CN111777950A - Water paint drier - Google Patents
Water paint drier Download PDFInfo
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- CN111777950A CN111777950A CN202010660959.3A CN202010660959A CN111777950A CN 111777950 A CN111777950 A CN 111777950A CN 202010660959 A CN202010660959 A CN 202010660959A CN 111777950 A CN111777950 A CN 111777950A
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- water
- based paint
- drier
- coating
- oxide
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 239000003973 paint Substances 0.000 title claims abstract description 142
- 238000000576 coating method Methods 0.000 claims abstract description 111
- 239000011248 coating agent Substances 0.000 claims abstract description 105
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 41
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 40
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 27
- 239000008139 complexing agent Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 21
- QUGUZZBEIJGVNX-UHFFFAOYSA-L azanium molybdenum(2+) phosphate Chemical compound [NH4+].P(=O)([O-])([O-])[O-].[Mo+2] QUGUZZBEIJGVNX-UHFFFAOYSA-L 0.000 claims abstract description 15
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 48
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 26
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 18
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 13
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 13
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 13
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 13
- 239000011787 zinc oxide Substances 0.000 claims description 13
- 230000003472 neutralizing effect Effects 0.000 claims description 12
- 230000000536 complexating effect Effects 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- OJDJHGIXNZPZFD-UHFFFAOYSA-N ethyl dihydrogen diphosphate Chemical compound CCO[P@](O)(=O)OP(O)(O)=O OJDJHGIXNZPZFD-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000001502 supplementing effect Effects 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 49
- 238000002360 preparation method Methods 0.000 abstract description 23
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000003960 organic solvent Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- 238000004945 emulsification Methods 0.000 abstract description 9
- 230000009471 action Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000003595 mist Substances 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 description 32
- 229920005749 polyurethane resin Polymers 0.000 description 24
- 239000000463 material Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 239000002184 metal Substances 0.000 description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- 229910052726 zirconium Inorganic materials 0.000 description 9
- LFLCPWCZNJYHRD-UHFFFAOYSA-N C(C)P(=O)(O)OP(=O)O Chemical compound C(C)P(=O)(O)OP(=O)O LFLCPWCZNJYHRD-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011527 polyurethane coating Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052747 lanthanoid Inorganic materials 0.000 description 4
- 150000002602 lanthanoids Chemical class 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000007605 air drying Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000010410 layer Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; DRIERS (SICCATIVES); TURPENTINE
- C09F9/00—Compounds to be used as driers (siccatives)
Abstract
The invention provides a water-based paint drier which comprises a metal oxide, ammonium phosphomolybdate, a monobasic acid, an ammonia neutralizer, a coordination complexing agent and water. And provides a preparation method of the water-based paint drier. The water-based paint drier utilizes the physical and chemical action of emulsification and coordination to prepare metal elements into a system completely compatible with water, can be added at any stage in the water-based paint manufacturing process, is easily dissolved in resin after water is volatilized, solves the problems of slow drying and drying loss of the water-based paint, and obviously improves the compatibility with the water-based paint; the ammonium molybdenum phosphate is adopted, so that the salt mist resistance and the water resistance of the dried coating are effectively improved; the coating has good dispersibility in the water-based paint, so that the coating formed by drying the water-based paint has smooth appearance and good glossiness; which can effectively improve the drying speed of the water paint coating. In the preparation method of the water-based paint drier, water is used for replacing an organic solvent, so that the use of the organic solvent is reduced, and the water-based paint drier is more environment-friendly.
Description
Technical Field
The invention belongs to the technical field of coating, and particularly relates to a water-based coating drier.
Background
With the continuous improvement of environmental protection laws and regulations, the control force on environmental protection is continuously increased, and the water-based paint is comprehensively replacing the oil-based paint. The single-component air-dried coating is a branch of anticorrosive coatings with the widest application and the largest dosage, and the coating can enable water-based air-dried resin in the coating to quickly react and crosslink to form a coating with anticorrosive performance by virtue of the catalytic action of a plurality of metal examples. The conventional drier used for the single-component water-based air-drying coating is naphthenic acid or isooctanoate of metals such as cobalt, zirconium and zinc. Such a drier must be uniformly dispersed in an aqueous air-drying paint under the condition that a sufficient amount of organic solvent exists in the system, and if the drier is directly added into an aqueous system, problems such as precipitation, reduction of glossiness and reduction of catalytic efficiency may be caused, and the prepared paint is easy to separate out in the storage and drying processes.
Conventional siccatives have problems such as poor dispersion or segregation in the aqueous coating material, which leads to loss of dryness or poor appearance of the aqueous coating material. That is, conventional siccatives have poor compatibility with aqueous coatings. Moreover, the effect of the drier is strongly dependent on the composition of the coating and no drier has been found which satisfies the better drying performance for all water-borne coatings.
Disclosure of Invention
One of the purposes of the invention is to overcome the defects in the prior art and provide the water-based paint drier which can be added at any stage in the preparation process of the water-based paint, has good compatibility with the water-based paint and good drying performance and has universality for the water-based paint.
The purpose of the invention is realized by the following technical scheme:
a water paint drier comprises metal oxide, ammonium molybdenum phosphate, monobasic acid, ammonia neutralizer, coordination complexing agent and water.
In one embodiment, the catalyst comprises, by mass, 5% -30% of metal oxide, 1% -10% of ammonium molybdenum phosphate, 10% -30% of monobasic acid, 5% -15% of ammonia neutralizer, 10% -25% of coordination complexing agent and the balance of water.
In one embodiment, the metal oxide includes cobalt oxide, zirconium oxychloride, manganese dioxide, calcium oxide, zinc oxide, and lanthanum oxide.
In one embodiment, the metal oxide comprises, by mass, 1% to 10% of cobalt oxide, 1% to 10% of zirconium oxychloride, 1% to 5% of manganese dioxide, 1% to 5% of calcium oxide, 1% to 5% of zinc oxide, and 1% to 5% of lanthanum oxide.
In one embodiment, the monobasic acid is nitric acid.
In one embodiment, the ammonia neutralizing agent is triethylamine or dimethylethanolamine.
In one embodiment, the complexing agent is tridentate ethyl diphosphate.
A preparation method of a water-based paint drier comprises the following steps:
dissolving: putting metal oxide into a reaction kettle, adding enough water, and dropwise adding monoacid while stirring;
neutralizing: under the heating condition, dropwise adding an ammonia neutralizing agent into the reaction kettle while stirring, and adjusting the pH value to 7-8;
complexing: adding a coordination complexing agent into the reaction kettle, stirring until the coordination complexing agent is completely dissolved and transparent, and supplementing residual water;
and (4) checking: and (5) cooling and checking.
In one embodiment, the temperature of the dissolution process in the dissolution step is 70 ℃ to 85 ℃.
In one embodiment, ammonium molybdenum phosphate is added before adjusting the pH and stirred until dissolution is complete in the neutralization step.
Compared with the prior art, the invention has at least the following advantages:
1. the water-based paint drier disclosed by the invention utilizes the physical and chemical actions of emulsification and coordination to prepare metal elements into a system completely compatible with water, can be added at any stage in the water-based paint manufacturing process, is easily dissolved in resin after water is volatilized, solves the problems of slow drying and drying loss of the water-based paint, and obviously improves the compatibility with the water-based paint;
2. the water-based paint drier has good dispersibility in water-based paint, so that a coating formed by drying the water-based paint has smooth appearance and good glossiness;
3. the water-based paint drier adopts the ammonium molybdenum phosphate, so that the salt mist resistance and the water resistance of a dried coating are effectively improved;
4. the water-based paint drier can effectively improve the drying speed of a water-based paint coating;
5. the water-based paint drier disclosed by the invention has the advantages that the water replaces an organic solvent, so that the use of the organic solvent is reduced, and the water-based paint drier is more environment-friendly;
6. the addition mode, temperature, stirring speed and time of all the substances are controlled, so that the water-based paint drier with good emulsification and complexing effects can be obtained;
7. the preparation method of the water-based paint drier has simple steps and is easy to operate.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a flow chart illustrating the steps of a method for preparing a water-based paint drier according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not represent the only embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention relates to a water-based paint drier which comprises metal oxide, ammonium molybdenum phosphate, monobasic acid, an ammonia neutralizer, a coordination complexing agent and water.
In one embodiment, the aqueous coating drier comprises a metal oxide, ammonium molybdenum phosphate, a monobasic acid, an ammonia neutralizer, a complexing agent, and water. The metal oxide is dissolved in water, the metal element is made into a system completely compatible with water by utilizing the physical and chemical actions of emulsification and coordination, and the process needs the assistance of unit acid and ammonia neutralizer so as to achieve the optimal complexing and emulsifying effects.
In the water-based paint drier, the metal elements are prepared into a system completely compatible with water by utilizing the physical and chemical action of emulsification and coordination, the metal elements can be added at any stage in the water-based paint manufacturing process, and the metal elements are easily dissolved in resin after water is volatilized, so that the problems of slow drying and drying loss of the water-based paint are solved, and the compatibility with the water-based paint is obviously improved. The compatibility of the drier and the water-based paint can be effectively improved by the matching of the metal oxide, and the compatibility of the drier and the water-based paint is further improved by adding the ammonium molybdenum phosphate. The coating has good dispersibility in the water-based paint, so that the coating formed by drying the water-based paint has smooth appearance and good glossiness. The ammonium molybdenum phosphate is adopted, so that the salt mist resistance and the water resistance of the dried coating are effectively improved. Which can effectively improve the drying speed of the water paint coating. The water replaces the organic solvent, so that the use of the organic solvent is reduced, and the environment is protected.
Specifically, the emulsification and coordination process comprises the following steps: the metal ions and the coordination complexing agent are subjected to a complexing reaction, and the generated complex further forms an emulsifier with water. Further, the metal oxide is not limited to only one metal oxide, and may be a mixture of a plurality of metal oxides, and may also contain an oxide of a rare earth element.
Particularly, the ammonium molybdenum phosphate has good compatibility with the water-based paint, can form a water-resistant film, and can improve the water resistance and the salt fog resistance of the coating. Furthermore, the aqueous drier has the same characteristics with any aqueous paint, is suitable for various aqueous paints, and has universality.
In one embodiment, the catalyst comprises, by mass, 5% -30% of metal oxide, 1% -10% of ammonium molybdenum phosphate, 10% -30% of monobasic acid, 5% -15% of ammonia neutralizer, 10% -25% of coordination complexing agent and the balance of water. After 5-30% of metal oxide is dissolved in 10-30% of monobasic acid and water, 5-15% of ammonia neutralizer is added for neutralization, and then the metal oxide and 10-25% of coordination complexing agent form a complex compound, and the complex compound is further emulsified with water, so that the unlimited water-soluble water-based paint drier can be obtained. When the content of the metal oxide is 5-30%, the drying effect of the water-based paint can be effectively improved.
In one embodiment, the metal oxide includes cobalt oxide, zirconium oxychloride, manganese dioxide, calcium oxide, zinc oxide, and lanthanum oxide. Cobalt oxide, zirconium oxychloride, manganese dioxide, calcium oxide, zinc oxide and lanthanum oxide are matched to form a multi-metal oxide mixture, wherein the metal oxides have the effect of mutual promotion in the aspect of a water-based paint drier, so that the water-based paint is consistent in surface and inside drying speed, and wrinkling is avoided. And the cobalt, zirconium, zinc, manganese, zirconium and lanthanide rare earth elements are successfully prepared into a system completely compatible with water by utilizing the physical and chemical action of emulsification and coordination, and can be added at any stage in the process of preparing the water-based paint, so that the compatibility of the drier and the water-based paint is obviously improved. The metal oxides are used in a matched manner, so that the dispersibility of the drier in the water-based paint is effectively improved, and a coating formed by drying the water-based paint is smooth in appearance and good in glossiness.
In one embodiment, the metal oxide comprises, by mass, 1% to 10% of cobalt oxide, 1% to 10% of zirconium oxychloride, 1% to 5% of manganese dioxide, 1% to 5% of calcium oxide, 1% to 5% of zinc oxide, and 1% to 5% of lanthanum oxide. The matching of the above oxides is used, the mutual promotion effect among all the substances can be effectively stimulated, most obviously, the drying speed of the inner layer and the surface layer can be effectively improved, the surface condition of the coating is effectively improved, the wrinkling and the silk streak elimination are overcome, and the effect is better than that when all the metal oxides are used independently. Furthermore, the dispersibility of the water-based paint can be improved, and the water-based paint is prevented from generating precipitation.
In one embodiment, the monobasic acid is nitric acid. The nitric acid can promote the dissolution of metal oxide, and the formed lanthanum nitrate has an anticorrosion effect, so that the anticorrosion property of the aqueous drier can be improved, and the gloss of the paint can be improved.
The lanthanum nitrate can improve the bonding strength of the coating and improve the adsorbability of the coating. And the porosity of the coating can be reduced to improve the corrosion resistance of the coating, and lanthanum nitrate has good compatibility with the water-based paint through complexing and emulsifying with a coordination complex, so that the sedimentation is avoided, and the stability of the water-based paint coating is effectively improved. And lanthanum nitrate has the effect of promoting the drying performance of other metal oxides, so that the water-based paint drying agent has better drying performance.
In one embodiment, the ammonia neutralizing agent is triethylamine or dimethylethanolamine. The ammonia neutralizer is used for adjusting the pH value of the solution, so that the metal oxide and the coordination complex can achieve the optimal coordination and emulsification effects.
In one embodiment, the complexing agent is tridentate ethyl diphosphate. The complex of the cobalt, zirconium, zinc, manganese, zirconium and lanthanide rare earth elements is added at any stage in the process of preparing the water-based paint, so that the compatibility of the drier and the water-based paint is obviously improved. And the trident ethyl diphosphate and phenyl and aldehyde groups in the water-based paint can generate a crosslinking effect, so that the drying speed of the coating can be further increased.
The invention relates to a preparation method of a water-based paint drier, which comprises the following steps: dissolving: under the heating condition, the metal oxide is put into a reaction kettle, sufficient water is added, and the monoacid is dropwise added while stirring. Neutralizing: under another heating condition, dropwise adding an ammonia neutralizing agent into the reaction kettle while stirring, and adjusting the pH value to 7-8. Complexing: and adding a coordination complexing agent into the reaction kettle, stirring until the coordination complexing agent is completely dissolved and transparent, and supplementing residual water. And (4) checking: and (5) cooling and checking.
In the preparation method of the water-based paint drier, the addition modes of all the substances are set, and the temperature, the stirring speed and the time are controlled, so that the water-based paint drier with good emulsification and complexation effects can be obtained. And the preparation method has simple steps and is easy to operate.
It should be particularly noted that, in the preparation method of the water-based paint drier of the present invention, water is used to replace an organic solvent, and compared with the conventional water-based paint drier, the water-based paint drier can be uniformly dispersed only in the presence of a sufficient amount of organic solvent in the system, such that the use of organic solvent can be effectively reduced, the environmental pollution can be reduced, and the water-based paint drier is green and environment-friendly. The water-based paint drier prepared by the preparation method of the water-based paint drier is added into the water-based paint, has good dispersibility, cannot be precipitated in the storage and drying processes, and does not influence the use of the water-based paint.
It should be noted that, in one embodiment, the ratio of the used substances is, in mass percent, specifically: 1-10% of cobalt oxide, 1-10% of zirconium oxychloride, 1-5% of manganese dioxide, 1-5% of calcium oxide, 1-5% of zinc oxide, 1-5% of lanthanum oxide, 1-10% of ammonium phosphomolybdate, 10-30% of monobasic acid, 5-15% of ammonia neutralizer, 10-25% of trifurcate ethyl diphosphate and the balance of water. The following steps S100 to S400 refer to the present example for the mass percentages of the respective substances.
In one embodiment, referring to fig. 1, a method for preparing a water-based paint drier includes the following steps:
s100, dissolving: adding metal oxide into a reaction kettle, adding enough water, and dropwise adding monoacid while stirring. In one embodiment, 1-10% of cobalt oxide, 1-10% of zirconium oxychloride, 1-5% of manganese dioxide, 1-5% of calcium oxide, 1-5% of zinc oxide and 1-5% of lanthanum oxide are added into a reaction kettle according to mass percentage, 2/3 of the rest water is added, nitric acid is dropwise added while stirring under heating conditions, the stirring speed is controlled to be 80-120 r/min, stirring is carried out for 5-10 min, and the dissolved solution is cooled to normal temperature. In the above step S100, after adding nitric acid and water, the stirring speed and the stirring time are controlled so that the metal oxide is completely dissolved and further oxidation of the metal ions of the metal oxide is prevented.
S200, neutralization: and (3) under a heating condition, dropwise adding an ammonia neutralizing agent into the reaction kettle while stirring, and adjusting the pH value to 7-8. In one embodiment, the heating condition is 25-35 ℃, 5-15% of ammonia neutralizer is dropwise added into the reaction kettle while stirring, and the pH value is adjusted to 7-8. In the above step S200, the metal oxide and the coordination complex can be optimally coordinated and emulsified.
S300, complexing: and adding a coordination complexing agent into the reaction kettle, stirring until the coordination complexing agent is completely dissolved and transparent, and supplementing residual water. In one embodiment, 10-25% of trident ethyl diphosphate is added into a reaction kettle, the stirring speed is controlled to be 600-1000 r/min, the mixture is stirred until the mixture is completely dissolved and transparent, 1/3 residual water is supplemented, and the stirring is continued for 2-3 min. In the step S300, the stirring speed is controlled, the complexing, the emulsifying and the addition of the cobalt, the zirconium, the zinc, the manganese, the zirconium and the lanthanide rare earth elements are realized, a system completely compatible with water is prepared, and the system can be added at any stage in the water-based paint manufacturing process, so that the compatibility of the water-based paint drier and the water-based paint is obviously improved.
In the preparation method of the water-based paint drier, water is used for replacing an organic solvent, so that the use of the organic solvent is reduced, and the environment is protected.
S400, checking: and (5) cooling and checking. The prepared water-based paint drier needs to be detected to check whether the coating can be dried quickly or not, and the dried coating has smooth appearance and good glossiness, so that the quality of the water-based paint drier product can be improved.
In one embodiment, S400 includes the steps of:
s410, adding 3-6 wt% of water-based paint drier according to the weight percentage, and fully and uniformly stirring. The use amount of the water-based paint drier is small, the required drying requirement can not be met, and the problems of raw material waste and influence on the caking property of the water-based polyurethane resin paint caused by large addition amount can be avoided.
In step S410, 0.5 to 3 wt% of the drier is calculated based on the weight of the polyurethane resin, and the drier is added in an amount of 2 to 5 wt% in order to avoid waste of the drier for the aqueous coating material and reduce the influence on the adhesion of the aqueous polyurethane resin coating material. It should be explained that, the content of the drier is large, and the polyurethane resin, the cross-linking agent, the auxiliary agent and other components in the aqueous polyurethane coating are diluted, so that the cohesiveness of the aqueous polyurethane resin coating is reduced, and the service performance of the aqueous polyurethane resin coating is influenced.
And S420, quickly coating the metal plate and starting timing at the same time. The waterborne polyurethane resin coating containing 3-6 wt% of the waterborne coating drier is quickly coated on a metal plate, and timing is started at the same time to ensure that the drying time of the waterborne polyurethane resin coating catalyzed by the waterborne coating drier can be accurately obtained.
The aqueous urethane resin coating material containing the aqueous coating material drier can be quickly applied to the metal plate by the application roller, and the time for drying the aqueous urethane resin coating material by the catalysis, in which the aqueous coating material drier can be accurately obtained, can be ensured.
And S430, detecting the appearance of the aqueous polyurethane resin coating after drying.
In one of the examples, visual inspection was used to calculate the apparent flatness of the aqueous polyurethane resin coating. And (4) timing by using a Back-Koller drying time recorder to obtain the drying time of the waterborne polyurethane resin coating. The gloss of the aqueous polyurethane resin coating was determined using the Erichsen method.
In one embodiment, the temperature of the dissolution process in the dissolution step is 70 ℃ to 85 ℃. The dissolution temperature is 70-85 ℃, the dissolution of the metal oxide can be accelerated, and the further oxidation of the metal oxide can be avoided.
In one embodiment, ammonium molybdenum phosphate is added before adjusting the pH and stirred until dissolution is complete in the neutralization step. The pH value of the complexing and emulsifying agent needs to be strictly controlled, so that the cobalt, zirconium, zinc, manganese, zirconium and lanthanide rare earth elements are prepared into a system completely compatible with water, the complexing and emulsifying agent can be added at any stage in the process of preparing the water-based paint, the compatibility of the drier and the water-based paint is obviously improved, and therefore, ammonium molybdenum phosphate needs to be added before the pH value is adjusted, and the condition that the pH value cannot meet the requirement is avoided.
The following is an example section
Example 1
The water paint drier comprises 2% of cobalt oxide, 3% of zirconium oxychloride, 2% of manganese dioxide, 2% of calcium oxide, 2% of zinc oxide, 0.5% of lanthanum oxide, 3% of ammonium phosphomolybdate, 20% of monobasic acid, 10% of ammonia neutralizer, 20% of trident ethyl diphosphate and the balance of water.
Example 2
The water paint drier comprises 1% of cobalt oxide, 1% of zirconium oxychloride, 1% of manganese dioxide, 1% of calcium oxide, 1% of zinc oxide, 1% of lanthanum oxide, 1% of ammonium phosphomolybdate, 10% of monobasic acid, 5% of ammonia neutralizer, 10% of trident ethyl diphosphonic acid and the balance of water.
Example 3
The water paint drier comprises 10% of cobalt oxide, 10% of zirconium oxychloride, 5% of manganese dioxide, 5% of calcium oxide, 5% of zinc oxide, 5% of lanthanum oxide, 10% of ammonium phosphomolybdate, 30% of monobasic acid, 15% of ammonia neutralizer, 25% of trifurcate ethyl diphosphate and the balance of water.
Example 4
The water paint drier comprises 5% of cobalt oxide, 5% of zirconium oxychloride, 2% of manganese dioxide, 2% of calcium oxide, 2% of zinc oxide, 2% of lanthanum oxide, 3% of ammonium phosphomolybdate, 25% of monobasic acid, 10% of ammonia neutralizer, 20% of trident ethyl diphosphonic acid and the balance of water.
Example 5
The preparation method of the water-based paint drier comprises the following steps:
s110, putting metal oxide into a reaction kettle at the temperature of 70 ℃, adding enough water, dropwise adding monobasic acid while stirring, controlling the stirring speed to be 120r/min, stirring for 5min, and cooling the dissolved solution to normal temperature;
s210, dropwise adding an ammonia neutralizing agent into the reaction kettle while stirring at the temperature of 25 ℃, and adjusting the pH value to 7-8;
s310, adding the trident ethyl diphosphonic acid into the reaction kettle, controlling the stirring speed to be 1000r/min, stirring until the trident ethyl diphosphonic acid is completely dissolved and transparent, supplementing the residual water, and continuing stirring for 2 min.
Example 6
The preparation method of the water-based paint drier comprises the following steps:
s120, putting the metal oxide into a reaction kettle at the temperature of 80 ℃, adding enough water, dropwise adding the monobasic acid while stirring, controlling the stirring speed to be 100r/min, stirring for 8min, and cooling the dissolved solution to normal temperature;
s220, dropwise adding an ammonia neutralizing agent into the reaction kettle while stirring at the temperature of 30 ℃, and adjusting the pH value to 7-8;
s320, adding the trident ethyl diphosphonic acid into the reaction kettle, controlling the stirring speed to be 800r/min, stirring until the trident ethyl diphosphonic acid is completely dissolved and transparent, supplementing the residual water, and continuing stirring for 3 min.
Example 7
The preparation method of the water-based paint drier comprises the following steps:
s130, putting metal oxide into a reaction kettle at the temperature of 85 ℃, adding enough water, dropwise adding unit acid while stirring, controlling the stirring speed to be 80r/min, stirring for 10min, and cooling the dissolved solution to normal temperature;
s230, dropwise adding an ammonia neutralizing agent into the reaction kettle while stirring at the temperature of 35 ℃, and adjusting the pH value to 7-8;
s330, adding trident ethyl diphosphonic acid into the reaction kettle, controlling the stirring speed to be 600r/min, stirring until the trident ethyl diphosphonic acid is completely dissolved and transparent, supplementing the residual water, and continuing stirring for 3 min.
The water-based paint driers of examples 1 to 4 were prepared by the following preparation methods of examples 5 to 7, respectively, and the following detection methods were used to obtain detection data:
detection method 1
The detection method 1S411 comprises the steps of adding 3 wt% of water-based paint drier according to the weight percentage, and fully and uniformly stirring;
s421, quickly coating the coating on a metal plate, starting timing at the same time, and timing by using a Back-Koller drying time recorder to obtain the drying time of the waterborne polyurethane resin coating;
and S431, detecting the appearance of the aqueous polyurethane resin coating after drying, measuring the luster of the aqueous polyurethane resin coating by using an Erichsen method, and visually calculating the appearance flatness of the aqueous polyurethane resin coating.
Detection method 2
S412, adding 4 wt% of water-based paint drier according to the weight percentage, and fully and uniformly stirring;
s422, quickly coating the coating on a metal plate, starting timing at the same time, and timing by using a Back-Koller drying time recorder to obtain the drying time of the waterborne polyurethane resin coating;
and S432, after drying, detecting the appearance of the aqueous polyurethane resin coating, measuring the luster of the aqueous polyurethane resin coating by using an Erichsen method, and visually calculating the appearance flatness of the aqueous polyurethane resin coating.
Detection method 3
S413, adding 5 wt% of a water-based paint drier according to the weight percentage, and fully and uniformly stirring;
s423, quickly coating the coating on a metal plate, starting timing at the same time, and timing by using a Back-Koller drying time recorder to obtain the drying time of the waterborne polyurethane resin coating;
and S433, detecting the appearance of the aqueous polyurethane resin coating after drying, measuring the luster of the aqueous polyurethane resin coating by using an Erichsen method, and visually calculating the appearance flatness of the aqueous polyurethane resin coating.
In addition, during the implementation of the detection, the aqueous paint drier needs to be brought to room temperature and treated, and if the temperature is higher, the time for the aqueous paint drier to dry the aqueous paint is affected, the drying performance of the aqueous paint drier is affected, the drying time of the aqueous paint drier on the aqueous paint cannot be accurately obtained, and when the aqueous paint containing the aqueous paint drier of the invention is coated on a solid surface, the drying of the aqueous paint is accelerated, so that the coating surface is dried earlier, wrinkles are generated, and the appearance of the coating is affected.
The preparation method of the water-based paint drier and the detection of the water-based paint drier are as follows:
the detection purpose is as follows:
1. detecting the service performance of the water-based paint drier obtained by the preparation method of the water-based paint drier;
2. the service performance of the water-based paint drier is detected.
Detection 1: (detection method for detection purpose 1)
The aqueous coating material drier of example 1 was prepared using the preparation methods of the aqueous coating material drier of examples 5 to 7, and the above-described operations were repeated three times by performing the tests by the test methods 1 to 3, respectively.
And (3) detection results:
TABLE 1 Performance test results (hereinafter, three replicates, the average of three replicates)
It is noted that gloss is the ability of the coating surface to reflect light incident thereon in one direction, with higher reflectance giving higher gloss. Coating gloss is one of the main performance indicators for identifying the appearance quality of a coating.
The flatness detection criteria are as follows: smooth and flat is A, invisible and visible unevenness, the appearance influence is B, visible unevenness, the appearance influence is C, obvious and visible unevenness, and the appearance influence is D.
In the detection methods 1 to 3, the thickness of the coating formed by coating the aqueous polyurethane coating on the metal plate is 0.5 cm.
From the test results in table 1, it can be seen that the preparation method of the water-based paint drier in examples 5 to 7 is used to prepare the water-based paint drier in example 1, the drying time obtained after the detection by the detection methods 1 to 3 is 4 to 6 minutes, and the coating obtained is flat in appearance and has a glossiness of 60 to 80% without being coated for several times, which indicates that the water-based paint drier has a good drying effect, and the coating with a flat appearance can be obtained by coating once, and the surface of the coating added with the water-based paint drier has a good glossiness. Compared with the water-based paint drier on the market, the water-based paint drier has more excellent drying performance and coating surface appearance on the water-based paint coating. The water-based paint drier prepared by the method has more excellent drying performance and coating surface appearance.
And (3) detection 2: (detection method for detection purpose 1)
The aqueous coating material driers of examples 1 to 4 were prepared using the preparation method of the aqueous coating material driers of example 7, and the detection methods 1 to 3 were used to perform the detection, and the above-described operations were repeated three times.
And (3) detection results:
TABLE 2 Performance test results (hereinafter, three replicates, the average of three replicates)
It is noted that gloss is the ability of the coating surface to reflect light incident thereon in one direction, with higher reflectance giving higher gloss. Coating gloss is one of the main performance indicators for identifying the appearance quality of a coating.
The flatness detection criteria are as follows: smooth and flat is A, invisible and visible unevenness, the appearance influence is B, visible unevenness, the appearance influence is C, obvious and visible unevenness, and the appearance influence is D.
In the detection methods 1 to 3, the thickness of the coating formed by coating the aqueous polyurethane coating on the metal plate is 0.2 cm.
From the test results in table 2, it can be seen that the preparation methods of the water-based paint driers in example 7 are used to prepare the water-based paint driers in examples 1 to 4, the drying time obtained after the detection by the detection methods 1 to 3 is 2 minutes, and the obtained coatings are smooth in appearance and have gloss of more than 80% without being coated for several times, which indicates that the water-based paint driers of the present invention have good drying effect, and the coatings with smooth appearance can be obtained by one-time coating, and the coatings with the water-based paint driers of the present invention have good surface gloss. Compared with the water-based paint drier on the market, the water-based paint drier has more excellent drying performance and coating surface appearance on the water-based paint coating. The water-based paint drier has more excellent drying performance and coating surface appearance.
And (3) detection: (detection method for detection purpose 1)
The precipitation test was performed on the aqueous polyurethane coating containing the aqueous coating drier of the present invention, and the aqueous coating drier of examples 1 to 4 was prepared by using the preparation methods of the aqueous coating driers of examples 5 to 7, respectively, and the above operations were repeated three times.
And (3) detection results:
TABLE 3 Performance test results (hereinafter, three replicates, the average of three replicates)
The operation of the precipitation detection is as follows: the aqueous polyurethane paint of each aqueous paint drier is placed at room temperature for 10 days, and then is irradiated by a light pen to observe whether precipitation is found.
From the test results in table 3, it is understood that the precipitation test was performed on the aqueous polyurethane coating material containing the aqueous coating material drier of the present invention, in which the aqueous coating material drier of examples 1 to 4 prepared by the preparation method of the aqueous coating material drier of examples 5 to 7, respectively, and no precipitate was observed at the bottom. The water-based paint drier has good dispersibility in water-based paint, high stability and no precipitation.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The water-based paint drier is characterized by comprising metal oxide, ammonium phosphomolybdate, monobasic acid, ammonia neutralizer, coordination complexing agent and water.
2. The aqueous paint drier according to claim 1, characterized by comprising 5-30% of metal oxide, 1-10% of ammonium phosphomolybdate, 10-30% of monobasic acid, 5-15% of ammonia neutralizer, 10-25% of coordination complexing agent and the balance of water by mass percent.
3. The aqueous coating drier according to claim 1, wherein the metal oxides include cobalt oxide, zirconium oxychloride, manganese dioxide, calcium oxide, zinc oxide, and lanthanum oxide.
4. The aqueous paint drier according to claim 1, wherein the metal oxide comprises, by mass, 1% to 10% of cobalt oxide, 1% to 10% of zirconium oxychloride, 1% to 5% of manganese dioxide, 1% to 5% of calcium oxide, 1% to 5% of zinc oxide, and 1% to 5% of lanthanum oxide.
5. The aqueous coating drier according to claim 1, wherein the monobasic acid is nitric acid.
6. The aqueous coating drier according to claim 1, wherein the ammonia neutralizer is triethylamine or dimethylethanolamine.
7. The aqueous coating drier according to claim 1, wherein the complexing agent is tridentate ethyl diphosphate.
8. A method for preparing an aqueous paint drier according to any of the claims 1 to 9, characterized in that it comprises the following steps:
dissolving: putting metal oxide into a reaction kettle, adding enough water, and dropwise adding monoacid while stirring;
neutralizing: under the heating condition, dropwise adding an ammonia neutralizing agent into the reaction kettle while stirring, and adjusting the pH value to 7-8;
complexing: adding a coordination complexing agent into the reaction kettle, stirring until the coordination complexing agent is completely dissolved and transparent, and supplementing residual water;
and (4) checking: and (5) cooling and checking.
9. The method for preparing the aqueous paint drier according to claim 8, wherein the temperature of the dissolving process in the dissolving step is 70 ℃ to 85 ℃.
10. The method for preparing the aqueous paint drier as claimed in claim 8, wherein in the neutralization step, the ammonium molybdenum phosphate is added before the pH is adjusted, and the solution is stirred until the ammonium molybdenum phosphate is completely dissolved.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316207A (en) * | 2021-12-22 | 2022-04-12 | 南雄市佳明化工有限公司 | Polyurethane drier, preparation method thereof and curing material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018015333A1 (en) * | 2016-07-19 | 2018-01-25 | Allnex Austria Gmbh | Drier compositions for alkyd resins |
| CN109321027A (en) * | 2018-09-21 | 2019-02-12 | 合肥市君科合成材料有限公司 | A kind of novel aqueous drier and preparation method thereof |
-
2020
- 2020-07-10 CN CN202010660959.3A patent/CN111777950A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018015333A1 (en) * | 2016-07-19 | 2018-01-25 | Allnex Austria Gmbh | Drier compositions for alkyd resins |
| CN109321027A (en) * | 2018-09-21 | 2019-02-12 | 合肥市君科合成材料有限公司 | A kind of novel aqueous drier and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 中国腐蚀与防护学会 主编: "《腐蚀科学与防腐蚀工程技术新进展 中国腐蚀与防护学会成立二十周年论文集》", 31 October 1999, 化学工业出版社 * |
| 北京师范大学化学系无机化学教研室编: "《简明化学手册》", 30 June 1980, 北京出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316207A (en) * | 2021-12-22 | 2022-04-12 | 南雄市佳明化工有限公司 | Polyurethane drier, preparation method thereof and curing material |
| CN114316207B (en) * | 2021-12-22 | 2024-04-16 | 南雄市佳明化工有限公司 | Polyurethane drier, preparation method thereof and curing material |
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