CN101775189B - Acrylic emulsion and application thereof - Google Patents
Acrylic emulsion and application thereof Download PDFInfo
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- CN101775189B CN101775189B CN2010101051322A CN201010105132A CN101775189B CN 101775189 B CN101775189 B CN 101775189B CN 2010101051322 A CN2010101051322 A CN 2010101051322A CN 201010105132 A CN201010105132 A CN 201010105132A CN 101775189 B CN101775189 B CN 101775189B
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- ketone
- acrylic
- resin
- fluorine
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Abstract
The invention relates to acrylic emulsion comprising fluorine ketone hydroxyl acrylic resin, ADH as cross-linking agent and water-soluble amino resin. Firstly, ketone carbonyl in the luorine ketone hydroxyl acrylic resin is crosslinked with the ADH; secondly, fluorine-containing monomer is added in the acrylic resin to improve the water resistance and corrosion resistance of the resin; and thirdly, crosslinking of the hydroxyl in the fluorine ketone hydroxyl acrylic with the amino resin as well as crosslinking of the ketone hydroxyl with the ADH forms double crosslinking. The three aspects act together to greatly improve the corrosion resistance of the acrylic emulsion. The acidic fog resistant time of water paint made by using the emulsion as the main film forming matter reaches 72 hours, and other performances are close to or even exceed the performance of oil paint.
Description
Technical field
The present invention relates to a kind of raw material that is used to make water-borne coatings, relate in particular to a kind of ACRYLIC EMULSION, as film forming matter main in the water-borne coatings.
Background technology
Aqueous acrylic emulsion is widely used in the water-borne coatings, such as: interior outer wall building coating almost all adopts aqueous acrylic emulsion.Usually aqueous acrylic emulsion, is formed through letex polymerization in water in the presence of emulsifying agent by monomers such as Acrylic Acid Monomer, vinyl acetate between to for plastic and vinylbenzene.Typical letex polymerization and rubber-emulsion paint preparation technology can be referring to " coating process " (third edition) volume two, Chemical Industry Press 1997,197-229 pages or leaves.
There are two significant disadvantage in aqueous acrylic emulsion: at first be that paint film is softer; This is because aqueous acrylic emulsion need the fusion through micro emulsion form the successive paint film in water solvent volatilization back; Do not have crosslinking reaction,, cause the film forming difficulty if polymer glass temperature (Tg) is too high; The inevitable hardness of the low then paint film of Tg is low, and nail can scratch usually; Second shortcoming is that Corrosion Protection is bad; This is because water soluble acrylic acid relies on the wetting ability of monomeric wetting ability or emulsifying agent to form stable emulsion; These hydrophilic radicals just cause the water tolerance extreme difference of paint film after film forming; Thereby the general salt spray resistance of rust proof paint that common water soluble acrylic acid is made can only reach 100-200 hour, and solvent typely generally can reach 500-1000 hour.
Can overcome the above problems well through crosslinked film forming method.Through crosslinked, the hardness and the Corrosion Protection of paint film all are greatly improved.The simplest method is the bi-component acrylic polyurethane coating: be the A component with the ACRYLIC EMULSION, vulcabond or POLYMETHYLENE POLYPHENYLISOCYANATE are the B component, and two components can be constructed after mixing.The shortcoming of this method is that the water in the ACRYLIC EMULSION can consume the part isocyanic ester, causes crosslinked difficulty, and because too much water and isocyanic ester produce carbonic acid gas, thereby cause the paint film bubbling.
Present reasonable crosslinking technological is the self-cross linking type ACRYLIC EMULSION: introduce the ketone carbonyl on the polymer macromolecule chain in hydrotropisms's polymer emulsion, and it is normal temperature crosslinked as linking agent emulsion to be realized with hydrazine or hydrazides.The unsaturated monomer that can on the polymer macromolecule chain, introduce the ketone carbonyl comprises diacetone-acryloamide(DAA) (DAAM), (methyl) propenal, methyl vinyl ketone, (methyl) vinylformic acid acetoxyl group ethyl ester etc.Because little, the easy purchase of DAAM toxicity can also strengthen the paint adhesion performance, so now mainly on the ACRYLATE COPOLYMER EMULSION chain, introduce the ketone carbonyl with DAAM as the functional monomer.Linking agent commonly used mainly is adipic dihydrazide (ADH).ADH can directly join (coatings industry, 2008,38 (12), 30) in the acrylic ester emulsion of introducing the ketone carbonyl, when mechanism of crosslinking is water volatilization emulsion film forming, and ketone carbonyl and the amido generation hydrazone compounds that reacts, thus realize normal temperature crosslinked.
Even but carry out crosslinkedly according to the method described above, and the Corrosion Protection of aqueous acrylic emulsion is still not ideal enough, and salt mist experiment can only reach 200-300 hour usually.
Summary of the invention
One object of the present invention is to provide a kind of ACRYLIC EMULSION, and this emulsion contains fluorine ketone Hydroxylated acrylic resin, makes the anti-corrosion capability of ACRYLIC EMULSION significantly improve.
Another object of the present invention is to provide a kind of water soluble acrylic acid coating; The ACRYLIC EMULSION that will contain fluorine ketone Hydroxylated acrylic resin cooperates with other component as main film forming matter again, and performances such as not only sticking power is good, hardness is high for the coating that makes, snappiness and chemical resistance are also very excellent.
A kind of ACRYLIC EMULSION provided by the invention comprises fluorine ketone Hydroxylated acrylic resin, and as the adipic dihydrazide (ADH) and the water soluble amino resin of linking agent.
Fluorine ketone Hydroxylated acrylic resin of the present invention is in water, to carry out radical polymerization by the unsaturated monomer that contains the ketone carbonyl, hydroxyl acrylic monomer, vinyl monomer and fluorine-containing unsaturated monomer to make.
Another kind of fluorine ketone Hydroxylated acrylic resin provided by the invention carries out radical polymerization by the fluorine-containing unsaturated monomer of the vinyl monomer of the hydroxyl acrylic monomer of the unsaturated monomer that contains the ketone carbonyl that accounts for total monomer weight 0.5-10%, 2-10%, 50-95% and 2-30% and obtains in water.Radical polymerization is a kind of polymerization technique that those of ordinary skills use always, under the guidance of relevant high molecular polymer textbook, just can obtain fluorine ketone Hydroxylated acrylic resin of the present invention.
The unsaturated monomer that contains the ketone carbonyl of the present invention is selected from following one or more monomeric combinations: diacetone-acryloamide(DAA), propenal, Methylacrylaldehyde, methyl vinyl ketone, vinylformic acid acetoxyl group ethyl ester or methylacrylic acid acetoxyl group ethyl ester, preferentially select diacetone-acryloamide(DAA).
Hydroxyl acrylic monomer of the present invention is selected from structural formula
The monomeric combination of shown one or more, wherein R1 is independently selected from the alkyl of H or C1-C6, and wherein, R2 is independently selected from the substituted C1-C5 straight chained alkyl of hydroxyl, preferentially selects the substituted alkyl of terminal hydroxyl, as :-CH
2OH ,-CH
2CH
2OH ,-CH
2CH
2CH
3OH ,-CH
2CH
2CH
2CH
3OH and-CH
2CH
2CH
2CH
2CH
3OH.
Vinyl monomer of the present invention is selected from following one or more monomeric combinations: the compound shown in vinylbenzene, alpha-methyl styrene, vinyl acetate between to for plastic, vinyl cyanide and the structural formula
; Wherein R3 is independently selected from the alkyl of H or C1-C6, and R4 is independently selected from hydroxyalkyl, replacement or unsubstitued furyl, replacement or unsubstituted phenmethyl, replacement or unsubstituted glycidyl, replacement or the unsubstituted isobornyl of the naphthenic base of the alkyl of H, C1-C20, the substituted C3-C10 of C1-C3 alkyl, C1-C6 or methoxyl group C1-C6 alkyl ester.
Fluorine-containing unsaturated monomer of the present invention is selected from following one or more monomeric combinations: trifluorochloroethylene, vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, methylacrylic acid hexafluoro butyl ester, vinylformic acid ten difluoro fat in heptan, methylacrylic acid ten difluoro fat in heptan, vinylformic acid ten trifluoro monooctyl esters and methylacrylic acid ten trifluoro monooctyl esters.
Water soluble amino resin of the present invention is selected from the terpolycyantoamino-formaldehyde resin of the complete methyl-etherified that can be dissolved in water or the urea-formaldehyde resin of complete methyl-etherified, preferably HMMM resin (HMMM).
ACRYLIC EMULSION provided by the invention, its preparation process was divided into for three steps: at first be to use emulsion polymerization technology in water, to obtain fluorine ketone Hydroxylated acrylic resin through copolymerization, in emulsion, add ADH and water soluble amino resin then.Before adding ADH, need to use ammoniacal liquor or amine adjustment emulsion pH to be 7-9.
Emulsion polymerization technology belongs to the general operation technical ability that those of ordinary skills should possess, and also can prepare according to the guidance of " coating process (third edition) " (coating process editorial committee compiles, Chemical Industry Press, 1997) book.
A kind of preparation technology of ACRYLIC EMULSION: earlier reaction kettle is drained air, the monomer of emulsifying agent, buffer reagent, deionized water, initiator and 10-20w/w% is all added in the still high speed dispersion 30 minutes; Be warming up to 80 ℃, treat to continue to drip residual monomer and initiator after the peak heat release appearance; Be incubated to level of response and reach more than 90%, add initiator then 1-2 time, continue insulation 1-2 hour; Be cooled to room temperature, promptly obtain fluorine ketone Hydroxylated acrylic resin emulsion.
Then, adding organic amine adjustment emulsion pH such as ammoniacal liquor or ethamine, diethylamine to fluorine ketone Hydroxylated acrylic resin emulsion is 7-9, adds ADH and water soluble amino resin again.Usually, ADH is 0.3: 1 to 3: 1 with the weight ratio that contains the unsaturated monomer of ketone carbonyl.And the ratio of fluorine ketone Hydroxylated acrylic resin and water soluble amino resin solids constituent weight is 3: 1 to 10: 1.
The ACRYLIC EMULSION that makes with the present invention is the water-borne coatings of main film forming matter preparation; The preparation of coating belongs to those of ordinary skills' the general technical ability that should possess; Also can be according to " coating process (third edition) " (coating process editorial committee volume; Chemical Industry Press, 1997) guidance of a book prepares.For rust-inhibiting paint or stress the priming paint of Corrosion Protection, should comprise that usually rust-stabilising pigment is to strengthen Corrosion Protection.Typical rust-stabilising pigment has red lead, zinc yellow, zn phosphate, strontium chromate and zinc molybdate.Coating to Corrosion Protection is less demanding then needn't be used above-mentioned rust-stabilising pigment.Form according to general coating, the raw material that can use also comprises: tinting pigment, as: iron oxide red, white titanium pigment, carbon black, phthalocyanine blue and zinc oxide etc.; Pigment extender, as: permanent white, talcum powder, lime carbonate, china clay and mica powder etc.; Auxiliary agent comprises: flow agent, as: polyurethanes, polyether modified siloxane multipolymer, polyether modified silicon oil, alkylaryl modified organic silicon and fluoropolymer etc.; Skimmer, wetting dispersing agent and adhesion promoter etc.; Film coalescence aid, as: 1-Methoxy-2-propyl acetate, dipropylene glycol methyl ether acetate, ethylene glycol monoethyl ether, DBE or the like.
The beneficial effect that technical scheme of the present invention realizes:
ACRYLIC EMULSION provided by the invention comprises fluorine ketone Hydroxylated acrylic resin, and as the ADH and the water soluble amino resin of linking agent.Make ketone carbonyl and ADH in the fluorine ketone Hydroxylated acrylic resin crosslinked mutually; Next is in vinyl resin, to add fluorochemical monomer, and then improves the water tolerance and the Corrosion Protection of resin; The 3rd, hydroxy component in the fluorine ketone Hydroxylated acrylic resin and aminoresin crosslinked, dual crosslinked with the crosslinked formation of ketone carbonyl and ADH.These three aspect actings in conjunction; The anti-corrosion capability of ACRYLIC EMULSION is greatly enhanced; With the water-borne coatings that emulsion of the present invention is processed as main film forming matter, the acidic fog resistance time reached more than 720 hours, other performance also near in addition surpass the performance of oil paint.
Term involved in the present invention is identical with notion as the one of which.
Described " alkyl of C1-C6 ", " alkyl of C1-C20 ", " naphthenic base of the substituted C3-C10 of C1-C3 alkyl " and " hydroxyalkyl of C1-C6 "; Letter C is represented carbon atom; Thereafter numeral is a positive integer, as: 1,2,3,4 or 5 etc., the contained carbon atom number of expression group; Said " alkyl " includes the straight or branched alkyl.
Described " solids constituent " promptly refers to the weight percentage of contained resin solid in the resin.
Described " rust-stabilising pigment ", " tinting pigment ", " pigment extender ", " auxiliary agent " and " solvent " are material commonly used in the paint field.
Described " water-borne coatings " is meant and calculates by weight that water accounts for the coating more than 70% in the volatile matter.
Described " oil paint " is meant and calculates by weight that organism accounts for the coating more than 90% in the volatile matter.
Embodiment
Below describe technical scheme of the present invention in detail.The embodiment of the invention is only unrestricted in order to technical scheme of the present invention to be described; Although the present invention is specified with reference to preferred embodiment; Those of ordinary skill in the art is to be understood that; Can make amendment or be equal to replacement the technical scheme of invention, and not break away from the spirit and the scope of technical scheme of the present invention, it all should be encompassed in the claim scope of the present invention.
The reagent that the present invention is used is not if clearly indicate, then all available from Sigma-aldrich (Sigma-Aldrich).
The preparation of embodiment 1 fluorine ketone Hydroxylated acrylic resin emulsion
It is as shown in the table to fill a prescription
Press three kinds of fluorine ketone Hydroxylated acrylic resin emulsions of the listed various component preparations of table 1, numerical value is weight part in the table.
Table 1 fluorine ketone Hydroxylated acrylic resin emulsion
Polymerization technique: the initiator of emulsifying agent, buffer reagent, deionized water, 15w/w% and the monomer of 20w/w% are all added in the still, and high speed dispersion 30 minutes is warming up to 80 ℃; After treating that peak heat release occurs; Continue to drip residue 80% monomer and 65% initiator, 80-85 ℃ is incubated to level of response and reaches more than 90%, divides then and adds remaining 20% initiator for 1-2 time; Continue insulation 1-2 hour, be cooled to room temperature.
The preparation of embodiment 2 ACRYLIC EMULSIONs
Adding ammoniacal liquor or diethylamine adjustment pH is 7-9 in the fluorine ketone Hydroxylated acrylic resin emulsion in embodiment 1, presses table 2 then and adds ADH and water soluble amino resin, and add-on is as shown in the table, and numerical value is weight part in the table.
Table 2 ACRYLIC EMULSION
After the stirring at low speed 2 hours, the discharging of sieving.
The preparation of embodiment 3 water-borne coatingss
Numerical value in the present embodiment is weight part
Following starting material are mixed:
Water 43 pigment dispersing agents (25% effective constituent) 10
Ucar 35 40 wetting agents 2
Skimmer 2 dimethylethanolamines 2
After mixing, add following component:
White titanium pigment 250 miniaturization kaolin 58
After the high speed dispersion, under low speed, add following component:
The water-borne coatings solids constituent 40-45% that makes, viscosity 70-90KU (stormer viscosity).
This water-borne coatings is diluted to the viscosity that is suitable for spraying with deionized water, sprays on the tinplate, 150 ℃ of bakings 30 minutes; The performance that detection is filmed is as shown in table 3: (the prescription 1 shown in the table; Prescription 2, prescription 3 are meant the water-borne coatings with the emulsion preparation of corresponding prescription among the embodiment 1,2)
Table 3 water soluble acrylic acid coating film forming properties
Compare according to test result and with certain commercially available waterborne anti-rust lacquer, water-borne coatings provided by the invention is superior to this commercially available water-borne coatings greatly on performance, and similar with the oil paint performance.
Claims (6)
1. ACRYLIC EMULSION is characterized in that comprising fluorine ketone Hydroxylated acrylic resin, as the adipic dihydrazide and the water soluble amino resin of linking agent; Wherein, described fluorine ketone Hydroxylated acrylic resin carries out radical polymerization by the fluorine-containing unsaturated monomer of the vinyl monomer of the hydroxyl acrylic monomer of the unsaturated monomer that contains the ketone carbonyl that accounts for total monomer weight 0.5-10%, 2-10%, 50-95% and 2-30% and obtains in water; The described unsaturated monomer that contains the ketone carbonyl is selected from a kind of or several kinds of monomeric combinations of diacetone-acryloamide(DAA), propenal, Methylacrylaldehyde, methyl vinyl ketone, vinylformic acid acetoxyl group ethyl ester and methylacrylic acid acetoxyl group ethyl ester; Described vinyl monomer is selected from following one or more monomeric combinations: the combination of the compound shown in vinylbenzene, alpha-methyl styrene, vinyl acetate between to for plastic, vinyl cyanide and the structural formula
a kind of or several kinds; Wherein R3 is independently selected from the alkyl of H or C1-C6, and R4 is independently selected from the hydroxyalkyl of the naphthenic base of the alkyl of H, C1-C20, the substituted C3-C10 of C1-C3 alkyl, C1-C6, furyl, phenmethyl, glycidyl, isobornyl or methoxyl group C1-C6 alkyl ester; Described fluorine-containing unsaturated monomer is selected from a kind of or several kinds of monomeric combinations of trifluorochloroethylene, vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, methylacrylic acid hexafluoro butyl ester, vinylformic acid ten difluoro fat in heptan, methylacrylic acid ten difluoro fat in heptan, vinylformic acid ten trifluoro monooctyl esters and methylacrylic acid ten trifluoro monooctyl esters;
Described hydroxyl acrylic monomer; Be selected from one or more the monomeric combinations shown in the structural formula
; Wherein R1 is independently selected from H or methyl, and R2 is independently selected from the substituted C1-C5 straight chained alkyl of hydroxyl.
2. ACRYLIC EMULSION according to claim 1 is characterized in that said adipic dihydrazide and the said weight ratio that contains the unsaturated monomer of ketone carbonyl are 0.3: 1 to 3: 1.
3. ACRYLIC EMULSION according to claim 1, the ratio that it is characterized in that said fluorine ketone Hydroxylated acrylic resin and said water soluble amino resin solids constituent is 3: 1 to 10: 1.
4. ACRYLIC EMULSION according to claim 1 is characterized in that described R2 is selected from-CH
2OH or-CH
2CH
2OH.
5. ACRYLIC EMULSION according to claim 1 is characterized in that described water soluble amino resin, is selected from the terpolycyantoamino-formaldehyde resin of complete methyl-etherified or the urea-formaldehyde resin of complete methyl-etherified.
6. one kind with the water-borne coatings of the described ACRYLIC EMULSION of one of claim 1-5 as main film forming matter preparation.
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|---|---|---|---|
| CN2010101051322A CN101775189B (en) | 2010-02-03 | 2010-02-03 | Acrylic emulsion and application thereof |
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|---|---|---|---|
| CN2010101051322A CN101775189B (en) | 2010-02-03 | 2010-02-03 | Acrylic emulsion and application thereof |
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| CN101775189B true CN101775189B (en) | 2012-06-27 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571117A (en) * | 2012-07-18 | 2014-02-12 | 西安榕森漆业有限责任公司 | Preparation method for high performance acrylic waterborne resin |
| CN103409002A (en) * | 2013-06-21 | 2013-11-27 | 天长市润达金属防锈助剂有限公司 | Environment-friendly anticorrosive acrylic acid water-based coating and preparation method thereof |
| CN104804125A (en) * | 2015-04-16 | 2015-07-29 | 佛山市顺德区巴德富实业有限公司 | Adipic dihydrazide modified acrylic ester emulsion for removing formaldehyde and preparation method of emulsion |
| CN109161260A (en) * | 2018-09-05 | 2019-01-08 | 马鞍山市金韩涂料制造有限公司 | A kind of production technology for road mark paint |
| CN109652007B (en) * | 2018-12-06 | 2021-05-18 | 成都硅宝科技股份有限公司 | Oil-seepage-resistant bi-component silicone sealant and preparation method thereof |
| CN111560100A (en) * | 2020-06-28 | 2020-08-21 | 广西贵港和乐门业有限公司 | Novel acrylic resin and preparation method and application thereof |
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| US6300411B1 (en) * | 1998-03-20 | 2001-10-09 | Mitsubishi Chemical Corporation | Aqueous resin composition |
| CN1896113A (en) * | 2006-06-15 | 2007-01-17 | 南开大学 | Printing fluorinated acrylic ester self-crosslinked emulsion and its preparation |
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