CN103382344A - Water-based acrylate resin exterior wall coating containing fluoride and preparation method thereof - Google Patents

Water-based acrylate resin exterior wall coating containing fluoride and preparation method thereof Download PDF

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CN103382344A
CN103382344A CN2013103405325A CN201310340532A CN103382344A CN 103382344 A CN103382344 A CN 103382344A CN 2013103405325 A CN2013103405325 A CN 2013103405325A CN 201310340532 A CN201310340532 A CN 201310340532A CN 103382344 A CN103382344 A CN 103382344A
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fluorine
acrylate resin
monomer
containing aqueous
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CN103382344B (en
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闫福安
唐金勇
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Wuhan Hua Yuan Science and Technology Ltd.
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Wuhan Institute of Technology
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Abstract

The invention relates to a water-based acrylate resin exterior wall coating containing fluoride and a preparation method thereof and includes synthesis of water-based acrylate emulsion containing the fluoride and preparation of the coating. The coating is water-based coating containing the fluoride, overcomes the defect that acrylate resin is easy to contaminate and has the advantages of being self-cleaning, high in gloss, large in adhesive force, good in corrosion resistance and the like. Meanwhile, by selecting auxiliaries containing the fluoride preferentially, the defect that coatings containing the fluoride are poor in wettability and prone to hole shrinkage is overcome, and excellent performance of the coating containing the fluoride is well revealed.

Description

Fluorine-containing aqueous acrylate resin exterior coating and preparation method thereof
Technical field
The present invention relates to a kind of fluorine-containing aqueous acrylate resin exterior coating and preparation method thereof.
Background technology
Along with the enhancing of people's environmental consciousness, water-borne coatings has obtained developing rapidly.Compare with conventional solvent type coating water-borne coatings have price lower, use safety, saving resource and the energy, environmental contamination reduction and the advantage such as nuisanceless.The exterior wall latex paint great majority that use at present both at home and abroad be with acrylic resin as main film forming substance, there are the shortcomings such as hot sticky cold crisp, abrasion resistance, erosion resistance, resistance to soiling, self-cleaning be poor in it.It has preferably early stage water resisting property and erosion resistance although patent No. CN 101338099A has announced a kind of exterior coating, due to its use be common ACRYLIC EMULSION, so have hot sticky cold crisp and the easy shortcoming of contamination.
Demand in view of market, people developed have overlength weathering resistance, resistance to soiling and acid resistance, alkali-proof fluorocarbon coating, it is invested greatly for fluorocarbon coating, starting material are expensive, cost is high and production technique is relatively complicated, and this marketing to fluorocarbon coating is very unfavorable.Patent No. CN 101845261A has invented a kind of exterior wall and has had self-cleaning and stain resistant performance with self-cleaning water-based fluorocarbon paint, can make exterior wall surface keep permanent as new state.
Because so being uses the fluorine carbon emulsion cost higher.Obtain polyacrylic acid fluorine band alkane esters by introduce fluoro-containing group in acrylic ester polymer; because the electronegativity of fluorine is large; C-F key is very stable; fluorine-containing side chain can be to main chain and interior molecules shielding protection; make acrylate not only keep its primary characteristic; also can effectively improve its stability, weathering resistance, pollution resistance and oil-proofness water tolerance, reduce production costs.What patent No. CN 101348595A had invented that a kind of fluorine-silicon modified self-crosslinking acrylic ester emulsion and preparation method thereof uses is this complex operation of hud polymerization technique, its fluorinated monomer is to be aggregated on shell, due to fluorine monomer and other acrylic monomer copolymerizables poor, this can cause the fluorine-containing latex low conversion rate, the low surface energy due to fluorine element can be from trend interface enrichment in film process for fluorine-containing latex, need not deliberately its design to be aggregated on the micelle shell, and it is not described in detail when being mixed with exterior coating.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of fluorine-containing aqueous acrylate resin exterior coating and preparation method thereof for the deficiency of above-mentioned prior art existence, prepared fluorine-containing exterior coating has resistance to acids and bases, washability and contamination resistance preferably, has overcome fluorine-containing latex and the poor coating surface of conventional additive compatibility is prone to the problems such as pin hole, bubble.
The present invention is that the technical scheme that the problem of the above-mentioned proposition of solution adopts is:
The preparation method of fluorine-containing aqueous acrylate resin exterior coating, it comprises the following steps:
(1) the fluorine-containing aqueous acrylate resin emulsion is synthetic:
(a) get the raw materials ready: take mix monomer, reactive emulsifier, deionized water and initiator, reactive emulsifier is the 1%-5% of mix monomer total mass, and initiator is the 0.2%-0.6% of mix monomer total mass; The deionized water consumption is the 150%-300% of mix monomer total mass, and deionized water is divided into A, B, C three parts; Reactive emulsifier is divided into a, b two portions, and a accounts for reactive emulsifier total mass 50%-90%, and surplus is b; Initiator is divided into I, II two portions, and I accounts for initiator total mass 15%-30%, and surplus is II, and the initiator II is dissolved in deionized water C;
(b) with deionized water A and reactive emulsifier a in mixing and stirring, then add mix monomer under agitation condition, obtain the monomer pre-emulsion, the monomer pre-emulsion is divided into α, β two portions, α accounts for the 6%-14% of monomer pre-emulsion total mass, and surplus is β, and is standby;
Add deionized water B, reactive emulsifier b in reaction vessel, and add pH buffer reagent NaHCO 3, keeping the PH of reaction system is 6-8, stirs and is warming up to 83-87 ℃, then adds monomer pre-emulsion α and initiator I; After emulsion became indigo plant and the obvious monomers flow back of nothing, beginning at the uniform velocity dripped monomer pre-emulsion β and initiator II, and the initiator II is dissolved in deionized water C, and controlling time for adding is 3-4 hour; Dropwise rear insulation one hour; Be warming up to 90-93 ℃ and carry out rear elimination, reacted 30 minutes; Being cooled at last room temperature, is 7.5-8.5 with ammonia neutralization to pH value, then filters, and discharging obtains the fluorine-containing aqueous acrylate resin emulsion;
(2) preparation of coating
Weighing by mass percentage, the mass ratio of described each component is deionized water: propylene glycol: dispersion agent: wetting agent: flow agent: defoamer: 2-amino-2-methyl-1-propanol (AMP-95): titanium dioxide: barium sulfate: fluorine-containing aqueous acrylate resin emulsion: film coalescence aid: thickening material=10% ~ 17%:1% ~ 3%:0.1% ~ 1%:0.1% ~ 1%:0.1% ~ 1%:0.1% ~ 4%:0.18% ~ 0.5%:14% ~ 30%:3% ~ 20%:45% ~ 61%:1% ~ 6%:0.4% ~ 4%, wherein defoamer adds at twice, adds 1/2nd of total amount at every turn;
under agitation in order with deionized water, propylene glycol, wetting agent, dispersion agent, flow agent, defoamer (adds defoamer for the first time, total amount 1/2nd), 2-amino-2-methyl-1-propanol (AMP-95), titanium dioxide, after fully mixing, barium sulfate carries out 2000r/min ~ 3000r/min high speed dispersion 20 ~ 30 minutes, be dispersed to fineness less than 40 μ m, then under agitation add the fluorine-containing emulsion, film coalescence aid, the defoamer of surplus (adding for the second time defoamer), thickening material mixes rear filtration discharging, can obtain fluorine-containing aqueous acrylate resin exterior coating.
Press such scheme, the account for 35%-60% of ionized water total mass of the account for 10%-15% of ionized water total mass of described deionized water A, B, surplus is C.
Press such scheme, the preferred mass of each component described in step 2 is than being deionized water: propylene glycol: dispersion agent: wetting agent: flow agent: defoamer: 2-amino-2-methyl-1-propanol (AMP-95): titanium dioxide: barium sulfate: fluorine-containing aqueous acrylate resin emulsion: film coalescence aid: thickening material=13% ~ 17%:1% ~ 1.5%:0.1% ~ 0.3%:0.1% ~ 0.3%:0.1% ~ 0.2%:0.1% ~ 0.2%:0.18% ~ 0.4%:19% ~ 30%:3% ~ 11%:45% ~ 52%:1% ~ 1.5%:0.5% ~ 1%.
Press such scheme, described mix monomer is by acrylicacidandesters class monomer, fluorinated acrylate monomer, linking agent monomer composition, each components based on weight percentage is: methacrylic acid and esters monomer 45%-85% thereof, fluorinated Acrylic Acid Monomer 14%-47%, cross-linking monomer 0.5%-8%.
Press such scheme, described acrylicacidandesters class monomer is the mixture of any one or any two or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isobornyl acrylate, butyl acrylate, lauryl methacrylate(LMA), Tert-butyl Methacrylate, methacrylic acid, vinylformic acid, during any two above mixing be any than.
Press such scheme, described fluorinated acrylate monomer is one or both the mixture in trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate.
Press such scheme, described cross-linking monomer is the mixing of any one or any two or more in glycidyl methacrylate, acrylamide, γ-methacryloxypropyl trimethoxy silane, during any two above mixing be any than.
Press such scheme, described reactive emulsifier is any one or the two or more mixture in acrylamido sodium isopropyl xanthate (AMPS), sodium vinyl sulfonate (SVS), acrylic polyether phosphoric acid ester (APE-2003), is any proportioning during any two or more mixing.
Press such scheme, described initiator is any one in Potassium Persulphate, ammonium persulphate, Sodium Persulfate.
Press such scheme, described dispersion agent is one or both mixtures in any proportion in ammonium polyacrylate (BYK-154), sodium polyacrylate (Dispers 715W).
Press such scheme, described wetting agent is one or more the mixture in water-soluble ethoxy base class non-ionic type fluorocarbon surfactant (FSN-100 E.I.Du Pont Company), polyoxyethylene groups ethers non-ionic type fluorocarbon surfactant (FS0-100 E.I.Du Pont Company), water-soluble phosphate anionoid type fluorocarbon surfactant (FSP E.I.Du Pont Company).
Press such scheme, described flow agent is one or both mixtures in any proportion in fluorine-carbon modified flow agent (Efka 3570), fluorine-carbon modified polyacrylic ester (Efka 3772 BASF AG).
Press such scheme, described defoamer is the special siliceous and multiple mixture of oil base (A10 Kening Co.,Ltd) in ore deposit, hydrophobic solid and broken bubble polysiloxane one or both mixtures in any proportion in polyglycol (the German Bi Ke of BYK028 company).
Press such scheme, described titanium dioxide is Rutile type Titanium Dioxide.
Press such scheme, described film coalescence aid is one or both mixtures in any proportion in Diethylene Glycol butyl ether, alcohol ester 12.
Press such scheme, described thickening material is one or both mixtures in any proportion in acrylic acid series alkali swelling consonance type thickening material (TT-615 the U.S. Rhom and Hass), non-ionic polyurethane associative thickener (RM-2020).
The fluorine-containing aqueous acrylate resin exterior coating for preparing with raw material according to the method described above all belongs to protection scope of the present invention.
The present invention uses the omnidistance technique that drips of pre-emulsification, at first the 6%-14% with monomer pre-emulsion reacts at reactor, superpolymer after this part pre-emulsion monomer polymerization reactions is equivalent to seed in the reaction in later stage, after a part of fluorine monomer is aggregated on macromolecular chain, played the effect that is similar to emulsifying agent in the middle of follow-up polymerization, because fluorochemical monomer has very strong hydrophobicity, fluorine-containing polymkeric substance can reduce the surface tension of emulsion, this is conducive to the carrying out of polymerization, thereby has improved the transformation efficiency of emulsion.Easily produce the defectives such as shrinkage cavity, froth breaking is incomplete, levelling property is bad when being used in conjunction with for fluorine-containing latex and general aqueous promoter, thereby the problems referred to above that the present invention has passed through the successful solution of preferred use fluorinated auxiliary agent make fluorine-containing latex can bring into play better its performance in use.
Compared with prior art, the invention has the beneficial effects as follows:
First, the exterior coating that the present invention produces is aqueous fluorine-containing coating, and it has overcome the shortcoming that acrylic resin easily stains, and has self-cleaning, the advantages such as glossiness is high, strong adhesion, surface hydrophobicity are good, excellent anti-corrosion performance, the simple easy handling of its production technique, cost is relatively low;
The second, the present invention has overcome the easy hot sticky cold crisp of conventional acrylic ester emulsion, the problem of fluorine-containing latex and the easy shrinkage cavity of ordinary adjuvants compatibility film coated surface;
The 3rd, particularly the use of fluorinated auxiliary agent has overcome that the fluoro-containing coating froth breaking is incomplete, wettability is bad in the present invention, the problem that levelling property is poor.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
The preparation method of fluorine-containing aqueous acrylate resin exterior coating, it comprises the following steps:
(1) the fluorine-containing aqueous acrylate resin emulsion is synthetic:
(a) get the raw materials ready: take mix monomer, reactive emulsifier, deionized water and initiator, described mix monomer is comprised of 20g methyl methacrylate, 10g β-dimethyl-aminoethylmethacrylate, 15g butyl acrylate, 12g trifluoroethyl methacrylate, 3g glycidyl methacrylate, reactive emulsifier is 1.8g, deionized water 97g, initiator potassium persulfate total mass 0.24 gram;
(b) with deionized water and the 1.2g reactive emulsifier AMPS mixing and stirring in the pre-emulsification tank of 12g, then under agitation add described mix monomer (being above-mentioned load weighted 20g methyl methacrylate, 10g β-dimethyl-aminoethylmethacrylate, 15g butyl acrylate, 12g trifluoroethyl methacrylate, 3g glycidyl methacrylate), obtain monomer pre-emulsion 73.2g, standby;
Add 55g deionized water, 0.6g reactive emulsifier AMPS and 0.10g sodium bicarbonate (pH buffer reagent) in four-hole boiling flask, stir and be warming up to 83 ℃, the 10g that gets the monomer pre-emulsion joins in four-hole boiling flask, adds the 0.065g initiator; After emulsion becomes indigo plant and the obvious monomers flow back of nothing, beginning at the uniform velocity drips residual monomer pre-emulsion 63.2g and residue 30.175g initiator solution (solid content 0.58%, the effective constituent of initiator is 0.175g, and deionized water is 30g), controlling time for adding is 3 hours; Dropwise rear insulation one hour; Be warming up to 93 ℃ and carry out rear elimination, reacted 30 minutes; Being cooled at last room temperature, is 8.5 with ammonia neutralization to pH value, then filters, and discharging obtains the fluorine-containing aqueous acrylate resin emulsion.
2) preparation of coating
Get the above-mentioned fluorine-containing aqueous acrylate resin emulsion of 100g standby;
get the 25g deionized water, the 2g propylene glycol, 0.4g the BYK-154(dispersion agent), 2-amino-2-methyl-1-propanol AMP-95 0.8g, 0.4g water-soluble ethoxy base class non-ionic type fluorocarbon surfactant FSN-100(wetting agent), 0.4g fluorine-carbon modified flow agent Efka3570(BASF AG), 0.2g defoamer A10 under agitation stirs, transfer to the 2000r/min high speed dispersion, add the 40g titanium dioxide, 20g barium sulfate, be dispersed to fineness less than 40 μ m, then under agitation add 100g fluorine-containing emulsion, 3g alcohol ester 12 (film coalescence aid), 0.2g the A10(defoamer), 1.2gRM-2020(thickening material), mix rear filtration discharging, can obtain fluorine-containing aqueous acrylate resin exterior coating.
Performance Detection:
(1) contamination resistance contrast: the contamination resistance of having measured fluorine-containing exterior coating and common exterior coating according to GB/T9755-2001;
(2) coating performance: the coating performance of having measured fluorine-containing exterior coating and common exterior coating according to GB/T17748-1999.
The prepared fluorine-containing aqueous acrylate resin exterior coating performance test results of embodiment 1 is as shown in table 1:
As can be seen from Table 1, compare with common exterior coating, the fluorine-containing aqueous acrylate resin exterior coating that the present invention is prepared, contamination resistance has improved 3 times, the washability number of times improves 5000 times, water tolerance, the row of anti-boiling water, acid resistance have all obtained better effect, and hardness, ageing resistance and outward appearance are also all fine simultaneously.
Embodiment 2:
The preparation method of fluorine-containing aqueous acrylate resin exterior coating, it comprises the following steps:
(1) the fluorine-containing aqueous acrylate resin emulsion is synthetic:
(a) get the raw materials ready: take mix monomer, reactive emulsifier, deionized water and initiator, described mix monomer is comprised of 13g methyl methacrylate, 6g isobornyl acrylate, 10g butyl acrylate, 10g lauryl methacrylate(LMA), 18g trifluoroethyl methacrylate, 2g glycidyl methacrylate, 1g γ-methacryloxypropyl trimethoxy silane, reactive emulsifier is 2.2g, deionized water 118g, initiator Sodium Persulfate total mass 0.25g;
(b) with deionized water, 0.8g reactive emulsifier AMPS and the 0.6g reactive emulsifier SVS mixing and stirring in the pre-emulsification tank of 13g, then under agitation add described mix monomer (being above-mentioned load weighted 20g methyl methacrylate, 10g β-dimethyl-aminoethylmethacrylate, 15g butyl acrylate, 12g trifluoroethyl methacrylate, 3g glycidyl methacrylate), obtain monomer pre-emulsion 74.4g, standby;
Add 45g deionized water, 0.6g reactive emulsifier AMPS, 0.2g reactive emulsifier SVS and 0.10g sodium bicarbonate in four-hole boiling flask, stir and be warming up to 83 ℃, the 8g that gets the monomer pre-emulsion joins in four-hole boiling flask, adds the 0.07g initiator; After emulsion became indigo plant and the obvious monomers flow back of nothing, beginning at the uniform velocity dripped residual monomer pre-emulsion 66.4g and remains 60.18g initiator solution (solid content 0.3%, the effective constituent of initiator is 0.18g), and the control time for adding is 4 hours; Dropwise rear insulation one hour; Be warming up to 92 ℃ and carry out rear elimination, reacted 30 minutes; Being cooled at last room temperature, is 7.5 with ammonia neutralization to pH value, then filters, and discharging obtains the fluorine-containing aqueous acrylate resin emulsion.
2) preparation of coating
Get the above-mentioned fluorine-containing aqueous acrylate resin emulsion of 100g standby
get the 30g deionized water, 2.5g propylene glycol, 0.4g dispersion agent sodium polyacrylate Dispers 715W, AMP-95 0.6g, 0.4g FSO-100(E.I.Du Pont Company), 0.4gEfka3772(BASF AG), 0.2g A10 (defoamer) stirs under stirring at low speed, transfer to 2000r/min ~ 3000r/min high speed dispersion, advance the 55g titanium dioxide, the 10g process white, be dispersed to fineness less than 40 μ m, then under agitation add 100g fluorine-containing emulsion, 3g Diethylene Glycol butyl ether (film coalescence aid), 0.2g the BYK028(defoamer), the 2gRM-2020(thickening material), mix rear filtration discharging and can obtain fluorine-containing aqueous acrylate resin exterior coating.
Performance Detection:
(1) contamination resistance contrast: the contamination resistance of having measured fluorine-containing exterior coating and common exterior coating according to GB/T9755-2001;
(2) coating performance: the coating performance of having measured fluorine-containing exterior coating and common exterior coating according to GB/T17748-1999.
The prepared fluorine-containing aqueous acrylate resin exterior coating performance test results of embodiment 2 is as shown in table 2:
As can be seen from Table 2, compare with common exterior coating, the fluorine-containing aqueous acrylate resin exterior coating that the present invention is prepared, contamination resistance has improved 4 times, the washability number of times improves 8000 times, water tolerance, the row of anti-boiling water, acid resistance have all obtained better effect, and hardness, ageing resistance and outward appearance are also all fine simultaneously.
Embodiment 3:
The preparation method of fluorine-containing aqueous acrylate resin exterior coating, it comprises the following steps:
(1) the fluorine-containing aqueous acrylate resin emulsion is synthetic:
(a) get the raw materials ready: take mix monomer, reactive emulsifier, deionized water and initiator, described mix monomer is comprised of 15g isobornyl acrylate, 18g butyl acrylate, 5g lauryl methacrylate(LMA), 13g trifluoroethyl methacrylate, 6g vinylformic acid hexafluoro butyl ester, 2g glycidyl methacrylate, 1g acrylamide, reactive emulsifier APE-2003 is 3g, deionized water 100g, initiator Sodium Persulfate total mass 0.36 gram;
(b) with deionized water and the 2g response type emulsification APE-2003 mixing and stirring in the pre-emulsification tank of 10g, then under agitation add mix monomer, stir and obtain monomer pre-emulsion 72g, standby.
Add 45g deionized water, 1g reactive emulsifier APE-2003 and 0.10g sodium bicarbonate in four-hole boiling flask, stir and be warming up to 83 ℃, the 10g that gets monomer pre-emulsion joins in four-hole boiling flask, adds the 0.06g initiator; Until emulsion change indigo plant and after without obvious monomers flow back, beginning at the uniform velocity dropping remains 62g monomer pre-emulsion and 45.3g residue initiator solution (admittedly contain 0.66%, the effective constituent of initiator is 0.3g), and the control time for adding is 3.5 hours; Dropwise rear insulation one hour; Be warming up to 92 ℃ and carry out rear elimination, reacted 30 minutes; Being cooled at last room temperature, is 8.5 with ammonia neutralization to pH value, then filters, and discharging obtains the fluorine-containing aqueous acrylate resin emulsion.
2) preparation of coating
Get the above-mentioned fluorine-containing aqueous acrylate resin emulsion of 100g standby;
get the 36g deionized water, the 3g propylene glycol, 0.6g sodium polyacrylate Dispers 715W(dispersion agent), AMP-95 0.4g, 0.2g wetting agent FSP(E.I.Du Pont Company), 0.2gEfka3772, 0.2g flow agent Efka3570(BASF AG), 0.1g A10 (defoamer) under agitation stirs, transfer to 2000r/min ~ 3000r/min high speed dispersion, advance the 65g titanium dioxide, the 8g process white, be dispersed to fineness less than 40 μ m, then add 100g fluorine-containing emulsion under stirring at low speed, 3g alcohol ester 12 (film coalescence aid), 0.2g the BYK028(defoamer), the 2gRM-2020(thickening material), mix rear filtration discharging, can obtain fluorine-containing aqueous acrylate resin exterior coating.
Performance Detection:
(1) contamination resistance contrast: the contamination resistance of having measured fluorine-containing exterior coating and common exterior coating according to GB/T9755-2001;
(2) coating performance: the coating performance of having measured fluorine-containing exterior coating and common exterior coating according to GB/T17748-1999.
The prepared fluorine-containing aqueous acrylate resin exterior coating performance test results of embodiment 3 is as shown in table 3:
As can be seen from Table 3, compare with common exterior coating, the fluorine-containing aqueous acrylate resin exterior coating that the present invention is prepared, contamination resistance has improved 4 times, the washability number of times improves 10000 times, water tolerance, ageing resistance, the row of anti-boiling water, acid resistance have all obtained better effect, and hardness and outward appearance are also all fine simultaneously.

Claims (10)

1. the preparation method of fluorine-containing aqueous acrylate resin exterior coating is characterized in that it comprises the following steps:
(1) the fluorine-containing aqueous acrylate resin emulsion is synthetic:
(a) get the raw materials ready: take mix monomer, reactive emulsifier, deionized water and initiator, reactive emulsifier is the 1%-5% of mix monomer total mass, and initiator is the 0.2%-0.6% of mix monomer total mass; The deionized water consumption is the 150%-300% of mix monomer total mass, and deionized water is divided into A, B, C three parts; Reactive emulsifier is divided into a, b two portions, and a accounts for reactive emulsifier total mass 50%-90%, and surplus is b; Initiator is divided into I, II two portions, and I accounts for initiator total mass 15%-30%, and surplus is II, and the initiator II is dissolved in deionized water C;
(b) with deionized water A and reactive emulsifier a mixing and stirring, then add mix monomer under agitation condition, obtain the monomer pre-emulsion, the monomer pre-emulsion is divided into α, β two portions, α accounts for the 6%-14% of monomer pre-emulsion total mass, and surplus is β, and is standby;
Add deionized water B, reactive emulsifier b in reaction vessel, and add pH buffer reagent NaHCO 3, keeping the pH of reaction system is 6-8, stirs and is warming up to 83-87 ℃, then adds monomer pre-emulsion α and initiator I; After emulsion became indigo plant and the obvious monomers flow back of nothing, beginning at the uniform velocity dripped monomer pre-emulsion β and initiator II, and the initiator II is dissolved in deionized water C, and controlling time for adding is 3-4 hour; Dropwise rear insulation one hour, be warming up to 90-93 ℃ and carry out rear elimination, reacted 30 minutes; Being cooled at last room temperature, is 7.5-8.5 with ammonia neutralization to pH value, then filters, and discharging obtains the fluorine-containing aqueous acrylate resin emulsion;
(2) preparation of coating
Weighing by mass percentage, the mass ratio of described each component is deionized water: propylene glycol: dispersion agent: wetting agent: flow agent: defoamer: 2-amino-2-methyl-1-propanol: titanium dioxide: barium sulfate: fluorine-containing aqueous acrylate resin emulsion: film coalescence aid: thickening material=10% ~ 17%:1% ~ 3%:0.1% ~ 1%:0.1% ~ 1%:0.1% ~ 1%:0.1% ~ 4%:0.18% ~ 0.5%:14% ~ 30%:3% ~ 20%:45% ~ 61%:1% ~ 6%:0.4% ~ 4%, wherein defoamer adds at twice, adds 1/2nd of defoamer total amount at every turn;
Under agitation with deionized water, propylene glycol, wetting agent, dispersion agent, flow agent, defoamer total amount 1/2nd, 2-amino-2-methyl-1-propanol, titanium dioxide, barium sulfate carry out 2000r/min ~ 3000r/min high speed dispersion 20 ~ 30 minutes after fully mixing, be dispersed to fineness less than 40 μ m, then under agitation add defoamer, the thickening material of fluorine-containing aqueous acrylate resin emulsion, film coalescence aid, surplus to mix rear filtration discharging, can obtain fluorine-containing aqueous acrylate resin exterior coating.
2. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1 is characterized in that the account for 10%-15% of ionized water total mass of described deionized water A, the account for 35%-60% of ionized water total mass of B, and surplus is C.
3. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, the mass ratio that it is characterized in that each component described in step 2 is deionized water: propylene glycol: dispersion agent: wetting agent: flow agent: defoamer: 2-amino-2-methyl-1-propanol: titanium dioxide: barium sulfate: fluorine-containing aqueous acrylate resin emulsion: film coalescence aid: thickening material=13% ~ 17%:1% ~ 1.5%:0.1% ~ 0.3%:0.1% ~ 0.3%:0.1% ~ 0.2%:0.1% ~ 0.2%:0.18% ~ 0.4%:19% ~ 30%:3% ~ 11%:45% ~ 52%:1% ~ 1.5%:0.5% ~ 1%.
4. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, it is characterized in that described mix monomer is by acrylicacidandesters class monomer, fluorinated Acrylic Acid Monomer, linking agent monomer composition, each components based on weight percentage is: methacrylic acid and esters monomer 45%-85% thereof, fluorinated acrylate monomer 14%-47%, cross-linking monomer 0.5%-8%.
5. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, it is characterized in that described acrylicacidandesters class monomer is the mixture of any one or any two or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isobornyl acrylate, butyl acrylate, lauryl methacrylate(LMA), Tert-butyl Methacrylate, methacrylic acid, vinylformic acid, during any two above mixing be any than; Described fluorinated acrylate monomer is one or both the mixture in trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate; Described cross-linking monomer is the mixing of any one or any two or more in glycidyl methacrylate, acrylamide, γ-methacryloxypropyl trimethoxy silane, during any two above mixing be any than.
6. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, it is characterized in that described reactive emulsifier is any one or the two or more mixture in acrylamido sodium isopropyl xanthate, sodium vinyl sulfonate, acrylic polyether phosphoric acid ester, is any proportioning during any two or more mixing.
7. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, is characterized in that described initiator is any one in Potassium Persulphate, ammonium persulphate, Sodium Persulfate; Described dispersion agent is one or both mixtures in any proportion in ammonium polyacrylate, sodium polyacrylate.
8. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, is characterized in that described wetting agent is one or more mixtures in any proportion in water-soluble ethoxy base class non-ionic type fluorocarbon surfactant, polyoxyethylene groups ethers non-ionic type fluorocarbon surfactant, water-soluble phosphate anionoid type fluorocarbon surfactant; Described flow agent is one or both mixtures in any proportion in fluorine-carbon modified flow agent, fluorine-carbon modified polyacrylic ester.
9. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, is characterized in that described defoamer is the siliceous and multiple mixture of the special oil base in ore deposit, hydrophobic solid and broken bubble polysiloxane one or both mixtures in any proportion in polyglycol; Described film coalescence aid is one or both mixtures in any proportion in Diethylene Glycol butyl ether, alcohol ester 12; Described thickening material is one or both mixtures in any proportion in acrylic acid series alkali swelling consonance type thickening material, non-ionic polyurethane associative thickener.
10. the resulting fluorine-containing aqueous acrylate resin of the described preparation method of claim 1-9 exterior coating.
CN201310340532.5A 2013-08-07 2013-08-07 Fluorine-containing aqueous acrylate resin exterior coating and preparation method thereof Active CN103382344B (en)

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CN104449154A (en) * 2014-11-28 2015-03-25 合肥工业大学 Water-based chromium-free fingerprint-resistant paint for galvanized steel plate
CN104610833A (en) * 2015-01-20 2015-05-13 扬州豪扬新型建筑材料有限公司 Preparation method of anti-fouling waterproof coating adopting modified acrylic acid
CN104725923A (en) * 2015-03-26 2015-06-24 湖州科达化工燃料有限公司 Novel thickening agent for emulsion architecture coating and preparation method thereof
CN105199514A (en) * 2015-10-27 2015-12-30 北京东方雨虹防水技术股份有限公司 Fluorocarbon elastic waterproof paint for metal color steel roofing and preparation method thereof
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CN106117413A (en) * 2016-06-27 2016-11-16 南京信息工程大学 Fluorine carbon emulsion without soap prepared by a kind of perfluoroalkyl acrylate copolymerization and preparation method thereof
CN107189005A (en) * 2017-05-26 2017-09-22 华中科技大学 A kind of mode of laser pressing print hologram recording material emulsion and its preparation and application
CN108129616A (en) * 2017-12-14 2018-06-08 江苏飞天玻璃实业有限公司 A kind of self-cleaning temperature-regulating glass and preparation method thereof
CN108559352A (en) * 2018-04-03 2018-09-21 佛山科学技术学院 A kind of thermal conductivity functional paint and preparation method
CN109096857A (en) * 2018-07-26 2018-12-28 深圳市莱莉雅环保科技有限公司 The aqueous anti-graffiti coating and its preparation process of scintilla water dispersion
CN109385150A (en) * 2018-10-09 2019-02-26 刘鹏 A kind of water-proof climate resisting bi-component exterior wall latex paint
CN109679438A (en) * 2018-12-25 2019-04-26 沈阳化工研究院有限公司 A kind of environment-friendly type hydrophobicity fluorine-containing clear coat composition and preparation method thereof
CN109852186A (en) * 2019-01-21 2019-06-07 长安大学 A kind of fluorocarbon coating for the erosion of paralic environment antiseptic concrete
CN110790858A (en) * 2019-10-08 2020-02-14 武汉长弢新材料有限公司 Environment-responsive coating and preparation method thereof
WO2020058810A1 (en) * 2018-09-21 2020-03-26 Ppg Industries Ohio, Inc. Coating composition providing increased adhesion and/or uv durability to a substrate
CN112266678A (en) * 2020-10-29 2021-01-26 扬州工业职业技术学院 Waterproof coating for external wall and preparation method thereof
CN112920667A (en) * 2021-02-01 2021-06-08 淄博职业学院 Organic-inorganic antibacterial antifouling interior wall coating and preparation method thereof

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CN103724563A (en) * 2013-12-26 2014-04-16 中昊北方涂料工业研究设计院有限公司 Fluoroacrylate-containing modified polysiloxane resin and preparation method of coating made therefrom
CN103724563B (en) * 2013-12-26 2016-04-27 中昊北方涂料工业研究设计院有限公司 The preparation method of a kind of fluorine-containing modified polysiloxane resin and coating composition thereof
CN104449154A (en) * 2014-11-28 2015-03-25 合肥工业大学 Water-based chromium-free fingerprint-resistant paint for galvanized steel plate
CN104610833A (en) * 2015-01-20 2015-05-13 扬州豪扬新型建筑材料有限公司 Preparation method of anti-fouling waterproof coating adopting modified acrylic acid
CN104725923A (en) * 2015-03-26 2015-06-24 湖州科达化工燃料有限公司 Novel thickening agent for emulsion architecture coating and preparation method thereof
CN105199514A (en) * 2015-10-27 2015-12-30 北京东方雨虹防水技术股份有限公司 Fluorocarbon elastic waterproof paint for metal color steel roofing and preparation method thereof
CN105623451A (en) * 2015-12-31 2016-06-01 南京福臻再生资源科技股份有限公司 Self-cleaning fluorocarbon paint and preparation method thereof
CN106117413A (en) * 2016-06-27 2016-11-16 南京信息工程大学 Fluorine carbon emulsion without soap prepared by a kind of perfluoroalkyl acrylate copolymerization and preparation method thereof
CN107189005B (en) * 2017-05-26 2019-09-24 华中科技大学 A kind of mode of laser pressing print hologram recording material lotion and its preparation and application
CN107189005A (en) * 2017-05-26 2017-09-22 华中科技大学 A kind of mode of laser pressing print hologram recording material emulsion and its preparation and application
CN108129616A (en) * 2017-12-14 2018-06-08 江苏飞天玻璃实业有限公司 A kind of self-cleaning temperature-regulating glass and preparation method thereof
CN108559352A (en) * 2018-04-03 2018-09-21 佛山科学技术学院 A kind of thermal conductivity functional paint and preparation method
CN109096857A (en) * 2018-07-26 2018-12-28 深圳市莱莉雅环保科技有限公司 The aqueous anti-graffiti coating and its preparation process of scintilla water dispersion
WO2020058810A1 (en) * 2018-09-21 2020-03-26 Ppg Industries Ohio, Inc. Coating composition providing increased adhesion and/or uv durability to a substrate
CN109385150A (en) * 2018-10-09 2019-02-26 刘鹏 A kind of water-proof climate resisting bi-component exterior wall latex paint
CN109385150B (en) * 2018-10-09 2021-04-16 广东彩居建筑工程有限公司 Waterproof weather-resistant double-component exterior wall emulsion paint
CN109679438A (en) * 2018-12-25 2019-04-26 沈阳化工研究院有限公司 A kind of environment-friendly type hydrophobicity fluorine-containing clear coat composition and preparation method thereof
CN109852186A (en) * 2019-01-21 2019-06-07 长安大学 A kind of fluorocarbon coating for the erosion of paralic environment antiseptic concrete
CN110790858A (en) * 2019-10-08 2020-02-14 武汉长弢新材料有限公司 Environment-responsive coating and preparation method thereof
CN112266678A (en) * 2020-10-29 2021-01-26 扬州工业职业技术学院 Waterproof coating for external wall and preparation method thereof
CN112920667A (en) * 2021-02-01 2021-06-08 淄博职业学院 Organic-inorganic antibacterial antifouling interior wall coating and preparation method thereof
CN112920667B (en) * 2021-02-01 2021-10-29 淄博职业学院 Organic-inorganic antibacterial antifouling interior wall coating and preparation method thereof

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