CN101775189A - Acrylic emulsion and application thereof - Google Patents
Acrylic emulsion and application thereof Download PDFInfo
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- CN101775189A CN101775189A CN201010105132A CN201010105132A CN101775189A CN 101775189 A CN101775189 A CN 101775189A CN 201010105132 A CN201010105132 A CN 201010105132A CN 201010105132 A CN201010105132 A CN 201010105132A CN 101775189 A CN101775189 A CN 101775189A
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- acrylic emulsion
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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 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 by micro emulsion form the successive paint film in water solvent volatilization back, there is not crosslinking reaction, if polymer glass temperature (Tg) is too high, cause the film forming difficulty, 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 by crosslinked film forming method.By 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 polyisocyanates 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 introduce the ketone carbonyl on the polymer macromolecule chain 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 mainly on the ACRYLATE COPOLYMER EMULSION chain, introduce the ketone carbonyl as the functional monomer now with DAAM.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 to carry out radical polymerization by the unsaturated monomer that contains the ketone carbonyl, hydroxyl acrylic monomer, vinyl monomer and fluorine-containing unsaturated monomer in water 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 methacrylic 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 C1-C5 straight chained alkyl that replaces in hydroxyl, the alkyl of preferentially selecting terminal hydroxyl to replace, 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: vinylbenzene, alpha-methyl styrene, vinyl acetate between to for plastic, vinyl cyanide and structural formula
Shown compound, wherein R3 is independently selected from the alkyl of H or C1-C6, and R4 is independently selected from the cycloalkyl of the C3-C10 of the alkyl of H, C1-C20, the replacement of C1-C3 alkyl, hydroxyalkyl, replacement or unsubstitued furyl, replacement or unsubstituted phenmethyl, replacement or unsubstituted glycidyl, replacement or unsubstituted isobornyl or the methoxyl group C1-C6 alkyl ester of C1-C6.
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, methacrylic acid hexafluoro butyl ester, vinylformic acid ten difluoro fat in heptan, methacrylic acid ten difluoro fat in heptan, vinylformic acid ten trifluoro monooctyl esters and methacrylic 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 to obtain fluorine ketone Hydroxylated acrylic resin through copolymerization in water, add ADH and water soluble amino resin then in emulsion.Before adding ADH, need adjust emulsion pH with ammoniacal liquor or amine is 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 reactor is drained air, all add the monomer of emulsifying agent, buffer reagent, deionized water, initiator and 10-20w/w% in the still, high speed dispersion 30 minutes is warming up to 80 ℃, treats after the peak heat release appearance, continue to drip residual monomer and initiator, 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 amines 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, zinc phosphate, strontium chromate and zinc molybdate.Then needn't use above-mentioned rust-stabilising pigment to the less demanding coating of Corrosion Protection.Form according to general coating, the raw material that can use also comprises: tinting pigment, as: iron oxide red, titanium dioxide, carbon black, phthalocyanine blue and zinc oxide etc.; Pigment extender, as: barium sulfate, 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.; Defoamer, 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 solution 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 to add fluorochemical monomer in acrylic resin, 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 made 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 its general notion.
Described " alkyl of C1-C6 ", " alkyl of C1-C20 ", " cycloalkyl of the C3-C10 that the C1-C3 alkyl replaces " 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; Described " 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 that calculating by weight water in the volatile matter accounts for coating more than 70%.
Described " oil paint " is meant that calculating by weight organism in the volatile matter accounts for coating more than 90%.
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 had been described in detail 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 breaking away from the spirit and scope of technical solution 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: all add the initiator of emulsifying agent, buffer reagent, deionized water, 15w/w% and the monomer of 20w/w% in the still, high speed dispersion 30 minutes, be 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 EMULSION
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
Propylene glycol 40 wetting agents 2
Defoamer 2 dimethylethanolamines 2
After mixing, add following component:
Titanium dioxide 250 miniaturization kaolin 58
After the high speed dispersion, under low speed, add following component:
ACRYLIC EMULSION (embodiment 2 preparations, solids constituent 40-45%) 450
Neopentyl glycol mono isobutyrate 14
2-octyl group-4-isothiazole woods-3-ketone (mould inhibitor) 2
Defoamer 6
Tetrapropylammonium acetate benzyl ester (sanitas) 2
Water 30
2.5% hydroxyethyl cellulose aqueous solution 142.4
Propylene glycol 35
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 better than this commercially available water-borne coatings greatly on performance, and similar to the oil paint performance.
Claims (10)
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.
2. ACRYLIC EMULSION according to claim 1 is characterized in that described adipic dihydrazide and the described weight ratio that contains the unsaturated monomer of ketone carbonyl are 0.3: 1 to 3: 1.
3. ACRYLIC EMULSION according to claim 1 is characterized in that the ratio of described fluorine ketone Hydroxylated acrylic resin and described water soluble amino resin solids constituent weight is 3: 1 to 10: 1.
4. ACRYLIC EMULSION according to claim 1 is characterized in that the described unsaturated monomer that contains the ketone carbonyl is selected from one or more monomeric combinations of diacetone-acryloamide(DAA), propenal, Methylacrylaldehyde, methyl vinyl ketone, vinylformic acid acetoxyl group ethyl ester and methacrylic acid acetoxyl group ethyl ester.
5. ACRYLIC EMULSION according to claim 1 is characterized in that described hydroxyl acrylic monomer, 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 C1-C5 straight chained alkyl that replaces in hydroxyl.
6. ACRYLIC EMULSION according to claim 5 is characterized in that described R2 is selected from-CH
2OH ,-CH
2CH
2OH ,-CH
2CH
2CH
3OH ,-CH
2CH
2CH
2CH
3OH or-CH
2CH
2CH
2CH
2CH
3OH.
7. ACRYLIC EMULSION according to claim 1 is characterized in that described vinyl monomer is selected from following one or more monomeric combinations: vinylbenzene, alpha-methyl styrene, vinyl acetate between to for plastic, vinyl cyanide and structural formula
The combination of one or more of shown compound, wherein R3 is independently selected from the alkyl of H or C1-C6, and R4 is independently selected from the cycloalkyl of the C3-C10 of the alkyl of H, C1-C20, the replacement of C1-C3 alkyl, hydroxyalkyl, replacement or unsubstitued furyl, replacement or unsubstituted phenmethyl, replacement or unsubstituted glycidyl, replacement or unsubstituted isobornyl or the methoxyl group C1-C6 alkyl ester of C1-C6.
8. ACRYLIC EMULSION according to claim 1 is characterized in that described fluorine-containing unsaturated monomer is selected from one or more monomeric combinations of trifluorochloroethylene, vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester, vinylformic acid ten difluoro fat in heptan, methacrylic acid ten difluoro fat in heptan, vinylformic acid ten trifluoro monooctyl esters and methacrylic acid ten trifluoro monooctyl esters.
9. 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.
10. one kind with the water-borne coatings of the described ACRYLIC EMULSION of one of claim 1-9 as main film forming matter preparation.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN109652007A (en) * | 2018-12-06 | 2019-04-19 | 成都硅宝科技股份有限公司 | Impervious oily bi-component silicone sealant of one kind 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0629657A3 (en) * | 1993-06-14 | 1997-03-26 | Ajinomoto Kk | Crosslinkable resin composition in aqueous dispersion form. |
| 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 |
| CN101560353A (en) * | 2009-05-05 | 2009-10-21 | 陕西科技大学 | Method for preparing water-resistant and solvent-resistant acrylics coating agent |
-
2010
- 2010-02-03 CN CN2010101051322A patent/CN101775189B/en not_active Expired - Fee Related
Cited By (7)
| 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 |
| CN109652007A (en) * | 2018-12-06 | 2019-04-19 | 成都硅宝科技股份有限公司 | Impervious oily bi-component silicone sealant of one kind and preparation method thereof |
| 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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