Remaining monomer, after cooling plus ammonium hydroxide neutralizes, that is, is made using high glass transition temperature resin as core, and low Tg resin is the core of shell
Shell structure acrylic emulsion.
The core-shell structure acrylic emulsion specific the preparation method is as follows:
(1) take 3-5 parts of softened waters, the solution that the second initiator is made into 3-5% be added, takes 3-5 part softened waters, be added it is negative from
Son and nonionic emulsifier are made into 30% emulsifier solution, and glass is added in a part of softened water, emulsifier solution and mix monomer
In glass or rustless steel container, high-speed stirred 15 minutes, monomer pre-emulsion A is obtained；
It should be noted that the mix monomer is methyl methacrylate, styrene, butyl acrylate and acrylic acid；
The monomer pre-emulsion A being prepared into has relatively high glass transition temperature；
(2) part softened water, emulsifier solution, monomer pre-emulsion A are added in flask, is warming up to 75 ± 2 DEG C, leads to nitrogen
Part initiator solution is added in gas, keeps the temperature blue to liquid；
(3) residual monomer pre-emulsion A is added dropwise, while the second initiator solution is added dropwise, adds within 1.5 hours, insulation reaction is extremely
Substantially without reflux；
(4) remaining softened water, emulsifier solution and mix monomer are added in glass or rustless steel container, high-speed stirred
15 minutes, obtain monomer pre-emulsion B；
It should be noted that the mix monomer is remaining methyl methacrylate, styrene, butyl acrylate and third
Olefin(e) acid；The monomer pre-emulsion B being prepared into has relatively low glass transition temperature.
(5) monomer pre-emulsion B is added dropwise in the flask of step (2), while the second initiator solution is added dropwise, adds within 1.5 hours
Complete, insulation reaction to without reflux, adding remaining second initiator solution, be warming up to 85 DEG C, insulation reaction half an hour substantially；
(6) 50-60 DEG C is cooled to, the second neutralizer is added to adjust pH value to 7-8, filtering and discharging.
The anion emulsifier is selected from neopelex, lauryl sodium sulfate, fatty alcohol polyoxyethylene ether
One of sodium sulphate, aliphatic alcohol polyethenoxy phosphate, alkylphenol-polyethenoxy sodium phosphate and sodium lauryl sulfate are a kind of
More than；
The nonionic emulsifier is selected from one of fatty alcohol polyoxyethylene ether and alkyl phenol polyoxyethylene ether or a kind of
More than；
Second initiator be selected from one of potassium peroxydisulfate and ammonium persulfate or more than one；
Second neutralizer is selected from ammonium hydroxide, 2-amino-2-methyl-1-propanol, N, N- dimethylethanolamine and triethylamine
One of or more than one.
Preferably, the phosphate modified acrylic emulsion is prepared from the following parts by weight of the components:
First synthesize phosphate ester-containing and polyether group acrylic resin soln, then with the acrylic resin soln be protection
Glue carries out emulsion polymerization, and the phosphate modified acrylic emulsion is prepared.
The reactive emulsifier is selected from sodium olefin sulfonate, allyl -2- hydroxypropyl ether sodium sulfonate and allyl polyoxy second
One of alkene ether or more than one；
The third initiator is selected from potassium peroxydisulfate or ammonium persulfate；
The third neutralizer is in ammonium hydroxide, 2-amino-2-methyl-1-propanol, N, N- dimethylethanolamine, triethylamine
One or more.
Auxiliary base-material of the phosphate modified acrylic emulsion as vinylidene chloride acrylate copolymer emulsion is guaranteeing to paint
Under conditions of film has excellent closure, it can significantly improve that paint film is dry, wet adhesion, with acrylic acid, high chlorine, chlorination rubber
A variety of overcoatabilities such as glue, polyurethane are good.
The method and step of the phosphate modified acrylic emulsion preparation is as follows:
(1) it takes softened water that the initiator solution that third initiator is made into 3-5% is added, takes softened water that response type emulsification is added
Agent is made into 30% emulsifier solution, by acrylic resin soln, reactive emulsifier solution, methyl methacrylate, benzene second
Alkene, butyl acrylate, acrylic acid are added in glass or rustless steel container, high-speed stirred 15 minutes, obtain monomer dispersion liquid；
(2) the monomer dispersion of softened water 4-6 parts, 0.5-1 parts of reactive emulsifier solution, step (2) is added in flask
10-15 parts of liquid, 0.6-1.1 parts of third initiator solution are added, is warming up to 75 ± 2 DEG C, logical nitrogen, heat preservation are blue to liquid；
(3) residual monomer dispersion liquid is added dropwise, while being added dropwise 2-3 parts of third initiator, adds within 2-3 hours, insulation reaction is extremely
Substantially without reflux；
(4) 0.5-1.0 parts of third initiator are added, is warming up to 80 DEG C, insulation reaction is to substantially without reflux；
(5) 85 DEG C are warming up to, half an hour is kept the temperature；
(6) 50-60 DEG C is cooled to, adds 1-2 parts of adjusting pH values of third neutralizer to 6.5, filtering and discharging.
Preferably, the acrylic resin soln is prepared from the following parts by weight of the components:
The phosphate ester monomer is 2- hydroxyethyl methacrylic acid phosphate；
The unsaturated carboxylic acid be selected from one of acrylic acid and methacrylic acid or more than one；
The acrylate be selected from one of methyl methacrylate, ethyl acrylate and butyl acrylate or it is a kind of with
On；
4th initiator be selected from one of benzoyl peroxide and cumyl peroxide or more than one；
4th neutralizer is selected from ammonium hydroxide, triethylamine, dimethylethanolamine, N-ethylmorpholine, 2- amino-2-methyl-
One of 1- propyl alcohol or more than one.
The acrylic resin soln specific the preparation method is as follows:
(1) propylene glycol monomethyl ether 50-100 parts, 50-100 parts of propandiol butyl ether are added in the reaction vessel, starts stirring, leads to
Nitrogen is warming up to 115-125 DEG C, keeps slight boiling condition；
(2) by 50-75 parts of phosphate ester monomer, 50-75 parts of unsaturated carboxylic acid, 150-200 parts of acrylate and styrene 80-
120 parts are added drop-wise in reaction vessel under nitrogen protection with the good high position dropwise adding tank that is added of 5-20 parts of mixtures of the 4th initiator, drip
2-3h between added-time, in 115-125 DEG C of insulation reaction 1-2h after adding；
(3) 60-70 DEG C is cooled to, the 4th neutralizer is added, gradually adds water and stirs, obtains acrylic resin soln.
It is a further object to provide the preparation methods of above-mentioned aqueous rusty anti-corrosive primer, and steps are as follows:
(1) softened water 50-100 parts, 3-15 parts of dispersing agent, 1-3 parts of wetting agent, propylene glycol 5-20 are added in container with slurry
Part, 0.5-1 parts of defoaming agent, 1-3 parts of preservative, 1-3 parts of multifunctional assistant, are stirred evenly with adjustable high-speed dispersion machine；
(2) addition pigment, filler, high-speed stirred 20-30 minutes；
(3) 1/3 thickener is added, stirs evenly；
(4) fineness is ground to up to 40 μm with sand mill hereinafter, obtaining pigments and fillers slurry；
(5) pigments and fillers slurry, 1-2 parts of first neutralizer, vinylite lotion of step (4) are added in paint container
400-600 parts, 100-300 parts of core-shell structure acrylic emulsion, acrylic emulsion 100-200 parts phosphate modified, coalescing agent
10-15 parts, 0.5-2 parts of defoaming agent, 1-5 parts of levelling agent turn agent 50-150 parts of rust, stir evenly；
(6) remaining 2/3 thickener is added, stirs evenly, filters, obtains finished product.
The vinylite lotion be acrylic acid modified vinylidene chloride lotion, solid content 60%,
The dispersing agent is non-ionic macromolecule dispersing agent；
The wetting agent is alkyl butynediols polyoxyethylene ether；
The levelling agent is selected from the one or more of fluorocarbon surfactant, organic silicon modified by polyether type auxiliary agent；
The defoaming agent be selected from one of mineral oil, polyethers, organic siliconresin or more than one；
The preservative is water-soluble isothiazolinone compound；
The mould inhibitor is selected from benzoisothiazolinone, the one or more of n-octyl-isothiazolin ketone；
First neutralizer be selected from ammonium hydroxide, triethylamine, N, one of N- dimethylethanolamine and N-ethylmorpholine or
More than one；
The pigment is selected from iron oxide red, iron oxide black, iron oxide yellow, rutile type titanium white, BGS phthalocyanine blue and carbon black
One or more；
The rust resisting pigment is selected from the one of trbasic zinc phosphate, modified zinc phosphate, composite phosphate, aluminium triphosphate and phosphomolybdic acid zinc
Kind or more than one；
The filler is selected from the one or more of calcium carbonate, kaolin, mica powder or talcum powder；
The thickener is polyether-polyurethane type thickener；
Described turn of rust agent is selected from the aqueous solution of organic acid, and the organic acid is selected from tannic acid, pyrogallic acid, tannin evergreen chinquapin
The one or more of glue, citric acid, tartaric acid or oxalic acid；
The multifunctional assistant is 2-amino-2-methyl-1-propanol；
The coalescing agent is alcohol ester 12.
Beneficial effects of the present invention: the present invention has synthesized that VOC content is low, stability is good, dry with core-shell emulsion polymerization method
Fastly, the good core-shell structure acrylic emulsion of flexibility prepares phosphate modified acrylic emulsion with surfactant- free emulsion polymerization, then with
Vinylite lotion and above two acrylic emulsion are that base-material and pigments and fillers, auxiliary agent cooperate, and the processes such as ground, dispersion add
Work is at above-mentioned aqueous rusty anti-corrosive primer.The coating VOC content is low, is free of benzene homologues, non-ignitable, low smell, low pollution can be used
A variety of method constructions such as brushing, roller coating, spraying, fast drying is safe and convenient to use, and paint film high mechanical strength, and adhesive force is strong, prevents
Rotten performance is good, can with epoxy, polyurethane, acrylic acid, vinyl is various aqueous and solvent type finishing coat matches, be used for ship
It is repaired with container, passenger train from goods train, automobile and agricultural vehicle, pipelines and petrochemical pipelines, basin and steel construction, construction steel structure and roofing etc.
Facility has got rusty and has been inconvenient to the protective coating of steel material to derust, has a good application prospect.
Core-shell structure acrylic emulsion of the invention is by the core compared with high glass transition temperature and compared with the shell of low Tg
It constitutes, rigid stratum nucleare assigns the higher hardness of coating, and the lower glass transition temperature of shell can guarantee film formation at low temp, reduces and applies
Expect VOC content.Phosphate modified acrylic emulsion is copolymerized to obtain emulsion acrylic resin with phosphate ester monomer and acrylic monomers,
Using this resin solution as protective glue, phosphate modified acrylic emulsion is prepared using surfactant- free emulsion polymerization.Acrylic acid solution point
Son amount and glass transition temperature are lower, and phosphate ester-containing monomer, can chemically react with iron rust but also with ground metal, can
To improve coating film formation compactness and in the wet adhesion of metal surface.Conventional anion and non-is substituted with response type initiator
Ionic emulsifying agent improves the stability and paint film water resistance of coating in acid condition, compared with common aqueous rusty priming paint,
With more significant paint stability, the rate of drying of paint film, adhesive force and antiseptic property.
Specific embodiment:
The following are some representative embodiments of the invention, but the present invention is not limited in these examples.
One, core-shell structure acrylic emulsion synthesizes
Core-shell structure acrylic emulsion formula is shown in Table 1, and the performance test results are shown in Table 2.
1 core-shell structure acrylic emulsion synthetic example of table
Core-shell structure acrylic emulsion the preparation method is as follows:
(1) 20 grams of softened waters are taken, 0.8 gram of ammonium persulfate is added and is made into initiator solution, take 20 grams of softened waters, OPP- is added
10 emulsifiers (alkyl phenol polyoxyethylene ether sodium phosphate) and TX-15 emulsifier are made into emulsifier solution, by 80 grams of softened waters, 12 grams
Emulsifier solution, the methyl methacrylate in serial number 1-3, styrene, butyl acrylate, be added beaker in, high-speed stirred
15 minutes, obtain monomer pre-emulsion A；
(2) softened water of 20 grams of addition, 5 in the four-hole boiling flask equipped with blender, thermometer, condenser pipe and addition funnel
Gram emulsifier solution, 50 grams of monomer pre-emulsion A, be warming up to 75 ± 2 DEG C, lead to nitrogen, be added 4-6 grams initiator it is molten
Liquid is kept the temperature blue to liquid；
(3) monomer pre-emulsion A is added dropwise, while being added dropwise 6-8 grams of initiator solution, adds within about 1.5 hours, insulation reaction is extremely
Substantially without reflux；
(4) by methyl methacrylate, the styrene, third in 60 grams of softened water, 9 grams of emulsifier solution, serial number 4-7
Olefin(e) acid butyl ester, acrylic acid are added in glass or rustless steel container, high-speed stirred 15 minutes, obtain monomer pre-emulsion B；
(5) monomer pre-emulsion B is added dropwise in above-mentioned four-hole boiling flask, while being added dropwise 6-8 grams of initiator solution, about 1.5 is small
When add, insulation reaction is to without reflux, being warming up to 85 DEG C, insulation reaction half an hour substantially.
(6) 50-60 DEG C is cooled to, ammonium hydroxide is added to adjust pH value to 7-8, filtering and discharging.
2 core-shell structure acrylic emulsion performance of table
Emulsifier total amount is the 5% of monomer in embodiment 1-3, and anion emulsifier and nonionic emulsifier ratio are respectively
4:1,3:2,2:3, embodiment 4,5 emulsifiers are reduced to 4% and 3%, obtain blue light exquisiteness homogeneous latex emulsion.Only make in comparative example 1
With anion emulsifier, emulsion appearance is fine and smooth, but gained lotion freeze-thaw stability and Calcium ion stability are bad.Comparative example 2 is non-
Ion and anion emulsifier ratio are bigger than normal, and anionic surfactant dose is smaller, and gained emulsion appearance whitens, gel compared with
It is more.
2, the preparation of acrylic resin soln
The preparation formula of acrylic resin soln is shown in Table 3, and the performance test results are shown in Table 4.
Table 3
Acrylic resin soln the preparation method is as follows:
(1) equipped with blender, thermometer, condenser, dropping tank reaction vessel in be added propylene glycol monomethyl ether, dipropyl two
Alcohol methyl ether starts stirring, leads to nitrogen, is warming up to 115--125 DEG C, keeps slight boiling condition；
(2) HEMAP, acrylic acid, acrylate monomer and styrene and initiator benzoyl peroxide mixture is good, enter
High-order dropping tank is added drop-wise in reaction vessel under nitrogen protection, time for adding 2-3h, anti-in 115-125 DEG C of heat preservation after adding
Answer 1-2h；
(3) 60-70 DEG C is cooled to, neutralizer triethylamine and ammonium hydroxide is added, gradually adds water and stirs, obtains acrylic size
Liquid solution, the protective glue as emulsion polymerization.
The performance of 4 acrylic resin soln of table
The modest viscosity of the acrylic resin soln of embodiment 6-8, appearance transparent is in good condition, and 4 acrylic acid of comparative example is used
Measure relatively low, water-soluble slightly worse, 4 acrylic acid dosage of comparative example is bigger than normal, and the viscosity of obtained acrylic resin soln is higher.
3, the preparation of phosphate modified acrylic emulsion
Phosphate modified lotion synthesizing formula is shown in Table 5, and emulsion property test result is shown in Table 6.
The phosphate modified acrylic emulsion formula of table 5
Phosphate modified acrylic emulsion the preparation method is as follows:
(1) part methyl acrylic acid is added in the four-hole boiling flask equipped with blender, thermometer, condenser pipe and addition funnel
Methyl esters, styrene, butyl acrylate, acrylic resin soln (preparation of embodiment 10), α-sodium olefin sulfonate, deionized water mixing
Object is warming up to 75 DEG C, leads to nitrogen, part initiator is added, keep the temperature blue to liquid；
(2) it is added dropwise by acrylic acid and vinyl monomer, acrylic resin soln (preparation of embodiment 9), methacrylic sulphur
The pre-emulsion of sour sodium, deionized water composition, while initiator ammonium persulfate is added dropwise, it adds within about 2 hours, adds continuation insulation reaction
To substantially without reflux；
(3) 85 DEG C are warming up to, appropriate initiator ammonium persulfate is added, keeps the temperature half an hour；
(4) 50-60 DEG C is cooled to, ammonium hydroxide is added to adjust pH value to 7-8, filtering and discharging.
The phosphate modified acrylic emulsion performance of table 6
The emulsion viscosity of embodiment 9-10 is moderate, and varnish film water resistance is good.Comparative example 6 is protected using acrylic resin soln
It is on the high side to protect glue, the decline of varnish film water resistance.Comparative example 7 is free of acrylic resin soln, and paint film adhesion and water resistance are
It reduces.
4, the preparation of aqueous rusty anti-corrosive primer coating
Aqueous rusty anti-corrosive primer formulation for coating material is shown in Table 7:
7 aqueous rusty anti-corrosive primer coating formulation for coating material example of table
The preparation method is as follows:
(1) softened water, dispersing agent, wetting agent, defoaming agent, preservative, mould inhibitor, multifunctional assistant are added in container with slurry
Agent is stirred evenly with adjustable high-speed dispersion machine (similarly hereinafter)；
(2) mica powder, talcum powder, AZP-02 preservative is added, stirs evenly, high-speed stirred 1 hour；
(4) thickener of formula ratio 1/3 is added, stirs evenly；
(5) fineness is ground to up to 40 μm with sand mill hereinafter, obtaining graining paste；
(6) graining paste, neutralizer, acrylic emulsion, coalescing agent, carbon black color paste are added in paint container, stirring is equal
It is even；
7. remaining 2/3 thickener is added, stir evenly, filters, obtain finished product.
Above-mentioned dispersing agent is this FX-600 of hamming；Wetting agent is the SURFYNOL440 of American Gas Chemical Company, defoaming
Agent is this DF-677 of hamming；Preservative is the PG520 of SK company；6130 multifunctional assistants are volatile organic amines, are Qingdao
Fu Ruixi chemical company product, Permax805 are Lubrizol Corp.'s products, core-shell structure acrylic emulsion and are changed without soap phosphate
Property acrylic emulsion be prepared by previous embodiment 1 and embodiment 10 respectively, 1250 mesh talcum powder are Pingdu talcum mineral products,
600 mesh mica powders are the sharp Products of Chuzhou lattice, and AZP-02 rust resisting pigment is the prosperous permanent dimerization work modified zinc phosphate in Qingdao, turn rust agent
1 by 20 parts of tannic acid, 10 parts of pyrogallic acid, and 70 parts of water are formulated, and turns rust agent 2 by 20 parts of tannic acid, 10 parts of citric acid,
70 parts of water are formulated, and turn rust agent 3 by 20 parts of tannic acid of tannic acid, 0 part of phosphatase 11,70 parts of water are formulated, and alcohol ester ten is second is that river
2,2,4- trimethyl -1,3- pentanediol mono isobutyrate of Su Runtai chemical company product, 821 thickeners are the prosperous permanent dimerization works in Qingdao
Products polyether-polyurethane type thickener.
Aqueous rusty anti-corrosive primer coating property test result is shown in Table 8
8. aqueous rusty anti-corrosive primer coating property of table
Salt-fog resistant test is the aqueous rusty anti-corrosive primer that the synthesis of one of embodiment and comparative example is brushed on rust iron plate,
It is 6 hours dry or more, one of water-based acrylic acid top-coat is brushed, 50-60 μm of paint film overall thickness tests salt-fog resistant time.
Embodiment 12,13,14 uses same amount of vinyl emulsion and phosphate modified acrylic emulsion, different number
Turn rust agent, the properties of gained aqueous rusty anti-corrosive primer coating are excellent: adhesive force reaches level-one, resistance in carbon steel sheet getting rusty
Salt fog reaches 500h or more, and antiseptic property is excellent.Embodiment 15,16,17 is changed using same amount of vinyl emulsion and phosphate
Property acrylic emulsion, different cultivars turns rust agent, and coating adhesion reaches level-one, and getting rusty, salt spray resistance in carbon steel sheet reaches 500h
More than, antiseptic property is excellent.Comparative example 8 uses less phosphate modified acrylic acid soap-free emulsion, and comparative example 9 is not used without soap
Lotion, it is intended to which early stage blisters, and paint film adhesion is also poor.
Content of the present invention is not limited in embodiment content of the present invention.
Specific case used herein is expounded structure of the invention and embodiment, the explanation of above embodiments
It is merely used to help understand the core idea of the present invention.It should be pointed out that for those skilled in the art,
Without departing from the principles of the invention, can be with several improvements and modifications are made to the present invention, these improvement and modification are also fallen
Enter in the protection scope of the claims in the present invention.
Claims (9)
1. a kind of aqueous rusty anti-corrosive primer, which is characterized in that be prepared from the following parts by weight of the components:
2. aqueous rusty anti-corrosive primer as described in claim 1, which is characterized in that the vinylite lotion is acrylic acid
Modified vinylidene chloride lotion, solid content 60%；
The dispersing agent is non-ionic macromolecule dispersing agent；
The wetting agent is alkyl butynediols polyoxyethylene ether；
The levelling agent is selected from the one or more of fluorocarbon surfactant and organic silicon modified by polyether type auxiliary agent；
The defoaming agent is selected from mineral oil, polyethers closes the one or more of organic siliconresin；
The preservative is water-soluble isothiazolinone compound；
The mould inhibitor is selected from the one or more of benzoisothiazolinone and n-octyl-isothiazolin ketone；
First neutralizer is selected from ammonium hydroxide, triethylamine, N, one of N- dimethylethanolamine and N-ethylmorpholine or a kind of
More than；
The pigment is selected from the one of iron oxide red, iron oxide black, iron oxide yellow, rutile type titanium white, BGS phthalocyanine blue and carbon black
Kind or more than one；
The rust resisting pigment be selected from trbasic zinc phosphate, modified zinc phosphate, composite phosphate, aluminium triphosphate and phosphomolybdic acid zinc one kind or
More than one；
The filler is selected from the one or more of calcium carbonate, kaolin, mica powder and talcum powder；
The thickener is polyether-polyurethane type thickener；
Described turn of rust agent is the aqueous solution of organic acid, and the organic acid is selected from tannic acid, pyrogallic acid, tannin tannin extract, lemon
The one or more of lemon acid, tartaric acid and oxalic acid；
The multifunctional assistant is 2-amino-2-methyl-1-propanol；
The coalescing agent is alcohol ester 12.
3. aqueous rusty anti-corrosive primer as described in claim 1, which is characterized in that the core-shell structure acrylic emulsion by with
The component of lower parts by weight is prepared:
The anion emulsifier is selected from neopelex, lauryl sodium sulfate, fatty alcohol polyoxyethylene ether sulfuric acid
The one or more of sodium, aliphatic alcohol polyethenoxy phosphate, alkylphenol-polyethenoxy sodium phosphate and sodium lauryl sulfate；
The nonionic emulsifier is selected from fatty alcohol polyoxyethylene ether or alkyl phenol polyoxyethylene ether；
Second initiator is selected from potassium peroxydisulfate or ammonium persulfate；
Second neutralizer is in ammonium hydroxide, 2-amino-2-methyl-1-propanol, N, N- dimethylethanolamine and triethylamine
It is one or more kinds of.
4. aqueous rusty anti-corrosive primer as described in claim 1, which is characterized in that the phosphate modified acrylic emulsion by
The component of following parts by weight is prepared:
The reactive emulsifier is selected from sodium olefin sulfonate, allyl -2- hydroxypropyl ether sodium sulfonate and allyl polyethenoxy ether
One or more；
The third initiator is selected from potassium peroxydisulfate or ammonium persulfate；
The third neutralizer is selected from ammonium hydroxide, 2-amino-2-methyl-1-propanol, N, and one in N- dimethylethanolamine, triethylamine
Kind or more than one.
5. aqueous rusty anti-corrosive primer as claimed in claim 4, which is characterized in that the acrylic resin soln is by following heavy
The component of amount part is prepared:
The phosphate ester monomer is 2- hydroxyethyl methacrylic acid phosphate；
The unsaturated carboxylic acid is selected from the one or more of acrylic acid and methacrylic acid；
The acrylate be selected from one of methyl methacrylate, ethyl acrylate and butyl acrylate or more than one；
4th initiator is selected from the one or more of benzoyl peroxide and cumyl peroxide；
4th neutralizer is selected from ammonium hydroxide, triethylamine, dimethylethanolamine, N-ethylmorpholine and 2- amino-2-methyl -1- third
One of alcohol or more than one.
6. aqueous rusty anti-corrosive primer as claimed in claim 3, which is characterized in that the system of the core-shell structure acrylic emulsion
Preparation Method, steps are as follows:
(1) take 3-5 parts of softened waters that the initiator solution that the second initiator is made into 3-5% is added, take 3-5 part softened waters be added it is negative from
Son and nonionic emulsifier are made into 30% emulsifier solution, take softened water, emulsifier solution and mix monomer that glass or not is added
It becomes rusty in steel container, high-speed stirred 15 minutes, obtains monomer pre-emulsion A；
(2) softened water, emulsifier solution, monomer pre-emulsion A are added in flask, is warming up to 75 ± 2 DEG C, leads to nitrogen and is added and draw
Agent solution is sent out, is kept the temperature blue to liquid；
(3) residual monomer pre-emulsion A is added dropwise, while initiator solution is added dropwise, adds within 1.5 hours, insulation reaction to no reflux；
(4) it by remaining softened water, emulsifier solution and mix monomer, is added in glass or rustless steel container, high-speed stirred 15
Minute, obtain monomer pre-emulsion B；
(5) monomer pre-emulsion B is added dropwise in the flask of step (2), while the second initiator is added dropwise, adds within 1.5 hours, heat preservation is anti-
Ying Zhiwu reflux, adds the second initiator and is warming up to 85 DEG C, insulation reaction half an hour；
(6) 50-60 DEG C is cooled to, the second neutralizer is added to adjust pH value to 7-8, filtering and discharging.
7. aqueous rusty anti-corrosive primer as claimed in claim 4, which is characterized in that the phosphate modified acrylic emulsion
Steps are as follows for preparation method:
(1) it takes softened water that the initiator solution that third initiator is made into 3-5% is added, takes softened water that reactive emulsifier is added and match
At 30% emulsifier solution, by acrylic resin soln, reactive emulsifier solution, methyl methacrylate, styrene, third
Olefin(e) acid butyl ester and acrylic acid are added in glass or rustless steel container, high-speed stirred 15 minutes, obtain monomer dispersion liquid；
(2) in flask be added softened water 4-6 parts, 0.5-1 parts of reactive emulsifier solution, step (1) monomer dispersion liquid 10-
15 parts, 0.6-1.1 parts of third initiator are added, is warming up to 75 ± 2 DEG C, logical nitrogen, heat preservation are blue to liquid；
(3) remaining monomer dispersion liquid is added dropwise, while being added dropwise 2-3 parts of third initiator, adds within 2-3 hours, insulation reaction to nothing
Reflux；
(4) 0.5-1.0 parts of third initiator solution are added, is warming up to 80 DEG C, insulation reaction to no reflux；
(5) 85 DEG C are warming up to, half an hour is kept the temperature；
(6) 50-60 DEG C is cooled to, adds 1-2 parts of third neutralizer, adjusts pH value to 6.5, filtering and discharging.
8. aqueous rusty anti-corrosive primer as claimed in claim 5, which is characterized in that the preparation side of the acrylic resin soln
Steps are as follows for method:
(1) propylene glycol monomethyl ether 50-100 parts, 50-100 parts of propandiol butyl ether are added in the reaction vessel, stir logical nitrogen and heats up
To 115-125 DEG C, slight boiling condition is kept；
(2) by 50-75 parts of phosphate ester monomer, 50-75 parts of unsaturated carboxylic acid, 150-200 parts of acrylate, 80-120 parts of styrene
High-order dropwise adding tank is added with 5-20 parts of mixtures of the 4th initiator, is added drop-wise in reaction vessel under nitrogen protection, time for adding 2-
3h, in 115-125 DEG C of insulation reaction 1-2h after adding；
(3) 60-70 DEG C is cooled to, the 4th neutralizer is added, gradually adds water and stirs, obtains the acrylic resin soln.
9. a kind of method for preparing the aqueous rusty anti-corrosive primer as described in claim any one of 1-5, which is characterized in that step is such as
Under:
(1) in container with slurry be added softened water 50-100 parts, 3-15 parts of dispersing agent, 1-3 parts of wetting agent, 5-20 parts of propylene glycol,
0.5-1 parts of defoaming agent, 1-3 parts of preservative and 1-3 parts of multifunctional assistant, are stirred evenly with adjustable high-speed dispersion machine；
(2) addition pigment and filler, high-speed stirred 20-30 minutes；
(3) 1/3 thickener is added, stirs evenly；
(4) fineness is ground to up to 40 μm with sand mill hereinafter, obtaining pigments and fillers slurry；
(5) pigments and fillers slurry, 1-2 parts of first neutralizer, vinylite lotion 400- of step (4) are added in paint container
600 parts, 100-300 parts of core-shell structure acrylic emulsion, acrylic emulsion 100-200 parts phosphate modified, coalescing agent 10-15
Part, 0.5-2 parts of defoaming agent, 1-5 parts of levelling agent turn agent 50-150 parts of rust, stir evenly；
(6) remaining 2/3 thickener is added, stirs evenly, filters, obtains finished product.
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| CN111138916B (en) * | 2019-12-25 | 2023-03-31 | 中国人民解放军陆军装甲兵学院 | Water-based in-situ directional protective coating and preparation method thereof |
| CN111234641A (en) * | 2020-03-23 | 2020-06-05 | 深圳安盾海洋新材料有限公司 | Water-based acrylic energy-storage luminescent paint and preparation method thereof |
| CN111234641B (en) * | 2020-03-23 | 2021-11-19 | 深圳安盾海洋新材料有限公司 | Water-based acrylic energy-storage luminescent paint and preparation method thereof |
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| CN114835859B (en) * | 2022-07-04 | 2022-09-06 | 山东兴鲁环保新材料有限公司 | Reactive emulsion with rust conversion function and preparation method thereof |
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Application publication date: 20190913 |