CN103467747A - Preparation method for water-based acrylic acid modified alkyd emulsion and its amino baking varnish - Google Patents
Preparation method for water-based acrylic acid modified alkyd emulsion and its amino baking varnish Download PDFInfo
- Publication number
- CN103467747A CN103467747A CN2013103509875A CN201310350987A CN103467747A CN 103467747 A CN103467747 A CN 103467747A CN 2013103509875 A CN2013103509875 A CN 2013103509875A CN 201310350987 A CN201310350987 A CN 201310350987A CN 103467747 A CN103467747 A CN 103467747A
- Authority
- CN
- China
- Prior art keywords
- acid
- water
- weight
- based acrylic
- acrylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to a water-based acrylic acid modified alkyd emulsion, the synthetic formula of which consists of the following components (by weight percentage): 9%-11% of diol or polyol; 9%-11% of polycarboxylic acid or anhydride; 0.01%-0.2% of a catalyst; 14%-19% of unsaturated fatty acid; 4%-6% of (methyl) acrylic ester or a vinyl monomer; 2%-4% of methacrylic acid; 0.1%-0.5% of an initiator; 4%-6% of a cosolvent; 1.5%-2.5% of a neutralizing agent; and 45%-55% of deionized water. The water-based alkyd amino baking varnish based on the water-based acrylic acid modified alkyd emulsion involved in the invention has the advantages of: (1) good storage stability; (2) good self-crosslinking; (3) excellent water resistance and rust resistance; and (4) safe and convenient use.
Description
Technical field
The present invention relates to a kind of preparation method of water-based acrylic acid modified alcoholic acid emulsion, simultaneously, also relate to a kind of preparation method of this acrylic modified alkyd emulsion as base-material preparation water alcohol acid amino-stoving varnish of take.
Background technology
Synolac is one of kind that in coating synthetic resins, development the earliest, consumption is maximum, purposes is the widest.The Synolac film forming properties is good, and the coating film gloss degree is high, but its hardness of film is low, water tolerance and weathering resistance poor.In order to improve the performance of Synolac, can carry out modification to Synolac with vinylformic acid.Adopt acrylic acid or the like to carry out modification to Synolac, prepare acrylic acid modified alkyd resin, can make Synolac there is the advantages such as excellent guarantor's light tint retention, weathering resistance, weather resistance and erosion resistance and quick-drying, high rigidity.
Enhancing along with national environmental consciousness, restriction VOC(Volatile Organic Compounds, the english abbreviation of volatile organic compounds) formulation of the laws and regulations of quantity discharged, and the anxiety of petroleum-based energy, traditional solvent based coating just is being subject to increasing challenge, and the Water-borne modification trend of coating is more and more distincter.Water-borne modification research for acrylic acid modified alkyd resin just more and more is subject to people's attention.
At present, the method of acrylic acid modified alkyd resin being carried out to Water-borne modification mainly contains following several: (one) additional emulsifying agent method: by adding suitable emulsifying agent, solvent-type acrylic modified alkyd resin prepared by traditional method carries out forced emulsification or Phase inversion emulsification and makes.Chinese patent CN 101307137 A are exactly by additional emulsifying agent method, adopt Phase inversion emulsification technique to prepare the water-based acrylic acid modified alcoholic acid emulsion.Along with the further raising to the water-based acrylic acid modified alcoholic acid performance requriements, it is found that additional emulsifying agent method exists some shortcomings, for example, resulting water-based acrylic acid modified alcoholic acid emulsion latex particle size is thicker, stability in storage is not good, and paint film dryness and hardness rise slower; Due to the emulsifying agent that has used more amount, emulsifying agent moves to coating surface, makes paint film water tolerance variation, and film-forming properties and antiseptic property variation.(2) emulsion polymerization: its preparation method is first to prepare a kind of water soluble alkyd resin that contains certain hydrophilic radical, and this water soluble alkyd resin is molten
In Xie Shui, form the water miscible liquid of Synolac, then in this emulsion, drip Acrylic Acid Monomer, by the mode of letex polymerization, prepare the water-based acrylic acid modified alcoholic acid emulsion.Chinese patent CN 1546544 A, CN 1272865 A, CN 1272854 A and CN 1365368 A all adopt this emulsion polymerization to prepare the water-based acrylic acid modified alcoholic acid emulsion.Dryness and the erosion resistance of the paint film of water-based acrylic acid modified alcoholic acid emulsion prepared by the method increase, but stability in storage decline, and level of residual monomers is more, and toxicity is larger.(3) vinyl method after: its preparation method is first to prepare the oil soluble Synolac, by the esters of acrylic acid mix monomer of this Synolac and predetermined acid number, in organic solvent, carry out free-radical polymerized again, form copolymerization product, this is carried out obtaining the water-based acrylic acid modified alcoholic acid emulsion after the water dilution after amine (or ammonia) neutralization for copolymerization product.After Chinese patent CN 1375535 A, CN 1405254 A and CN 102086253 A all adopt this, the vinyl method prepares the water-based acrylic acid modified alcoholic acid emulsion.Water-based acrylic acid modified alcoholic acid emulsion prepared by the method has good stability in storage, and dryness and the erosion resistance of paint film increase, but the method also has many deficiencies: (1) reaction process is wayward, and gel easily occurs; (2), in building-up process, owing to having consumed the unsaturated double-bond on the abundant fatty acid, the later stage dryness of resin is improved not quite owing to lacking unsaturated double-bond; (3) resinous acid value is higher, and water tolerance and the erosion resistance of paint film are poor; (4) residual monomer is more, and toxicity is larger.(4) front vinyl method: its preparation method is divided into following step: (1) radical polymerizable vinyl monomer prepares carboxylic vinyl polymer A; (2) preparation is containing the Synolac B of certain hydroxy radical content; (3) A is joined in B, makes in A hydroxyl reaction in carboxyl and B and make acrylic acid modified alkyd resin C, in (4) and C, then add water and disperse after obtain the water-based acrylic acid modified alcoholic acid emulsion.Chinese patent CN 102127213 A, CN 1474838 A and CN 101955721 A all adopt this front vinyl method to prepare the water-based acrylic acid modified alcoholic acid emulsion.Although the method has overcome the standby water-based acrylic acid modified alcoholic acid emulsion water tolerance of front vinyl legal system and erosion resistance is not good, and paint film dryness and the hardness slow shortcoming that rises, reaction process is wayward, and gel easily occurs.
Summary of the invention
The present invention is intended to overcome above-mentioned some shortcomings that prepare in water-based acrylic acid modified alcoholic acid emulsion process, and improving one's methods of a kind of synthetic water-based acrylic acid modified alcoholic acid emulsion is provided.The inventor finds:
(1) some (methyl) acrylate or vinyl monomer can carry out with some unsaturated fatty acids radical polymerization under the initiator effect, (methyl) acrylate or vinyl monomer can be grafted on unsaturated fatty acids, the acrylic polymer that preparation contains fatty acid component.This preparation technology is simple, and transformation efficiency is high, and monomer residue is few, not there will be gelatin phenomenon, and residual monomer can be removed in ensuing reaction on a small quantity, makes the water-based acrylic acid modified alcoholic acid emulsion smell of final preparation very low.
(2) include carboxyl on lipid acid and the carboxyl on methacrylic acid on acrylic polymer, the activity of these two kinds of carboxyls is different.Due to the steric effect of methyl on methacrylic acid, make the reactive behavior of carboxyl on methacrylic acid be far smaller than the reactive behavior of carboxyl on lipid acid.With Synolac in the reaction process of hydroxyl, the carboxyl reaction on the preferential and lipid acid of hydroxyl, retained the carboxyl on methacrylic acid, the carboxyl of these reservations provides the hydrophilic radical of final resin.
(3) acrylic polymer that contains fatty acid component and Synolac carry out graft reaction, prepare the water-based acrylic acid modified alcoholic acid emulsion, lipid acid on acrylic polymer plays " bridge " effect between acrylic polymer and Synolac, improve acrylic polymer and be grafted to the probability on Synolac, do not contain the insoluble particles thing in the water-based acrylic acid modified alcoholic acid emulsion that makes to prepare.Whole synthesis technique is simple, safety, is difficult for gelatin phenomenon occurs, and building-up process and quality product are easily controlled.
(4) acrylic polymer is directly grafted on the Synolac main chain, makes on fatty acid ester to have retained a large amount of unsaturated double-bonds, makes the paint film of this water-based acrylic acid modified alcoholic acid emulsion have good self-crosslinking, has improved dryness and the water tolerance of paint film.Because acrylic polymer and Synolac are by chemical bond grafting modification, the consistency of these two kinds of resins is greatly improved, the glossiness of paint film is obviously improved.
(5) the vinylformic acid segment has coating function to the alkyd segment, form the structure of a kind of being similar to " core-shell ", using hydrolysis easily occurs alkyd as " core ", using the vinylformic acid of hydrolysis as " shell ", such structure makes this emulsion have good hydrolytic resistance and stability in storage.The latex particle size of emulsion is very thin, has good stability in storage and mechanical stability, and during painting, used water is directly diluted, and can with the direct sand milling of pigment, reduce the consumption of dispersion agent, further improve the water tolerance of paint film.Take the water alcohol acid amino-stoving varnish that this water-based acrylic acid modified alcoholic acid emulsion makes as base-material, its workability and paint film physical strength all can compare favourably with the solvent-borne type alkydpaints.
The present invention includes the preparation of water-based acrylic acid modified alcoholic acid emulsion, and take the water alcohol acid amino-stoving varnish that this water-based acrylic acid modified alcoholic acid emulsion makes as base-material.
The preparating mechanism of water-based acrylic acid modified alcoholic acid emulsion provided by the invention is as follows: first unsaturated fatty acids is reacted with (methyl) vinylformic acid (ester) or vinyl monomer, the acrylic polymer that preparation contains unsaturated fatty acids, then carrying out graft esterification with the Synolac that contains certain hydroxyl value reacts, after qualified to acid number, add solubility promoter and neutralizing agent, finally with deionized water, diluted and obtain the water-based acrylic acid modified alcoholic acid emulsion.
Water-based acrylic acid modified alcoholic acid emulsion provided by the invention, its synthesizing formula comprises following component (meter as weight percents): dibasic alcohol 9%--11%(weight) or polyvalent alcohol; 9%--11%(weight) polycarboxylic acid or acid anhydrides; 0.01%--0.2%(weight) catalyzer; 14%--19%(weight) unsaturated fatty acids; 4%--6%(weight) (methyl) acrylate or vinyl monomer; 2%--4%(weight) methacrylic acid; 0.1%--0.5%(weight) initiator; 4%--6%(weight) solubility promoter; 1.5%--2.5%(weight) neutralizing agent; 45%--55%(weight) deionized water.
Described dibasic alcohol or polyvalent alcohol are selected from neopentyl glycol, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, Dipentaerythritol, glycerine, ethylene glycol, propylene glycol, 1, ammediol, 1,3 butylene glycol, BDO, 1,5-pentanediol, 1,6-hexylene glycol, 1,2-CHDM, 1,3-CHDM, 1,4-cyclohexanedimethanol, 2,2,4-trimethylammonium-1, one or more in the 3-pentanediol.
Described polycarboxylic acid or acid anhydrides are selected from m-phthalic acid, terephthalic acid, Tetra hydro Phthalic anhydride, hexanodioic acid, succsinic acid, Tetra Hydro Phthalic Anhydride, dodecanedioic acid, sebacic acid, nonane diacid, 1,4-cyclohexane dicarboxylic acid, 1, one or more in 3-cyclohexane dicarboxylic acid, maleic anhydride, fumaric acid, pentanedioic acid.
Described unsaturated fatty acids is selected from one or more in ricinolic acid, dehydrated castor oleic acid, sylvic acid, linolic acid, linolenic acid, behenic acid, paulownia linolic acid, tall oil acid.
Described (methyl) acrylate or vinyl monomer are selected from one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, n octyl methacrylate, Isooctyl methacrylate, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl, Isooctyl acrylate monomer, vinylbenzene, Vinyl toluene.
Described initiator is selected from one or more in benzoyl peroxide (BPO), peroxidized t-butyl perbenzoate (TBPB), peroxidation di-t-butyl (DTBP), tert-butyl peroxide (TBHP), cyclohexanone peroxide (CHPO), peroxidation PIVALIC ACID CRUDE (25) tert-pentyl ester (TAPP), tert-Butyl peroxypivalate (TAPP).
Described solubility promoter is selected from one or more in n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, ethylene glycol monomethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene glycol propyl ether, propandiol butyl ether, diethylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, glycol methyl ether acetate, 1-Methoxy-2-propyl acetate.
Described neutralizing agent is selected from N, one or more in N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, ammoniacal liquor (25%), triethylamine, trolamine, diethylamine, diethanolamine.
The concrete preparation method of described water-based acrylic acid modified alcoholic acid emulsion is:
(1) unsaturated fatty acids of 1/3 gross weight is dropped in reactor, be warming up to gradually 135 ℃ under whipped state--145 ℃; (methyl) acrylate or vinyl monomer, methacrylic acid and initiator are mixed in rear input dropping liquid header tank, and at the uniform velocity be added drop-wise in reactor, time for adding is 6--8 hour; After dropwising, at 135 ℃--145 ℃ the insulation 3--4 hour, to transformation efficiency be 98 ± 1%, obtain acrylic polymer;
(2) drop into dibasic alcohol or polyvalent alcohol, polycarboxylic acid or acid anhydrides, the unsaturated fatty acids of 2/3 gross weight and the catalyzer of 1/2 gross weight in another reactor, be warming up to gradually 140--150 ℃, after material melts, start to stir; Continue to be warming up to 200--220 ℃, and remain on reaction in this temperature range; After reaction 3 hours, start to survey acid number, after acid number is less than 5mgKOH/g, start cooling; When being cooled to below 140 ℃, add acrylic polymer in above-mentioned (1) and the catalyzer of 1/2 gross weight, and be warming up to gradually 180--190 ℃, and remain on reaction in this temperature range, after being less than 45mgKOH/g to acid number, start cooling; Be cooled to 150 ℃, solubility promoter is dropped in reactor; Continue to be cooled to 90 ℃, neutralizing agent is dropped in reactor, stir 30--40 minute to disperseing fully; Deionized water is dropped into and drips in still, start to be added drop-wise in reactor; After dropwising, continue to stir 30--40 minute; Filter and discharging, obtain the water-based acrylic acid modified alcoholic acid emulsion, the acid number of this water-based acrylic acid modified alcoholic acid emulsion is 35--45mgKOH/g, and solid part is 35%--45%(weight).
The water alcohol acid amino-stoving varnish that the water-based acrylic acid modified alcoholic acid emulsion of usining is made as base-material, its formula comprises following composition: water-based acrylic acid modified alcoholic acid emulsion 52%--55%(weight); 2%--10%(weight) water-compatible amino resin; 20%--30%(weight) color stuffing; 2%--5%(weight) solubility promoter; 0.2%--0.4%(weight) neutralizing agent; 0.3%--0.5%(weight) wetting dispersing agent; 0.3%--0.5%(weight) siccative; 0.2%--0.4%(weight) defoamer; 0.5%--0.8%(weight) flow agent; 0.2%--0.4%(weight) thickening material; 8%--10%(weight) deionized water.
The preparation method of the water alcohol acid amino-stoving varnish based on the water-based acrylic acid modified alcoholic acid emulsion is as follows:
(1) master grind: add water-based acrylic acid modified alcoholic acid emulsion, solubility promoter, deionized water, neutralizing agent, wetting dispersing agent and defoamer in Scattered Kettle; After being uniformly dispersed, add color stuffing, ground with sand mill, until fineness is less than 30 microns, filter, standby;
(2) mix paint: add water-based acrylic acid modified alcoholic acid emulsion, water-compatible amino resin, siccative, flow agent and thickening material in Scattered Kettle, after being uniformly dispersed, slowly adding the mill base in above-mentioned (1), and be uniformly dispersed; Detect the pH value, adjusting the pH value is 7--9; With 80--120 purpose strainer filtering, packing, obtain the water alcohol acid amino-stoving varnish.
The solid content of described water-based acrylic acid modified alcoholic acid emulsion is 35%--45%.
Described water-compatible amino resin is selected from one or more in first (fourth) etherify melamine resin, first (fourth) etherify melamine methylal resin, first (fourth) etherify melamine-urea methylal resin.The water-compatible amino resin be specifically related to has the trades mark such as Cymel 300, Cymel 301, Cymel 303, Cymel 324, Cymel 350, Cymel 370, Cymel 373, Cymel 380, Cymel 385, and above water-compatible amino resin provides by the special company of U.S.'s cyanogen.
Described color stuffing is selected from one or more in carbon black, phthalocyanine blue, titanium dioxide, phthalocyanine green, medium chrome yellow medium yellow, lemon yellow, red, red iron oxide, iron oxide black, iron mica, zinc phosphate, modified zinc phosphate, zinc molybdate, aluminium triphosphate, modification aluminium triphosphate, strontium chromate, zinc-chrome yellow, mica powder, process white, kaolin, talcum powder, silica powder, calcined kaolin, diatomite.
Described solubility promoter is selected from one or more in sec-butyl alcohol, isopropylcarbinol, butyl glycol ether, propylene glycol monomethyl ether, propylene glycol propyl ether, Virahol, dipropylene glycol methyl ether, propyl carbinol, ethylene glycol monomethyl ether, propandiol butyl ether, diethylene glycol dimethyl ether, 1-Methoxy-2-propyl acetate, dipropylene glycol butyl ether, glycol methyl ether acetate.
Described neutralizing agent is selected from N, one or more in N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, ammoniacal liquor (25%), triethylamine, diethylamine, diethanolamine, trolamine.
Described wetting dispersing agent is selected from BYK-184(Germany Bi Ke chemical company), BYK-190(Germany Bi Ke chemical company), DISPERBYK(Germany Bi Ke chemical company), LACTIMON-WS(Germany Bi Ke chemical company), Borchi Gen 0650(borchers company), Dispers 755W(Di Gao company), Dispers 760W(Di Gao company), BYK-180(Germany Bi Ke chemical company), BYK-192(Germany Bi Ke chemical company), Hydropalat 535 N(Cognis companies) one or more in.
Described siccative is selected from the special company of ADDITOL VXW-4940(U.S. cyanogen), the special company of ADDITOL VXW-4952(U.S. cyanogen), the special company of ADDITOL VXW-6206(U.S. cyanogen), Octa Soligen 123 aqua(OMG companies), Octa Soligen 421 aqua(OMG companies), Borchers Dry 0347 aqua(OMG company) in one or more.
Described defoamer is selected from BYK-020(Germany Bi Ke chemical company), BYK-022(Germany Bi Ke chemical company), BYK-024(Germany Bi Ke chemical company), SN313(Germany Henkel company), EFKA 2550(Holland Efka company), Borchers AF 0671(OMG company), Foamex 810(Di Gao company) in one or more.
Described flow agent is selected from BYK-333(Germany Bi Ke chemical company), BYK-345(Germany Bi Ke chemical company), Borchi Gol LA 232(borchers company), BYK-300(Germany Bi Ke chemical company), RM-2020(Rhom and Hass) in one or more.
Described thickening material is selected from Borchi Gel 0434(borchers company), the modest company of WT-202(moral), Rheolate 255(U.S. Hai Mingsi company), the modest company of WT-204(moral), RM-8W(Rhom and Hass) in one or more.
Of the present inventionly take the water alcohol acid amino-stoving varnish that the water-based acrylic acid modified alcoholic acid emulsion is base-material and have the following advantages: (1) stability in storage is good; (2) self-crosslinking is good; (2) water tolerance and rustless property excellence; (4) safe and convenient to use.
Embodiment
Below by embodiment, the present invention is further described in detail, but the scope of protection of present invention is not limited in following instance.
embodiment 1:
Prepare acrylic polymer A1:
400 kilograms of dehydrated castor oil fatty acids are dropped in reactor, be warming up to gradually 135 ℃ under whipped states--145 ℃; 200 kilograms of methyl methacrylates, 200 kilograms of Propenoic acid, 2-methyl, isobutyl esters, 60 kilograms of vinylbenzene, 120 kg methacrylic acid and 20 kilograms of peroxidized t-butyl perbenzoates are mixed in rear input dropping liquid header tank, with constant flow pump, be added drop-wise in reactor, time for adding is 6--8 hour; After dropwising, at 135 ℃--145 ℃ the insulation 3--4 hour, to transformation efficiency be 98 ± 1%, obtain acrylic polymer A1, acid number is 156mgKOH/g.
embodiment 2:
Prepare acrylic polymer A2:
400 kilograms of linseed oil fatty acids are dropped in reactor, be warming up to gradually 135 ℃ under whipped states--145 ℃; 140 kilograms of methyl methacrylates, 180 kilograms of Propenoic acid, 2-methyl, isobutyl esters, 60 kilograms of Vinyl toluenes, 200 kilograms of methacrylic acids and 20 kilograms of di-t-butyl peroxide ethers are mixed in rear input dropping liquid header tank, with constant flow pump, be added drop-wise in reactor, time for adding is 6--8 hour; After dropwising, at 135 ℃--145 ℃ the insulation 3--4 hour, to transformation efficiency be 98 ± 1%, obtain acrylic polymer A2, acid number is 210 mgKOH/g.
embodiment 3:
Prepare acrylic polymer A3:
400 kilograms of linseed oil fatty acids are dropped in reactor, be warming up to gradually 135 ℃ under whipped states--145 ℃; 150 kilograms of n-BMAs, 70 kilograms of vinylbenzene, 160 kilograms of Vinyl toluenes, 200 kilograms of methacrylic acids and 20 kilograms of peroxidized t-butyl perbenzoates are mixed in rear input dropping liquid header tank, with constant flow pump, be added drop-wise in reactor, time for adding is 6--8 hour; After dropwising, at 135 ℃--145 ℃ the insulation 3--4 hour, to transformation efficiency be 98 ± 1%, obtain acrylic polymer A3, acid number is 210mgKOH/g.
embodiment 4:
Prepare water-based acrylic acid modified alcoholic acid emulsion B1:
Drop into 96 kilograms of TriMethylolPropane(TMP)s, 88 kilograms of m-phthalic acids, 96 kilograms of linolic acid and 0.2 kilogram of three isocaprylic acid butyl tin in another reactor, be warming up to gradually 140--150 ℃, after material melts, start to stir; Continue to be warming up to 200--220 ℃, and remain on reaction in this temperature range; After reaction 3 hours, start to survey acid number, after acid number is less than 5mgKOH/g, start cooling; When being cooled to below 140 ℃, add acrylic polymer A1 and 0.2 kilogram of three isocaprylic acid butyl tin in 120 kg embodiment 1, and be warming up to gradually 180--190 ℃, and remain on reaction in this temperature range, after being less than 45mgKOH/g to acid number, start cooling; Be cooled to 150 ℃, 45 kilograms of butyl glycol ethers are dropped in reactor; Continue to be cooled to 90 ℃, by 15 kilograms of N, the N-dimethylethanolamine drops in reactor, stirs 30--40 minute to disperseing fully; 540 kilograms of deionized waters are dropped into and drip in still, start to be added drop-wise in reactor; After dropwising, continue to stir 30--40 minute; Filter and discharging, obtain translucent water-based acrylic acid modified alcoholic acid emulsion B1, the acid number of this water-based acrylic acid modified alcoholic acid emulsion is 40mgKOH/g, and hydroxyl value is 100 mgKOH/g, and the pH value is 8.0, and solid part is 38%(weight).
embodiment 5:
Prepare water-based acrylic acid modified alcoholic acid emulsion B2:
Drop into 84 kilograms of tetramethylolmethanes, 100 kilograms of m-phthalic acids, 96 kilograms of behenic acids and 0.2 kilogram of three isocaprylic acid butyl tin in another reactor, be warming up to gradually 140--150 ℃, after material melts, start to stir; Continue to be warming up to 200--220 ℃, and remain on reaction in this temperature range; After reaction 3 hours, start to survey acid number, after acid number is less than 5mgKOH/g, start cooling; When being cooled to below 140 ℃, add acrylic polymer A2 and 0.2 kilogram of three isocaprylic acid butyl tin in 120 kg embodiment 2, and be warming up to gradually 180--190 ℃, and remain on reaction in this temperature range, after being less than 45mgKOH/g to acid number, start cooling; Be cooled to 150 ℃, 45 kilograms of butyl glycol ethers are dropped in reactor; Continue to be cooled to 90 ℃, by 15 kilograms of N, the N-dimethylethanolamine drops in reactor, stirs 30--40 minute to disperseing fully; 540 kilograms of deionized waters are dropped into and drip in still, start to be added drop-wise in reactor; After dropwising, continue to stir 30--40 minute; Filter and discharging, obtain translucent water-based acrylic acid modified alcoholic acid emulsion B2, the acid number of this water-based acrylic acid modified alcoholic acid emulsion is 42mgKOH/g, and hydroxyl value is 115 mgKOH/g, and the pH value is 8.1, and solid part is 38%(weight).
embodiment 6:
Prepare water-based acrylic acid modified alcoholic acid emulsion B3:
Drop into 96 kilograms of TriMethylolPropane(TMP)s, 88 kilograms of m-phthalic acids, 24 kilograms of linolic acid, 72 kilograms of linolenic acids and 0.2 kilogram of three isocaprylic acid butyl tin in another reactor, be warming up to gradually 140--150 ℃, after material melts, start to stir; Continue to be warming up to 200--220 ℃, and remain on reaction in this temperature range; After reaction 3 hours, start to survey acid number, after acid number is less than 5mgKOH/g, start cooling; When being cooled to below 140 ℃, add acrylic polymer A3 and 0.2 kilogram of three isocaprylic acid butyl tin in 120 kg embodiment 3, and be warming up to gradually 180--190 ℃, and remain on reaction in this temperature range, after being less than 45mgKOH/g to acid number, start cooling; Be cooled to 150 ℃, 45 kilograms of butyl glycol ethers are dropped in reactor; Continue to be cooled to 90 ℃, by 15 kilograms of N, the N-dimethylethanolamine drops in reactor, stirs 30--40 minute to disperseing fully; 540 kilograms of deionized waters are dropped into and drip in still, start to be added drop-wise in reactor; After dropwising, continue to stir 30--40 minute; Filter and discharging, obtain translucent water-based acrylic acid modified alcoholic acid emulsion B3, the acid number of this water-based acrylic acid modified alcoholic acid emulsion is 42mgKOH/g, and hydroxyl value is 85 mgKOH/g, and the pH value is 8.1, and solid part is 38%(weight).
embodiment 7:
Water-based acrylic acid modified alcoholic acid emulsion B1--B3 is prepared respectively to the water alcohol acid amino-stoving varnish by table 1 formula, and its performance index are in Table 2.
Table 1 water alcohol acid amino-stoving varnish formula
Table 2 water alcohol acid amino-stoving varnish performance index
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a water-based acrylic acid modified alcoholic acid emulsion, is characterized in that, the synthesizing formula of described water-based acrylic acid modified alcoholic acid emulsion comprises following component (meter as weight percents): dibasic alcohol 9%--11%(weight) or polyvalent alcohol; 9%--11%(weight) polycarboxylic acid or acid anhydrides; 0.01%--0.2%(weight) catalyzer; 14%--19%(weight) unsaturated fatty acids; 4%--6%(weight) (methyl) acrylate or vinyl monomer; 2%--4%(weight) methacrylic acid; 0.1%--0.5%(weight) initiator; 4%--6%(weight) solubility promoter; 1.5%--2.5%(weight) neutralizing agent; 45%--55%(weight) deionized water.
2. water-based acrylic acid modified alcoholic acid emulsion according to claim 1, it is characterized in that, described dibasic alcohol or polyvalent alcohol are selected from neopentyl glycol, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane, Dipentaerythritol, glycerine, ethylene glycol, propylene glycol, 1, ammediol, 1,3-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,2-CHDM, 1,3-CHDM, 1,4-cyclohexanedimethanol, 2,2,4-trimethylammonium-1, one or more in the 3-pentanediol.
3. water-based acrylic acid modified alcoholic acid emulsion according to claim 1, it is characterized in that, described polycarboxylic acid or acid anhydrides are selected from m-phthalic acid, terephthalic acid, Tetra hydro Phthalic anhydride, hexanodioic acid, succsinic acid, Tetra Hydro Phthalic Anhydride, dodecanedioic acid, sebacic acid, nonane diacid, 1,4-cyclohexane dicarboxylic acid, 1, one or more in 3-cyclohexane dicarboxylic acid, maleic anhydride, fumaric acid, pentanedioic acid.
4. water-based acrylic acid modified alcoholic acid emulsion according to claim 1, it is characterized in that, described unsaturated fatty acids is selected from one or more in ricinolic acid, dehydrated castor oleic acid, sylvic acid, linolic acid, linolenic acid, behenic acid, paulownia linolic acid, tall oil acid.
5. water-based acrylic acid modified alcoholic acid emulsion according to claim 1, it is characterized in that, described (methyl) acrylate or vinyl monomer are selected from one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, n octyl methacrylate, Isooctyl methacrylate, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylformic acid n-octyl, Isooctyl acrylate monomer, vinylbenzene, Vinyl toluene.
6. water-based acrylic acid modified alcoholic acid emulsion according to claim 1, it is characterized in that, described initiator is selected from one or more in benzoyl peroxide (BPO), peroxidized t-butyl perbenzoate (TBPB), peroxidation di-t-butyl (DTBP), tert-butyl peroxide (TBHP), cyclohexanone peroxide (CHPO), peroxidation PIVALIC ACID CRUDE (25) tert-pentyl ester (TAPP), tert-Butyl peroxypivalate (TAPP).
7. water-based acrylic acid modified alcoholic acid emulsion according to claim 1, it is characterized in that, described solubility promoter is selected from one or more in n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, ethylene glycol monomethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propylene glycol propyl ether, propandiol butyl ether, diethylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether, glycol methyl ether acetate, 1-Methoxy-2-propyl acetate.
8. water-based acrylic acid modified alcoholic acid emulsion according to claim 1, it is characterized in that, described neutralizing agent is selected from N, one or more in N-dimethylethanolamine, 2-amino-2-methyl-1-propanol, ammoniacal liquor (25%), triethylamine, trolamine, diethylamine, diethanolamine.
9. water-based acrylic acid modified alcoholic acid emulsion according to claim 1, is characterized in that, its concrete preparation method is:
(1) unsaturated fatty acids of 1/3 gross weight is dropped in reactor, be warming up to gradually 135 ℃ under whipped state--145 ℃; (methyl) acrylate or vinyl monomer, methacrylic acid and initiator are mixed in rear input dropping liquid header tank, and at the uniform velocity be added drop-wise in reactor, time for adding is 6--8 hour; After dropwising, at 135 ℃--145 ℃ the insulation 3--4 hour, to transformation efficiency be 98 ± 1%, obtain acrylic polymer;
(2) drop into dibasic alcohol or polyvalent alcohol, polycarboxylic acid or acid anhydrides, the unsaturated fatty acids of 2/3 gross weight and the catalyzer of 1/2 gross weight in another reactor, be warming up to gradually 140--150 ℃, after material melts, start to stir; Continue to be warming up to 200--220 ℃, and remain on reaction in this temperature range; After reaction 3 hours, start to survey acid number, after acid number is less than 5mgKOH/g, start cooling; When being cooled to below 140 ℃, add acrylic polymer in above-mentioned (1) and the catalyzer of 1/2 gross weight, and be warming up to gradually 180--190 ℃, and remain on reaction in this temperature range, after being less than 45mgKOH/g to acid number, start cooling; Be cooled to 150 ℃, solubility promoter is dropped in reactor; Continue to be cooled to 90 ℃, neutralizing agent is dropped in reactor, stir 30--40 minute to disperseing fully; Deionized water is dropped into and drips in still, start to be added drop-wise in reactor; After dropwising, continue to stir 30--40 minute; Filter and discharging, obtain the water-based acrylic acid modified alcoholic acid emulsion, the acid number of this water-based acrylic acid modified alcoholic acid emulsion is 35--45mgKOH/g, and solid part is 35%--45%(weight).
10. the water alcohol acid amino-stoving varnish that the water-based acrylic acid modified alcoholic acid emulsion of claim 1 of usining is made as base-material is characterized in that this water alcohol acid amino-stoving varnish comprises following composition: water-based acrylic acid modified alcoholic acid emulsion 52%--55%(weight); 2%--10%(weight) water-compatible amino resin; 20%--30%(weight) color stuffing; 2%--5%(weight) solubility promoter; 0.2%--0.4%(weight) neutralizing agent; 0.3%--0.5%(weight) wetting dispersing agent; 0.3%--0.5%(weight) siccative; 0.2%--0.4%(weight) defoamer; 0.5%--0.8%(weight) flow agent; 0.2%--0.4%(weight) thickening material; 8%--10%(weight) deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103509875A CN103467747A (en) | 2013-08-13 | 2013-08-13 | Preparation method for water-based acrylic acid modified alkyd emulsion and its amino baking varnish |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103509875A CN103467747A (en) | 2013-08-13 | 2013-08-13 | Preparation method for water-based acrylic acid modified alkyd emulsion and its amino baking varnish |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103467747A true CN103467747A (en) | 2013-12-25 |
Family
ID=49792803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013103509875A Pending CN103467747A (en) | 2013-08-13 | 2013-08-13 | Preparation method for water-based acrylic acid modified alkyd emulsion and its amino baking varnish |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103467747A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497221A (en) * | 2014-12-04 | 2015-04-08 | 北京金汇利应用化工制品有限公司 | Waterborne acrylic modified alkyd resin and preparation method of aqueous dispersion of alkyd resin |
| CN104559708A (en) * | 2015-02-04 | 2015-04-29 | 浙江天女集团制漆有限公司 | Water-borne acrylic modified alkyd enamel and preparation method thereof |
| CN104774522A (en) * | 2015-05-01 | 2015-07-15 | 李亮军 | Heat insulation paint preparation method |
| CN104788663A (en) * | 2015-04-17 | 2015-07-22 | 广西藤县通轩立信化学有限公司 | Water-soluble alkyd resin |
| CN104829790A (en) * | 2015-05-31 | 2015-08-12 | 山东帝高漆业有限公司 | Preparation method of water-soluble acrylic modified alkyd resin |
| CN104877084A (en) * | 2014-12-04 | 2015-09-02 | 北京金汇利应用化工制品有限公司 | Aqueous acrylic acid modified alkyd resin and water dispersion thereof |
| CN104945605A (en) * | 2015-05-20 | 2015-09-30 | 安徽省金盾涂料有限责任公司 | Acrylic-acid-modified water-based alkyd resin and preparation method thereof |
| CN105925042A (en) * | 2016-05-27 | 2016-09-07 | 广西梧州龙鱼漆业有限公司 | Quick drying paint |
| CN106380967A (en) * | 2016-09-05 | 2017-02-08 | 肇庆千江高新材料科技股份公司 | Ultra-high-weatherability water-based paint, water-based castor oil modified alkyd resin and preparation methods thereof |
| CN107955101A (en) * | 2017-12-19 | 2018-04-24 | 上海华谊精细化工有限公司 | A kind of preparation method of oxidation cross-linked type aqueous acrylic emulsion |
| CN108059695A (en) * | 2017-12-22 | 2018-05-22 | 帝斯曼先达合成树脂(佛山)有限公司 | A kind of preparation method of new bio matrix soap-free nucleocapsid aqueous acrylic emulsion |
| CN108727952A (en) * | 2018-05-08 | 2018-11-02 | 浙江大桥油漆有限公司 | A kind of self-emulsification aqueous alkyd resin and self-emulsification aqueous alkyd paint and preparation method |
| CN108977015A (en) * | 2018-08-17 | 2018-12-11 | 重庆南方漆业有限公司 | A kind of water alcohol acid finishing coat and its preparation method and application |
| CN108976399A (en) * | 2018-08-17 | 2018-12-11 | 重庆南方漆业有限公司 | A kind of aqueous alkide resin and preparation method thereof |
| CN116535949A (en) * | 2023-05-23 | 2023-08-04 | 太仓斯迪克新材料科技有限公司 | Quick-drying antistatic coating liquid for bottom coating, antistatic film and preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375535A (en) * | 2001-03-15 | 2002-10-23 | 海洋化工研究院 | Acrylic acid modified high-performance water-thinned alkyd enamal |
| CN1405254A (en) * | 2001-09-18 | 2003-03-26 | 海洋化工研究院 | Water-based acrylic acid modified alcoholic acid amino baking paint |
| WO2010023532A1 (en) * | 2008-08-26 | 2010-03-04 | Ennatura Technology Ventures (P) Ltd. | Water reducible alkyd resins |
| CN102675653A (en) * | 2011-03-18 | 2012-09-19 | 上海涂料有限公司技术中心 | Method for preparing waterborne acrylic modified alkyd emulsion |
-
2013
- 2013-08-13 CN CN2013103509875A patent/CN103467747A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375535A (en) * | 2001-03-15 | 2002-10-23 | 海洋化工研究院 | Acrylic acid modified high-performance water-thinned alkyd enamal |
| CN1405254A (en) * | 2001-09-18 | 2003-03-26 | 海洋化工研究院 | Water-based acrylic acid modified alcoholic acid amino baking paint |
| WO2010023532A1 (en) * | 2008-08-26 | 2010-03-04 | Ennatura Technology Ventures (P) Ltd. | Water reducible alkyd resins |
| CN102675653A (en) * | 2011-03-18 | 2012-09-19 | 上海涂料有限公司技术中心 | Method for preparing waterborne acrylic modified alkyd emulsion |
Non-Patent Citations (3)
| Title |
|---|
| 徐支有，等: ""水性丙烯酸改性醇酸氨基烤漆的制备与性能研究"", 《上海涂料》 * |
| 耿耀宗: "《现代水性涂料》", 31 March 2003, 中国石化出版社 * |
| 邓舜扬: "《新型涂料配方与工艺》", 30 June 2009, 中国石化出版社 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497221A (en) * | 2014-12-04 | 2015-04-08 | 北京金汇利应用化工制品有限公司 | Waterborne acrylic modified alkyd resin and preparation method of aqueous dispersion of alkyd resin |
| CN104877084A (en) * | 2014-12-04 | 2015-09-02 | 北京金汇利应用化工制品有限公司 | Aqueous acrylic acid modified alkyd resin and water dispersion thereof |
| CN104559708A (en) * | 2015-02-04 | 2015-04-29 | 浙江天女集团制漆有限公司 | Water-borne acrylic modified alkyd enamel and preparation method thereof |
| CN104788663A (en) * | 2015-04-17 | 2015-07-22 | 广西藤县通轩立信化学有限公司 | Water-soluble alkyd resin |
| CN104774522B (en) * | 2015-05-01 | 2017-01-11 | 温州市欧霖涂料有限公司 | Heat insulation paint preparation method |
| CN104774522A (en) * | 2015-05-01 | 2015-07-15 | 李亮军 | Heat insulation paint preparation method |
| CN104945605A (en) * | 2015-05-20 | 2015-09-30 | 安徽省金盾涂料有限责任公司 | Acrylic-acid-modified water-based alkyd resin and preparation method thereof |
| CN104829790A (en) * | 2015-05-31 | 2015-08-12 | 山东帝高漆业有限公司 | Preparation method of water-soluble acrylic modified alkyd resin |
| CN105925042A (en) * | 2016-05-27 | 2016-09-07 | 广西梧州龙鱼漆业有限公司 | Quick drying paint |
| CN106380967A (en) * | 2016-09-05 | 2017-02-08 | 肇庆千江高新材料科技股份公司 | Ultra-high-weatherability water-based paint, water-based castor oil modified alkyd resin and preparation methods thereof |
| CN107955101A (en) * | 2017-12-19 | 2018-04-24 | 上海华谊精细化工有限公司 | A kind of preparation method of oxidation cross-linked type aqueous acrylic emulsion |
| CN108059695A (en) * | 2017-12-22 | 2018-05-22 | 帝斯曼先达合成树脂(佛山)有限公司 | A kind of preparation method of new bio matrix soap-free nucleocapsid aqueous acrylic emulsion |
| CN108727952A (en) * | 2018-05-08 | 2018-11-02 | 浙江大桥油漆有限公司 | A kind of self-emulsification aqueous alkyd resin and self-emulsification aqueous alkyd paint and preparation method |
| CN108977015A (en) * | 2018-08-17 | 2018-12-11 | 重庆南方漆业有限公司 | A kind of water alcohol acid finishing coat and its preparation method and application |
| CN108976399A (en) * | 2018-08-17 | 2018-12-11 | 重庆南方漆业有限公司 | A kind of aqueous alkide resin and preparation method thereof |
| CN116535949A (en) * | 2023-05-23 | 2023-08-04 | 太仓斯迪克新材料科技有限公司 | Quick-drying antistatic coating liquid for bottom coating, antistatic film and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103467747A (en) | Preparation method for water-based acrylic acid modified alkyd emulsion and its amino baking varnish | |
| CN103467748A (en) | Preparation method for waterborne acrylic acid modified epoxy ester emulsion and its amino baking varnish | |
| CN101824209B (en) | Preparation method of polyester acrylate hybrid aqueous dispersion | |
| CN101942077B (en) | Air-drying water-reducible alkyd resin containing sulfonate base | |
| CN104877084A (en) | Aqueous acrylic acid modified alkyd resin and water dispersion thereof | |
| CN102643392B (en) | Synthesis method of styrene/acrylate-modified quick-drying water-based alkyd resin | |
| CN102675653B (en) | Method for preparing waterborne acrylic modified alkyd emulsion | |
| RU2484113C2 (en) | Plaste-forming resin for universal pigment paste | |
| CN1957048B (en) | Coating composition comprising a vinyl modified alkyd resin | |
| CN102807807B (en) | Paint used for coiled metal material | |
| CN104497221A (en) | Waterborne acrylic modified alkyd resin and preparation method of aqueous dispersion of alkyd resin | |
| CA2243297C (en) | Water-borne hybrid binder composition and use thereof | |
| CN103554381A (en) | Water-based acrylic acid modified saturated polyester resin and preparation method thereof | |
| CN103467727A (en) | Preparation method of water soluble polyester resin and its amino baking varnish | |
| CN102875945A (en) | Preparation method for polyester and acrylate mixed aqueous dispersoid | |
| CN104479087A (en) | Rapid dry type water-based epoxy ester emulsion and preparation method and application thereof | |
| JP2011511142A (en) | Wetting and dispersing agent | |
| CA1101576A (en) | Aqueous coating composition of an acrylic-vinyl oxazoline ester polymer | |
| CN110156933A (en) | A kind of high weather resistant water-thinned alkyd paint lotion of quick-drying bloom and preparation method | |
| CN101747500A (en) | Sulphonate-base water-reducible alkyd resin and amino baking paint thereof | |
| CN103360575A (en) | Aqueous organic salt modified epoxy ester resin, and preparation method and application thereof | |
| CN114773970A (en) | Water-based high-volume solid-content steel structure normal-temperature anticorrosive paint and preparation method thereof | |
| CN105949439A (en) | Preparation method of waterborne modified epoxy resin | |
| US8969438B2 (en) | Pigment concentrate | |
| CN112759720B (en) | Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131225 |