CN102174146A - Aqueous acrylic resin dispersion dried at normal temperature and preparation method and application thereof - Google Patents
Aqueous acrylic resin dispersion dried at normal temperature and preparation method and application thereof Download PDFInfo
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- CN102174146A CN102174146A CN 201110047445 CN201110047445A CN102174146A CN 102174146 A CN102174146 A CN 102174146A CN 201110047445 CN201110047445 CN 201110047445 CN 201110047445 A CN201110047445 A CN 201110047445A CN 102174146 A CN102174146 A CN 102174146A
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- 239000006185 dispersion Substances 0.000 title claims abstract description 58
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 40
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 239000011248 coating agent Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- -1 acrylic ester Chemical class 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000013530 defoamer Substances 0.000 claims description 13
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000007605 air drying Methods 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 10
- 230000008719 thickening Effects 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 238000002242 deionisation method Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012855 volatile organic compound Substances 0.000 abstract 2
- 230000000887 hydrating effect Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 23
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000013409 condiments Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
The invention relates to aqueous acrylic resin dispersion dried at normal temperature and a preparation method and application thereof, in particular to aqueous acrylic resin dispersion dried at normal temperature and high-performance waterborne coating prepared from the aqueous acrylic resin dispersion and used for metal surface protection. The preparation method of the acrylic resin dispersion dried at normal temperature comprises the following steps: A, preparing acrylic resin prepolymer, and B, hydrating the acrylic resin prepolymer. The invention also relates to a method for preparing the high-performance waterborne coating dried at normal temperature and used for metal surface protection from the aqueous acrylic resin dispersion. The coating process is completed at low and even normal temperature, the emission of VOC (volatile organic compounds) is restricted during automobile costing, the purpose of saving energy and reducing emissions are realized, and the high-performance waterborne coating is convenient to popularize and apply.
Description
Technical field
The present invention relates to a kind of protecting metallic surface with high-performance water-based coating condiments, specifically a kind of Air drying type acrylic dispersion and preparation thereof and the high-performance water-based coating of protecting metallic surface that makes with this dispersion.
Background technology
In the coating metal surfaces process, organic solvent type metal substrate environmental pollution is serious, the Water-borne modification of high-performance water-based metal substrate is very urgent, by introducing special carboxylic monomer, develop the substrate adhesion excellence, suppress to return the well behaved high-performance water-based coating of rust simultaneously and have important practical significance.
Along with the high speed development of Chinese industrial, the coating that present domestic protecting metallic surface is used is based on solvent system, and wherein a large amount of VOC pollution on the environments are on the rise, and the environmental issue in the application is put on agenda.Relevant laws and regulations have been worked out in succession with restriction coating VOC quantity discharged in countries in the world.For example requirement in the clean air rules that nineteen ninety-five come into force of Germany, during spraying application, the VOC quantity discharged is not more than 35g/ ㎡, and traditional about 125g/ ㎡ of solvent based coating VOC quantity discharged.State Bureau of Environmental Protection has been issued " application cleaner production standard " in August, 2008, for the first time VOC quantity discharged in the application has been made concrete regulation.In order to reach environmental requirement, the protecting metallic surface coating just develops in hydrotropismsization, high-solid level and powder coating direction, wherein the Water-borne modification technology be the most effective by way of one of.
After the present most popular solvent-borne type protecting metallic surface coating Water-borne modification, will make the VOC quantity discharged of whole coating reduce to 10g/ ㎡.The protecting metallic surface of this item association research and development with high-performance water-based coating have nontoxic, nonflammable, free from environmental pollution, safe and reliable, easy damaged is not by coating surface, advantage such as easy to operate, reach the peer-level of international like product, very friendly to environment.
Summary of the invention
In order to overcome the deficiency of present technology, the invention provides the high-performance water-based coating of a kind of Air drying shaped metal surfacecti proteon, coating process is finished at normal temperatures, realized energy-saving and emission-reduction when VOC discharges in the restriction coating metal surfaces process, be convenient to promote and use.
The invention provides a kind of preparation method of Air drying type acrylic resin water dispersion, it has comprised following steps:
The preparation of A, acrylic resin prepolymer
In stirring rake, thermometer, condenser reactor are housed, the solubility promoter that adds 5 ~ 10 weight parts is (as propylene glycol ethers or propylene glycol ether-ether class, wherein propylene glycol monomethyl ether (PM), dipropylene glycol methyl ether (DPM), propylene glycol monomethyl ether acetate (PMP) or 1-Methoxy-2-propyl acetate (PMA)), feed nitrogen temperature to reflux temperature; Under this temperature, drip non-functionality (methyl) acrylate (as methyl methacrylate or Jia Jibingxisuanyizhi) of 18 ~ 24 weight parts, (methyl) acrylate (as Jia Jibingxisuanyizhi or propyl acrylate) of 11 ~ 18 weight parts, (methyl) vinylformic acid (as acrylic or methacrylic acid) of 6 ~ 9 weight parts, 1 ~ 15 weight part contain small molecules epoxide group monomer (as molecular weight at 290 ~ 320 Resins, epoxy, described Resins, epoxy is glycidyl ester based epoxy resin or glycidyl ether based epoxy resin, as o-phthalic acid diglycidyl ester or propane type epoxy resin of di phenolic group), 0.25 the mixing solutions that the chain regulator of initiator of ~ 0.75 weight part (optional Diisopropyl azodicarboxylate or dibenzoyl peroxide) and 0.1 ~ 1 weight part (as lauryl mercaptan or thin basic ethanol) is formed, in 2 ~ 3h, dropwise, insulation 0.5 ~ 1h, the above-mentioned initiator of 0.25 ~ 0.75 weight part that adds again afterwards, insulation 2.0 ~ 2.5h can obtain the acrylic resin prepolymer;
The Water-borne modification of B, acrylic resin prepolymer
The acrylic resin vacuum distilling that above-mentioned A step is obtained removes most solvents, and making the content of consumption in resin of solvent is 0 ~ 8%, is preferably 0 ~ 3%; The resin solution that removes partial solvent is poured in the container, when treating that resin temperature is reduced to 60 ~ 80 ℃, add neutralizing agent (as ammoniacal liquor or triethylamine, degree of neutralization reaches 50 ~ 90% and is as the criterion) and carry out neutralization reaction with 1500 ~ 2000r/min under high speed disk dispersion machine, the reaction times is 0.5 ~ 1.5h; The revolution of rising dispersion machine, limit slowly drip the deionization waterside and disperse 1 ~ 2h with 1500 ~ 3000r/min speed, fully stir 25 ~ 30min discharging then, and the consolidating of final dispersion product contains and be controlled at 60 ~ 70% and promptly get product.
In another program of the present invention, provide the preparation method of a kind of Air drying shaped metal surfacecti proteon with high-performance water-based coating, it comprises:
(1), in claim 1 to 5, add flow agent, defoamer, water and optional thickening material in each the acrylic resin water dispersion, obtain component A, wherein the addition of each component following (is 100 parts in water dispersion weight):
Described water dispersion: 100
Flow agent (BYK346 of Bi Ke company): 1 ~ 5
Defoamer (BYK028 of Bi Ke company): 0.2 ~ 1, preferred 0.2 ~ 0.6
The thickening material Borchi Gel PW-25 of company (German Borchers): 0 ~ 0.8, preferred 0.2 ~ 0.5
Aqueous color paste (one or more mixing in aqueous dispersant, flow agent, defoamer, pigment, solubility promoter or the polyurethane thickener.): 0.2 ~ 0.8, preferred 0.4 ~ 0.6
Water: 20 ~ 70, preferred 30 ~ 60
(2), will mix according to the part by weight of A:B=1.5 ~ 3.0:1 (preferred about 1.5: 1) with component A as the polyisocyanates (using modification HDI) of the hydrophilic modifying of B component, can make the high-performance water-based coating of protecting metallic surface.
More than the polyisocyanates of hydrophilic modifying of the present invention be selected from one or both mixing among modification HDI or the modification IPDI.
Positively effect of the present invention is:
1, prepare the acrylic resin water dispersion of a kind of protecting metallic surface with high-performance water-based coating, and the high-performance water-based coating of finished product normal temperature type protecting metallic surface of allotment;
2, the discharging of ultralow VOC is strict controlled in the 10g/l, in the acrylic acid process of synthetic water-based, do not add organic solvent or add final stage earlier and again solvent is taken off, the amount of protecting metallic surface with organic solvent in the high-performance water-based coating is controlled in 1%.
3, in the process of synthetic water-based acrylic acid dispersion, adopts special function monomer make it to different metal substrates as: Marko's iron, galvanized sheet, aluminium, aluminium alloy etc. all have good sticking power under the prerequisite that directly sprays.
4, for single-component high bake type water soluble acrylic acid dispersion, its baking condition is dropped to about 100 ℃/30min from 140 ℃/30min, and its all physical and chemical performance is all constant, has effectively reduced energy consumption.
5,, under the prerequisite that reaches ultralow VOC discharging, can effectively keep the effect of Gao Guang for two component Air drying type water soluble acrylic acid dispersions.
6, the aqueous coating that forms of the water-dispersion that the poly-propylhomoserin dispersion copolymerization of above-mentioned synthetic water soluble acrylic acid dispersion and a spot of water-based is obtained has excellent inhibition and returns the rust performance.
7, the cost of water aluminum-silver slurry is high more a lot of than oiliness aluminium-silver slurry, to reasonably reduce product cost and make its opacifying power good, the sense of changeable colors along with angle metal is strong, selects the collocation of suitable water aluminum-silver slurry with relevant pigment, effectively guarantees the metal sense and the clarity of aqueous coating.
8, by adjusting construction technology protecting metallic surface is improved greatly with high-performance water-based execution of coating conformability, promote with high-performance water-based coating big area for protecting metallic surface and established solid basis.
9, this protecting metallic surface is lower than 1% with the organic solvent content of high-performance water-based coating products, be higher than the strictest environmental requirement fully, very friendly to environment, greatly alleviated use and dependence to organic solvent, saved the energy effectively, and paint film property is excellent and cost is low.
Embodiment
(1) raw material among the embodiment
The raw material that uses among the embodiment only is for example, should not be considered as to limit the scope of the invention.In an embodiment:
Solubility promoter (as propylene glycol ethers or propylene glycol ether-ether class, wherein propylene glycol monomethyl ether (PM), dipropylene glycol methyl ether (DPM), propylene glycol monomethyl ether acetate (PMP) or 1-Methoxy-2-propyl acetate (PMA).
Non-functionality (methyl) acrylate such as methyl methacrylate or Jia Jibingxisuanyizhi.(methyl) acrylate such as Jia Jibingxisuanyizhi or propyl acrylate.
Hydrophilically modified polyisocyanates is aliphatic diisocyanate HDI or the alicyclic diisocyanate IPDI behind the hydrophilic modifying.
(2) performance of water dispersion and testing method
The acrylic resin water dispersion is the performance material of protecting metallic surface with high-performance water-based coating, the performance of its performance final decision product.The performance index of institute's synthetic water dispersion are all within following table 1 scope in the following illustrated embodiment.
The concrete testing method of every performance is as follows:
1) mensuration of non-volatile component
Get the flat ware of glass of a cleaning, claim its quality.Taking a morsel, (1 ± 0.1g) testing sample is transferred in the baking oven of 125oC in the flat ware of the glass of cleaning, keeps taking out in baking oven behind the 2h, stirs sample with glass stick, and is in addition broken surface skining, again ware put back to baking oven.Treat after the sample constant weight ware is transferred to making it to be cooled to room temperature in the moisture eliminator, its quality of weighing is accurate to 1mg.Calculate the ratio that remaining solid part accounts for the sample total mass.Carry out twice replicate(determination), average.
The content of content of volatile matter (V) or non-volatile matter (N V) calculates with the test product massfraction, and calculation formula is as follows:
In the formula:
m
1---the quality of sample before the heating, mg;
m
2---the quality of heating back sample under defined terms, mg;
The content of V---volatile matter is represented with mass percent;
The content of NV---volatile matter is represented with mass percent.
2) mensuration of viscosity
The sample of an amount of inorganics impurity is placed beaker, remove air filled cavity.Cover watch-glass, be placed in 25 ± 0.1oC water bath with thermostatic control, intermittently stirring sample (but not introducing bubble) reaches evenly constant until specimen temperature.Select suitable rotor and rotating speed according to sample viscosity size.Install instrument, rotor is immersed in the sample, make sample reach the last graticule of rotor.Behind the constant 10min of 25 ± 0.1oC, unclamp the viscometer control lever, open motor rotor rotated continuously, treat that pointer is stable after, press the pointer control lever, close motor simultaneously, read reading to a decimal on the dish at quarter.Same sample repeats twice reading under same rotating speed.
The viscosity of sample is calculated as follows:
In the formula:
The viscosity of η---sample,
K---instrument parameter,
A---the arithmetical av of twice reading on the viscometer scale card.
3) mensuration of pH
Soak glass electrode and rectify an instrument by the specification sheets of acidometer.Measure in about 50mL water dispersion impouring beaker as sample with graduated cylinder, and beaker put into 23 ± 1 ℃ thermostatic bath, after the temperature for the treatment of specimen temperature and thermostatic bath reaches balance, to wash and insert in the beaker with distillation with the electrode that softish thieving paper is dried, measure behind the vibrational stabilization a little, getting continuous three mensuration fixed values is pH pH-value determination pH value, gets first of decimal.Same method is measured all the other two samples, makes the difference of pH value of three samples be not more than 0.3.The arithmetical av of getting three sample measured values is as net result.
4) mensuration of density
Under (23 ± 0.5) ℃, the weighing specific gravity flask also writes down its quality m
1Sample is filled with specific gravity flask, wipe with spongy material and overflow material, with rayon balls wiping gently, and the quality m of test product specific gravity flask filled with in record
2
The method of calculation of density are as follows:
In the formula, m
1---the quality of empty specific gravity flask, g;
m
2---fill the quality of the specific gravity flask of sample, g;
V
t---the volume of specific gravity flask, mL.
5) mensuration of acid number
Take by weighing sample 2.5g(and be accurate to 0.2mg) put into the 250ml Erlenmeyer flask, (by 2 parts of toluene and 1 part of volume fraction is that 95% ethanol is made into by volume, shakes Erlenmeyer flask sample is dissolved fully, can heat in case of necessity to add the 50ml mixing solutions.(concentration is 10g/L to add 4 ~ 10 phenolphthalein indicator solution in sample solution, by volume fraction is that 95% ethanol, methyl alcohol or the configuration of 2-propyl alcohol form), (with volume fraction is that 95% ethanol or methyl alcohol are mixed with the solution that concentration is 0.1mol/L to use the potassium hydroxide standard titration solution immediately, and deviate from carbonate, demarcate its concentration with Potassium Hydrogen Phthalate) titration is to blush occurring, keep the colour-fast terminal point that is of 30s, write down the potassium hydroxide solution milliliter number that is consumed.Making line space simultaneously tests in vain.
Be calculated as follows acid number A:
In the formula:
A---acid number is with the milligram number scale of every gram sample consumption KOH;
V
1---potassium hydroxide ethanol standard titration solution consumption during the titration sample, mL;
V
2---potassium hydroxide ethanol standard titration solution consumption during blank test, mL;
C---the concentration of potassium hydroxide ethanol standard titration solution, mol/L;
The quality of m---sample, g;
56.10---the molar mass of potassium hydroxide, g/mol.
(3) specific embodiment
Embodiment 1-product embodiments
In stirring rake, thermometer, condenser reactor are housed, the solubility promoter that adds 5 ~ 10 weight parts is (as propylene glycol ethers or propylene glycol ether-ether class, wherein propylene glycol monomethyl ether (PM), dipropylene glycol methyl ether (DPM), propylene glycol monomethyl ether acetate (PMP) or 1-Methoxy-2-propyl acetate (PMA)), feed nitrogen temperature to reflux temperature; Under this temperature, drip non-functionality (methyl) acrylate (as methyl methacrylate or Jia Jibingxisuanyizhi) of 18 ~ 24 weight parts, (methyl) acrylate (as Jia Jibingxisuanyizhi or propyl acrylate) of 11 ~ 18 weight parts, (methyl) vinylformic acid (as acrylic or methacrylic acid) of 6 ~ 9 weight parts, 1 ~ 15 weight part contain small molecules epoxide group monomer (as molecular weight at 290 ~ 320 Resins, epoxy, described Resins, epoxy is glycidyl ester based epoxy resin or glycidyl ether based epoxy resin, as o-phthalic acid diglycidyl ester or propane type epoxy resin of di phenolic group), 0.25 the mixing solutions that the chain regulator of initiator of ~ 0.75 weight part (optional Diisopropyl azodicarboxylate or dibenzoyl peroxide) and 0.1 ~ 1 weight part (as lauryl mercaptan or thin basic ethanol) is formed, in 2 ~ 3h, dropwise, insulation 0.5 ~ 1h, the above-mentioned initiator of 0.25 ~ 0.75 weight part that adds again afterwards, insulation 2.0 ~ 2.5h can obtain the acrylic resin prepolymer; The Hydroxylated acrylic resin vacuum distilling that above-mentioned A step is obtained removes partial solvent, and making the content of consumption in resin of solvent is 0 ~ 8%, is preferably 0 ~ 3%; The resin solution that removes partial solvent is poured in the container, when treating that resin temperature is reduced to 60 ~ 80 ℃, add neutralizing agent (as ammoniacal liquor or triethylamine, degree of neutralization reaches 50 ~ 90% and is as the criterion) and carry out neutralization reaction with 1500 ~ 2000r/min under high speed disk dispersion machine, the reaction times is 0.5 ~ 1h; The revolution of rising dispersion machine, limit slowly drip the deionization waterside and disperse 1 ~ 2h with 1500 ~ 3000r/min speed, fully stir 25 ~ 30min discharging then, and the consolidating of final dispersion product contains and be controlled at 60 ~ 70% and promptly get product.
Embodiment 2
In stirring rake, thermometer, condenser reactor are housed, add the dipropylene glycol methyl ether (DPM) of the solubility promoter propylene glycol ethers of 5 weight parts, feed nitrogen temperature to reflux temperature; Under this temperature, drip the Jia Jibingxisuanyizhi of non-functionality (methyl) acrylate of 14 weight parts, the Jia Jibingxisuanyizhi of (methyl) acrylate of the hydroxyl of 18 weight parts, (methyl) acrylic acid vinylformic acid of 11 weight parts, the o-phthalic acid diglycidyl ester of the molecular weight of 15 weight parts in 290 ~ 320 Resins, epoxy, 0.75 the mixing solutions that the lauryl mercaptan of the chain regulator of the Diisopropyl azodicarboxylate of the initiator of weight part and 1 weight part is formed, in 2h, dropwise, insulation 0.5h, the above-mentioned initiator of 0.75 weight part that adds again afterwards, insulation 1.5h can obtain the acrylic resin prepolymer; The above-mentioned acrylic resin vacuum distilling that obtains is removed partial solvent, and making the content of consumption in resin of solvent is 0%; The resin solution that removes partial solvent is poured in the container, and when treating that resin temperature is reduced to 60 ℃, the ammoniacal liquor (degree of neutralization reaches 50%) that adds neutralizing agent carries out neutralization reaction with 1500r/min under high speed disk dispersion machine, and the reaction times is 0.5h; The revolution of rising dispersion machine, limit slowly drip the deionization waterside and disperse 1h with 1500r/min speed, fully stir the 30min discharging then, and the consolidating of final dispersion product contains and be controlled at 60% and promptly get product.
Embodiment 3
Stirring rake is being housed, thermometer, in the condenser reactor, the propylene glycol monomethyl ether acetate (PMP) that adds the solubility promoter propylene glycol ether-ether class of 10 weight parts, feed nitrogen temperature to reflux temperature, under this temperature, drip the Jia Jibingxisuanyizhi of non-functionality (methyl) acrylate of 24 weight parts, the propyl acrylate of (methyl) acrylate of 18 weight parts, (methyl) acrylic acid methacrylic acid of 9 weight parts, the molecular weight of 1 weight part is at the propane type epoxy resin of di phenolic group of 290 ~ 320 Resins, epoxy, 0.25 the mixing solutions that the thin basic ethanol of the chain regulator of the dibenzoyl peroxide of the initiator of weight part and 0.1 weight part is formed, in 3h, dropwise, insulation 1h, the above-mentioned initiator of 0.25 weight part that adds again afterwards, insulation 2.5h can obtain the acrylic resin prepolymer; The above-mentioned acrylic resin vacuum distilling that obtains is removed partial solvent, and making the content of consumption in resin of solvent is 1%; The resin solution that removes partial solvent is poured in the container, and when treating that resin temperature is reduced to 80 ℃, the triethylamine (degree of neutralization reaches 90%) that adds neutralizing agent carries out neutralization reaction with 2000r/min under high speed disk dispersion machine, and the reaction times is 1h; The revolution of rising dispersion machine, limit slowly drip the deionization waterside and disperse 2h with 3000r/min speed, fully stir the 30min discharging then, and the consolidating of final dispersion product contains and be controlled at 70% and promptly get product.
Embodiment 4
In stirring rake, thermometer, condenser reactor are housed, add the dipropylene glycol methyl ether (DPM) of propylene glycol ethers of the solubility promoter of 7 weight parts, feed nitrogen temperature to reflux temperature; Under this temperature, drip the methyl methacrylate of non-functionality (methyl) acrylate of 20 weight parts, the hydroxyethyl methylacrylate of (methyl) acrylate of the hydroxyl of 15 weight parts, (methyl) acrylic acid methacrylic acid of 7 weight parts, the molecular weight of 8 weight parts is at the propane type epoxy resin of di phenolic group of 290 ~ 320 Resins, epoxy, 0.5 the mixing solutions that the lauryl mercaptan of the chain regulator of the Diisopropyl azodicarboxylate of the initiator of weight part and 0.6 weight part is formed, in 2.5h, dropwise, insulation 0.7h, the above-mentioned initiator of 0.5 weight part that adds again afterwards, insulation 2h can obtain the acrylic resin prepolymer; The above-mentioned acrylic resin vacuum distilling that obtains is removed partial solvent, and making the content of consumption in resin of solvent is in 1.5%; The resin solution that removes partial solvent is poured in the container, and when treating that resin temperature is reduced to 70 ℃, the triethylamine (degree of neutralization reaches 70%) that adds neutralizing agent carries out neutralization reaction with 1570r/min under high speed disk dispersion machine, and the reaction times is 0.7h; The revolution of rising dispersion machine, limit slowly drip the deionization waterside and disperse 1.5h with 1750r/min speed, fully stir the 22.5min discharging then, and the consolidating of final dispersion product contains and be controlled at 65% and promptly get product.
Embodiment 5
With embodiment 1, just the acrylic resin vacuum distilling that obtains is removed partial solvent, making the content of consumption in resin of solvent is in 1.5%.
The purposes (Application Example) of embodiment 6-product
Get the acrylic resin water dispersion for preparing in arbitrary example among the embodiment 1-5,, obtain component A, wherein the addition of each component following (is 100 parts in water dispersion weight) to wherein adding flow agent, defoamer, water and optional thickening material:
Acrylic resin water dispersion: 100
Flow agent (BYK346 of Bi Ke company): 1 ~ 5
Defoamer (BYK028 of Bi Ke company): 0.2 ~ 1, preferred 0.2 ~ 0.6
The thickening material Borchi Gel PW-25 of company (German Borchers): 0 ~ 0.8, preferred 0.2 ~ 0.5
(BYK 022 defoamer of BYK 191 aqueous dispersants of Bi Ke company, the BYK WS flow agent of Bi Ke company, Bi Ke company, 0622 polyurethane thickener of Bi Ke company, 1-Methoxy-2-propyl acetate PMA solubility promoter, the anti-plain boiled water of BCS, pigment are (after the mixing for aqueous color paste, be ground to 10 microns of fineness), the LA50 wetting dispersing agent): 5-60, preferred 10-20.
Water: 20 ~ 70, preferred 30 ~ 60.
To mix according to the part by weight of A:B=1.5 ~ 3.0:1 (preferred about 1.5: 1) as the polyisocyanates of the hydrophilic modifying of B component and component A, can make the high-performance water-based coating of protecting metallic surface.
More than the polyisocyanates of hydrophilic modifying of the present invention be selected from one or both mixing among modification HDI or the modification IPDI.
Embodiment 7
With embodiment 6, just the flow agent add-on among the component A is 3 weight parts of water dispersion weight, and the defoamer add-on is 0.4 weight part, do not add thickening material, the aqueous color paste add-on is 15 weight parts, and the water add-on is 45 weight parts, and the ratio of component A and B component is A:B=1.5:1.
Embodiment 8
With embodiment 6, just the flow agent add-on among the component A is 5 weight parts of water dispersion weight, the defoamer add-on is 1 weight part, the thickening material add-on is 0.8 weight part, the aqueous color paste add-on is 30 weight parts, the water add-on is 70 weight parts, and the ratio of component A and B component is A:B=2:1.
Embodiment 9
With embodiment 6, just the flow agent add-on among the component A is 4 weight parts of water dispersion weight, the defoamer add-on is 0.6 weight part, the thickening material add-on is 0.2 weight part, the aqueous color paste add-on is 25 weight parts, the water add-on is 60 weight parts, and the ratio of component A and B component is A:B=1.5:1.
Embodiment 10
With embodiment 6, just the flow agent add-on among the component A is 2 weight parts of water dispersion weight, the defoamer add-on is 0.3 weight part, the thickening material add-on is 0.5 weight part, the aqueous color paste add-on is 8 weight parts, the water add-on is 20 weight parts, and the ratio of component A and B component is A:B=3:1.
Above embodiment 6-10 uses common testing methods in the paint field, all obtains this protecting metallic surface with the correlated performance of high-performance water-based coating similar results as shown in table 2.
Claims (9)
1. the preparation method of an Air drying type acrylic resin water dispersion is characterized in that having the following steps:
The preparation of A, acrylic resin prepolymer
In stirring rake, thermometer, condenser reactor are housed, add the solubility promoter of 5 ~ 10 weight parts, feed nitrogen temperature to reflux temperature; Under this temperature, drip 18 ~ 24 weight parts non-functionality acrylate or derivatives thereof, 11 ~ 18 parts by weight of acrylic ester or derivatives thereofs, 6 ~ 9 parts by weight of acrylic or derivatives thereofs, 1 ~ 15 weight part contain small molecules epoxide group monomer, 0.25 the mixing solutions that the chain regulator of the initiator of ~ 0.75 weight part and 0.1 ~ 1 weight part is formed, in 2 ~ 3h, dropwise, insulation 0.5 ~ 1h, the above-mentioned initiator of 0.25 ~ 0.75 weight part that adds again afterwards, insulation 1.5 ~ 2.5h can obtain the acrylic resin prepolymer;
The Water-borne modification of B, acrylic resin prepolymer
The acrylic resin vacuum distilling that above-mentioned A step is obtained removes partial solvent, and making the content of consumption in resin of solvent is 0 ~ 8%; The resin solution that removes partial solvent is poured in the container, and when treating that resin temperature is reduced to 60 ~ 80 ℃, adding neutralizing agent degree of neutralization reaches 50 ~ 90% and is as the criterion, and carries out neutralization reaction with 1500 ~ 2000r/min under high speed disk dispersion machine, and the reaction times is 0.5 ~ 1h; The revolution of rising dispersion machine, limit slowly drip the deionization waterside and disperse 1 ~ 2h with 1500 ~ 3000r/min speed, fully stir 25 ~ 30min discharging then, and the consolidating of final dispersion product contains and be controlled at 60 ~ 70% and promptly get product.
2. the preparation method of a kind of Air drying type acrylic resin water dispersion according to claim 1, it is characterized in that described solubility promoter is selected from propylene glycol ethers or propylene glycol ether-ether class, include propylene glycol ethers or propylene glycol ether-ether class, wherein propylene glycol monomethyl ether (PM), dipropylene glycol methyl ether (DPM), propylene glycol monomethyl ether acetate (PMP) or 1-Methoxy-2-propyl acetate (PMA).
3. the preparation method of a kind of Air drying type acrylic resin water dispersion according to claim 1 is characterized in that described non-functionality acrylate or derivatives thereof is selected from methyl methacrylate or Jia Jibingxisuanyizhi; Described acrylate or derivatives thereof is selected from Jia Jibingxisuanyizhi or propyl acrylate; Described vinylformic acid or derivatives thereof is selected from acrylic or methacrylic acid.
4. the preparation method of a kind of Air drying type acrylic resin water dispersion according to claim 1, it is characterized in that described to contain small molecules epoxide group monomer be molecular weight at 290 ~ 320 Resins, epoxy, described Resins, epoxy is glycidyl ester based epoxy resin or glycidyl ether based epoxy resin, wherein the propane type epoxy resin of di phenolic group of the o-phthalic acid diglycidyl ester of glycidyl ester based epoxy resin or glycidyl ether based epoxy resin; Described initiator is selected from Diisopropyl azodicarboxylate or dibenzoyl peroxide; Described chain regulator is selected from lauryl mercaptan or dredges basic ethanol.
5. the preparation method of a kind of Air drying type acrylic resin water dispersion according to claim 1 is characterized in that acrylic resin vacuum distilling removes solvent in the B step, and the content of consumption in resin that makes solvent is for being preferably 0 ~ 5%; Described neutralizing agent is selected from ammoniacal liquor or triethylamine.
6. the acrylic resin water dispersion for preparing gained by each method of claim 1 to 5.
7. a protecting metallic surface is characterized in that having the following steps with the preparation method of high-performance water-based coating:
(1), under stirring state, slowly add flow agent, defoamer, water, aqueous color paste and optional thickening material in each acrylic resin water dispersion in claim 1 to 5, and be uniformly dispersed, obtain component A, wherein the addition of each component following (is 100 parts in water dispersion weight):
The described water dispersion of in the claim 1 to 5 each: 100
Flow agent: 1 ~ 5
Defoamer: 0.2 ~ 1
Thickening material: 0 ~ 0.8
Aqueous color paste: 10-20
Water: 20 ~ 70
(2), will mix according to the part by weight of A:B=1.5 ~ 3.0:1 as the polyisocyanates of the hydrophilic modifying of B component and component A, can make the high-performance water-based coating of protecting metallic surface.
8. a kind of Air drying shaped metal according to claim 7 surfacecti proteon is with the preparation method of high-performance water-based coating, and the polyisocyanates that it is characterized in that hydrophilic modifying is selected from one or both mixing among modification HDI or the modification IPDI; Described multifunctional assistant comprises one or more mixing in aqueous dispersant, flow agent, defoamer, colorant, solubility promoter or the polyurethane thickener.
9. the high-performance water-based coating of protecting metallic surface for preparing gained by the method for claim 7.
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| CN102627722A (en) * | 2012-02-17 | 2012-08-08 | 汤汉良 | Imino-containing acrylic resin, its preparation method and application |
| CN103571290A (en) * | 2012-07-18 | 2014-02-12 | 西安榕森漆业有限责任公司 | Water dispersible acrylic water-based resin |
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| CN110577614B (en) * | 2019-10-18 | 2021-07-20 | 江苏富琪森新材料有限公司 | Preparation of high-solid-content hydroxy acrylic acid dispersion |
| CN112759715A (en) * | 2020-12-29 | 2021-05-07 | 沧州优美特新材料科技有限公司 | High-hydroxyl-content aqueous acrylic acid dispersion and preparation method thereof |
| CN112759715B (en) * | 2020-12-29 | 2023-09-08 | 沧州优美特新材料科技有限公司 | High-hydroxyl-content aqueous acrylic acid dispersion and preparation method thereof |
| CN114292405A (en) * | 2021-12-31 | 2022-04-08 | 清远华湾材料研究院有限公司 | Polydextrose ethyl acrylate and preparation method and application thereof |
| CN114292405B (en) * | 2021-12-31 | 2023-02-10 | 清远华湾材料研究院有限公司 | Polydextrose ethyl acrylate and preparation method and application thereof |
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Application publication date: 20110907 Assignee: QINGYUAN HAOYU CHEMICAL TECHNOLOGY Co.,Ltd. Assignor: Tang Hanliang Contract record no.: 2015440000112 Denomination of invention: Aqueous acrylic resin dispersion dried at normal temperature and preparation method and application thereof Granted publication date: 20130220 License type: Exclusive License Record date: 20150506 |
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