CN102585693A - Method for preparing epoxy acrylate modified waterborne polyurethane coating - Google Patents

Method for preparing epoxy acrylate modified waterborne polyurethane coating Download PDF

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CN102585693A
CN102585693A CN2012100608592A CN201210060859A CN102585693A CN 102585693 A CN102585693 A CN 102585693A CN 2012100608592 A CN2012100608592 A CN 2012100608592A CN 201210060859 A CN201210060859 A CN 201210060859A CN 102585693 A CN102585693 A CN 102585693A
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epoxy acrylate
acrylate modified
polyurethane coating
aqueous polyurethane
preparing
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沈国俭
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CHANGSHU XIEXIN METALLURG MATERIAL Co Ltd
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CHANGSHU XIEXIN METALLURG MATERIAL Co Ltd
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Abstract

The invention discloses a method for preparing epoxy acrylate modified waterborne polyurethane coating and belongs to the technical field of chemical coatings. The method comprises the following steps: A) synthetizing modified epoxy acrylate; B) preparing an epoxy acrylate modified waterborne polyurethane emulsion; and C) preparing the finished product epoxy acrylate modified waterborne polyurethane coating. The epoxy acrylate modified waterborne polyurethane coating has the advantages of excellent bondability of epoxy resin, high modulus, high strength, high adhesive force, low shrink rate, water resistance and chemistry resistance. The epoxy acrylate modified waterborne polyurethane coating has excellent water resistance, physical property and weather resistance of acrylate ester; the raw materials are easy to obtain and have low cost; and the epoxy acrylate modified waterborne polyurethane coating has good physical performance and cold resistance of waterborne polyurethane and has environment protection property.

Description

The method for preparing the epoxy acrylate modified aqueous polyurethane coating
Technical field
The invention belongs to the chemistry painting industry technical field, be specifically related to a kind of method for preparing the epoxy acrylate modified aqueous polyurethane coating
Background technology
aqueous polyurethane has good physics characteristic and good winter hardiness, is to develop green material faster, still; Single polyaminoester emulsion poor from thickening property, solids content is low, and the water resistance of latex film is poor; Physical strength is low, and glossiness is low, and cost is high.Like the disclosed a kind of bicomponent polyurethane coating of Chinese patent publication number CN101457120A and working method, constructional method; Polyacrylate emulsion has preferably water tolerance, physics characteristic and weather resistance and is widely used in coating industry, like the disclosed a kind of acrylic emulsion coatings that is used for rubber item of Chinese patent publication number CN1179745A; Epoxy resin has advantages such as the outstanding ability of cohering, high-modulus, HS, good sticking power, low-shrinkage, water-fast and chemical resistant properties be good, is the important component part of traditional coating.Like the disclosed a kind of environment-friendly type normal temperature solidifying water epoxy resin coating of Chinese patent publication number CN101085898A.
still do not have the comparatively perfect polyurethane water-based paint of over-all properties in view of in the prior art; On performance, be difficult to satisfy people's demand again in view of simple aqueous polyurethane; Therefore utilize the outstanding ability of cohering of epoxy resin, high-modulus, HS, good sticking power, low-shrinkage and water-fast, advantage such as chemical resistant properties is good and propenoate water tolerance, physics characteristic and weather resistance and characteristics with low cost preferably; Through the graft copolymerization mode both resins are introduced in the aqueous polyurethane segment; Aqueous polyurethane is carried out modification, process the research that environmental protection and various aspects of performance all can be significantly improved by this and have positive effect.
Based on such background, the present inventor has done a large amount of further investigation work, and has done useful exploration, has invented to solve above-mentioned insufficient technical scheme
Summary of the invention
the purpose of this invention is to provide a kind of method for preparing the epoxy acrylate modified aqueous polyurethane coating; Not only have the outstanding ability of cohering of epoxy resin, high-modulus, HS, good sticking power, low-shrinkage, water-fast and chemical resistant properties by the coating of this method preparation; And have water tolerance, physics characteristic and weather resistance that propenoate stands out from one's fellows and characteristics with low cost, also have good physics characteristic and the good winter hardiness of aqueous polyurethane and have green environmental protection.
Task of the present invention is accomplished like this, and a kind of method for preparing the epoxy acrylate modified aqueous polyurethane coating may further comprise the steps:
A). synthesizing of modified epoxy acrylic ester
In four-hole boiling flask 1, add by weight epoxy resin 6-8 part, properties-correcting agent 0.2-0.4 part and catalyzer 0.002-0.003 part, be heated to 75-85 ℃, add stopper 0.01-0.04 part; The mixing solutions of dropwise addition of acrylic acid class monomer 2-3 part and catalyzer 0.001-0.003 part; In 30-60min, drip, then be warmed up to 85~90 ℃, every separated 60min sampling detecting acid number 1 time; When acid number during less than 5mgKOH/g, cooling obtains the epoxy acrylate of modification;
B). preparation epoxy acrylate modified waterborne polyurethane emulsion
By weight, in the four-hole boiling flask that whisking appliance, TM, prolong and nitrogen conduit are housed 2, add methyl-2,4-vulcabond 4-6 part; Drip properties-correcting agent 0.5-0.6 part at normal temperatures and under protection of nitrogen gas, be warming up to 60~65 ℃ after dropwising, and the variation of tracking-NCO massfraction; When near theoretical value n (NCO)/ modified epoxy acrylic ester and catalyzer 0.001-0.003 part that n (cool to 50 ℃ when OH) being 1.3~1.4, add dimethylol propionic acid 4-6 part and steps A) makes, slowly be warmed up to 75~80 ℃; After the dimethylol propionic acid small-particle disappears, be cooled to 50 ℃, add stopper 0.01-0.06 part, mixing; Dropwise addition of acrylic acid class monomer 6-11 part slowly is warmed up to 70~75 ℃ after being added dropwise to complete, be cooled to 50 ℃; Add neutralizing agent 3-8 part; In with the time be 12-18min, drip the dilution of deionized water 45-65 part at control rotating speed 750-850r/min whipped state, obtain epoxy acrylate modified waterborne polyurethane emulsion;
C). the epoxy acrylate modified aqueous polyurethane coating of preparation finished product
add step B in having the reactor drum of whisking appliance) the epoxy acrylate modified aqueous polyurethane emulsion that obtains; Open and stir; Under control rotating speed 200~300r/min whipped state, add initiator 0.05-0.1 part, auxiliary agent and water-based paint successively; After stirring 25-35min, filter discharging, promptly obtain the epoxy acrylate modified aqueous polyurethane coating.
in a concrete embodiment of the present invention, described acrylic monomer is more than one in vinylformic acid, Bing Xisuandingzhi, Hydroxyethyl acrylate and the TEB 3K.
in another concrete embodiment of the present invention, described stopper is a p methoxy phenol.
in another concrete embodiment of the present invention, described initiator is Potassium Persulphate or ammonium persulphate.
in another concrete embodiment of the present invention, described properties-correcting agent is W 166 (PPG600), W 166 (PPG1000) or W 166 (PPG2000).
also have among the concrete embodiment of the present invention, and described catalyzer is a dibutyl tin laurate.
are more of the present invention and among concrete embodiment, described epoxy resin is E-51 or E-44.
in of the present invention and then concrete embodiment, described neutralizing agent is a triethylamine.
of the present invention again more and among concrete embodiment, described auxiliary agent is more than one in solubility promoter, wetting agent, flow agent, scratch resistance, dispersion agent, skimmer, matting agent and the rheological agent.
are again of the present invention and then and among concrete embodiment, described water-based paint is red iron oxide, iron mica, Soxylat A 25-7 carbon black or disperses copper phthalcyanine.
The resulting epoxy acrylate modified aqueous polyurethane coating of preparation method provided by the invention has outstanding agglutinating value(of coal), high-modulus, HS, high adhesive force, low-shrinkage, the water-fast and chemical resistant properties of epoxy resin; The water tolerance of standing out from one's fellows, physical property and the weathering resistance and the raw material that also have propenoate are easy to get with low cost; And then have the good physicals and a cold tolerance of aqueous polyurethane; More has the feature of environmental protection.
Embodiment
Embodiment 1:
A). synthesizing of modified epoxy acrylic ester
In four-hole boiling flask, add 0.2 part of 6 parts of epoxy resin E-51, W 166 (PPG600) and 0.002 part of catalyzer dibutyl tin laurate by weight; Slowly be heated to 80 ℃, add 0.02 part of 0.01 part of stopper p methoxy phenol behind the reaction 15min, the mixing solutions of 2 parts of 1 part of dropwise addition of acrylic acid and Bing Xisuandingzhis and 0.002 part of catalyzer dibutyl tin laurate; About 0.5h drips; Slowly be warmed up to 75 ℃, every at a distance from 1h sampling detecting acid number 1 time, when acid number during less than 5mgKOH/g; Cooling obtains the LV modified epoxy acrylic ester;
B). preparation epoxy acrylate modified waterborne polyurethane emulsion
In the four-hole boiling flask that whisking appliance, TM, prolong and nitrogen conduit are housed, add the methyl-2 that takes by weighing by weight, 4 parts of 4-vulcabond drip properties-correcting agent W 166 (PPG600) 0.3 part under normal temperature and protection of nitrogen gas; After dropwising, slowly be warmed up to 60 ℃, reaction; The variation of tracking-NCO massfraction, when near theoretical value n (NCO)/0.001 part of modified epoxy acrylic ester that n (cool to 50 ℃ when OH) being 1.3, add 6.5 parts of dimethylol propionic acids to add by steps A) obtains and catalyzer dibutyl tin laurate; Slowly be warmed up to 75 ℃, reaction 18min is cooled to 50 ℃ after the dimethylol propionic acid small-particle disappears; Add 0.01 part of stopper p methoxy phenol, mix 6 parts of dropwise addition of acrylic acid hydroxyl ethyl esters; Slowly be warmed up to 70 ℃ after being added dropwise to complete, reaction 2h is cooled to 50 ℃; Add 3 parts of neutralizing agent triethylamines by weight; In be about 15min with the time, under control rotating speed 850r/min whipped state, drip 65 parts of dilutions of deionized water at leisure, obtain epoxy acrylate modified waterborne polyurethane emulsion;
C). preparation epoxy acrylate modified aqueous polyurethane coating
add step B in having the reactor drum of whisking appliance) the epoxy acrylate modified aqueous polyurethane emulsion that makes; Open and stir; Under control rotating speed 200r/min whipped state, adding initiator successively is that 0.05 part of Potassium Persulphate, auxiliary agent and water-based paint are 0.001 part of red iron oxide; After stirring 30min is uniformly dispersed; Filter discharging; Promptly obtain finished product epoxy acrylate modified aqueous polyurethane coating, wherein said auxiliary agent is: 2 parts of 0.2 part of 2 parts of solubility promoter Flow425 (the high reagent of German enlightening), wetting agent dispers 750w (Germany wins the wound chemistry), 1 part of dispersion agent Rewopal M 365 (Germany wins the wound chemistry), 0.2 part of skimmer byk-054 (German Bi Ke chemistry), matting agent CERAFLOUR 929 (German Bi Ke chemistry) and 0.5 part of rheological agent byk-E-420 (German Bi Ke chemistry).
Embodiment 2:
A). synthesizing of modified epoxy acrylic ester
0.2 part of adding 8 parts of epoxy resin E-51, W 166 (PPG1000) by weight and catalyzer dibutyl tin laurate are 0.002 part in four-hole boiling flask; Slowly be heated to 80 ℃; Add 0.02 part of 0.01 part of stopper p methoxy phenol behind the reaction 15min, the mixing solutions of 2 parts of 1 part of dropwise addition of acrylic acid and TEB 3Ks and 0.002 part of catalyzer dibutyl tin laurate, about 0.5h drips; Slowly be warmed up to 86 ℃; Every at a distance from 1h sampling detecting acid number 1 time, when acid number during less than 5mgKOH/g, cooling obtains the LV modified epoxy acrylic ester;
B). preparation epoxy acrylate modified waterborne polyurethane emulsion
In the four-hole boiling flask that whisking appliance, TM, prolong, nitrogen conduit are housed, add methyl-2 by weight, 4 parts of 4-vulcabond drip properties-correcting agent W 166 (PPG1000) 0.4 part under normal temperature and protection of nitrogen gas; After dropwising, slowly be warmed up to 65 ℃, the variation of reaction tracking-NCO massfraction; Near theoretical value n (NCO)/0.002 part of modified epoxy acrylic ester that n (be to cool to 50 ℃ at 1.3 o'clock OH), add 7 parts of dimethylol propionic acids by steps A) makes and catalyzer dibutyl tin laurate, slowly be warmed up to 80 ℃; Reaction 12min is cooled to 50 ℃ after the dimethylol propionic acid small-particle disappears, add 0.02 part of stopper p methoxy phenol; Mix, 8 parts of dropwise addition of acrylic acid hydroxyl ethyl esters slowly are warmed up to 75 ℃ after being added dropwise to complete; Reaction 2h; Be cooled to 50 ℃, add 5 parts of neutralizing agent triethylamines, in be about 15min with the time; Under control rotating speed 800r/min whipped state, drip 60 parts of dilutions of deionized water at leisure, obtain epoxy acrylate modified waterborne polyurethane emulsion;
C). preparation epoxy acrylate modified aqueous polyurethane coating
add by step B in the reactor drum that has whisking appliance) the epoxy acrylate modified aqueous polyurethane emulsion that makes; Open and stir; Under control rotating speed 200r/min whipped state, adding initiator by weight successively is that 0.06 part of ammonium persulphate, auxiliary agent and water-based paint are 0.003 part of iron mica; After stirring 30min is uniformly dispersed; Filter discharging; Promptly obtain finished product epoxy acrylate modified aqueous polyurethane coating, wherein said auxiliary agent is: 3 parts of 0.1 part of 3 parts of solubility promoter Flow425 (the high reagent of German enlightening), wetting agent dispers750w (Germany wins the wound chemistry), 0.1 part of flow agent byk-354 (German Bi Ke chemistry), 0.4 part of scratch resistance CERAFLOUR 996 (German Bi Ke chemistry), dispersion agent Rewopal M 365 (Germany wins the wound chemistry) and 0.5 part of skimmer byk-054 (German Bi Ke chemistry).
Embodiment 3:
A). synthesizing of modified epoxy acrylic ester
0.3 part of adding 7 parts of epoxy resin E-44s, W 166 (PPG2000) by weight and catalyzer dibutyl tin laurate are 0.003 part in four-hole boiling flask; Slowly be heated to 80 ℃; Add 0.03 part of 0.01 part of stopper p methoxy phenol behind the reaction 15min, the mixing solutions of 2 parts of dropwise addition of acrylic acid and 0.003 part of catalyzer dibutyl tin laurate, 0.5h drips; Slowly be warmed up to 88 ℃; Every at a distance from 1h sampling detecting acid number 1 time, when acid number during less than 5mgKOH/g, cooling obtains the LV modified epoxy acrylic ester;
B). preparation epoxy acrylate modified waterborne polyurethane emulsion
TM is equipped with the methyl-2 that adds in the four-hole boiling flask of whisking appliance, TM, prolong and nitrogen conduit by weight, 6 parts of 4-vulcabond, dropping properties-correcting agent W 166 (PPG2000) 0.5 part under normal temperature and protection of nitrogen gas; After dropwising, slowly be warmed up to 63 ℃, the variation of reaction tracking-NCO massfraction; Near theoretical value n (NCO)/0.003 part of modified epoxy acrylic ester that n (be to cool to 50 ℃ at 1.4 o'clock OH), add 7.5 parts of dimethylol propionic acids and steps A) makes and catalyzer dibutyl tin laurate, slowly be warmed up to 77 ℃; Reaction 15min is cooled to 50 ℃ after the dimethylol propionic acid small-particle disappears, add 0.03 part of stopper p methoxy phenol; Mix, 7 parts of dropwise addition of acrylic acid hydroxyl ethyl esters slowly are warmed up to 72 ℃ after being added dropwise to complete; Reaction 2h; Be cooled to 50 ℃, add 8 parts of neutralizing agent triethylamines, in be about 15min with the time; Under control rotating speed 800r/min whipped state, drip 55 parts of dilutions of deionized water at leisure, obtain epoxy acrylate modified waterborne polyurethane emulsion;
C). preparation epoxy acrylate modified aqueous polyurethane coating
add step B in the reactor drum that has whisking appliance) the epoxy acrylate modified aqueous polyurethane emulsion that makes; Open and stir; Under control rotating speed 200r/min whipped state, adding 0.09 part of initiator potassium persulfate, auxiliary agent and water-based paint by weight successively is 0.008 part of Soxylat A 25-7 carbon black; After stirring 30min is uniformly dispersed; Filter discharging; Promptly obtain finished product epoxy acrylate modified aqueous polyurethane coating, wherein said auxiliary agent is: 2 parts of 0.1 part of 3 parts of solubility promoter Flow425 (the high reagent of German enlightening), wetting agent dispers750w (Germany wins the wound chemistry), 0.1 part of flow agent byk-354 (German Bi Ke chemistry), 0.3 part of scratch resistance CERAFLOUR 996 (German Bi Ke chemistry), 1 part of dispersion agent Rewopal M 365 (Germany wins the wound chemistry), 0.1 part of skimmer byk-054 (German Bi Ke chemistry), matting agent CERAFLOUR 929 (German Bi Ke chemistry) and 1.4 parts of rheological agent byk-E-420 (German Bi Ke chemistry).
Embodiment 4:
A). synthesizing of modified epoxy acrylic ester
0.4 part of adding 7 parts of epoxy resin E-44s, W 166 (PPG600) by weight and catalyzer dibutyl tin laurate are 0.002 part in four-hole boiling flask; Slowly be heated to 80 ℃; Add 0.02 part of 0.01 part of stopper p methoxy phenol behind the reaction 15min, the mixing solutions that 1 part of dropwise addition of acrylic acid, 2 parts of Bing Xisuandingzhis and catalyzer dibutyl tin laurate are 0.002 part, about 0.5h drips; Slowly be warmed up to 90 ℃; Every at a distance from 1h sampling detecting acid number 1 time, when acid number during less than 5mgKOH/g, cooling obtains the LV modified epoxy acrylic ester;
B). preparation epoxy acrylate modified waterborne polyurethane emulsion
In the four-hole boiling flask that whisking appliance, TM, prolong and nitrogen conduit are housed, add methyl-2 by weight, 4 parts of 4-vulcabond drip properties-correcting agent W 166 (PPG600) 0.5 part under normal temperature and protection of nitrogen gas; After dropwising, slowly be warmed up to 65 ℃, the variation of reaction tracking-NCO massfraction; Near theoretical value n (NCO)/0.001 part of modified epoxy acrylic ester that n (be to cool to 50 ℃ at 1.3 o'clock OH), add 7 parts of dimethylol propionic acids and by steps A) makes and catalyzer dibutyl tin laurate, slowly be warmed up to 75 ℃; Reaction 15min is cooled to 50 ℃ after the dimethylol propionic acid small-particle disappears, add 0.02 part of stopper p methoxy phenol; Mix, 6 parts of dropwise addition of acrylic acid hydroxyl ethyl esters slowly are warmed up to 80 ℃ after being added dropwise to complete; Reaction 2h; Be cooled to 50 ℃, add 6 parts of neutralizing agent triethylamines, in be about 15min with the time; Under control rotating speed 800r/min whipped state, drip 45 parts of dilutions of deionized water at leisure, obtain epoxy acrylate modified waterborne polyurethane emulsion;
C). preparation epoxy acrylate modified aqueous polyurethane coating
add by step B in the reactor drum that has whisking appliance) the epoxy acrylate modified aqueous polyurethane emulsion that makes; Open and stir; Under control rotating speed 300r/min whipped state, add 0.1 part of initiator potassium persulfate, auxiliary agent and water-based paint by weight successively and disperse 0.01 part of copper phthalcyanine; After stirring 30min is uniformly dispersed; Filter discharging; Promptly obtain finished product epoxy acrylate modified aqueous polyurethane coating, wherein said auxiliary agent is: 3 parts of 0.5 part of 5 parts of solubility promoter Flow425 (the high reagent of German enlightening), wetting agent dispers750w (Germany wins the wound chemistry), 0.2 part of flow agent byk-354 (German Bi Ke chemistry), 0.5 part of scratch resistance CERAFLOUR 996 (German Bi Ke chemistry), 3 parts of dispersion agent Rewopal M 365 (Germany wins the wound chemistry), 0.5 part of skimmer byk-054 (German Bi Ke chemistry), matting agent CERAFLOUR 929 (German Bi Ke chemistry) and 2 parts of rheological agent byk-E-420 (German Bi Ke chemistry).
Embodiment 5:
A). synthesizing of modified epoxy acrylic ester
0.2 part of adding 6 parts of epoxy resin E-51, W 166 (PPG600) by weight and catalyzer dibutyl tin laurate are 0.002 part in four-hole boiling flask; Slowly be heated to 80 ℃; Add 0.01 part of 0.01 part of stopper p methoxy phenol behind the reaction 15min, the mixing solutions that 1 part of dropwise addition of acrylic acid, 3 parts of Bing Xisuandingzhis and catalyzer dibutyl tin laurate are 0.002 part, about 0.5h drips; Slowly be warmed up to 87 ℃; Every at a distance from 1h sampling detecting acid number 1 time, when acid number during less than 5mgKOH/g, cooling obtains the LV modified epoxy acrylic ester;
B). preparation epoxy acrylate modified waterborne polyurethane emulsion
add methyl-2 by weight in the four-hole boiling flask that whisking appliance, TM, prolong and nitrogen conduit are housed; 4 parts of 4-vulcabond; Under normal temperature and protection of nitrogen gas, drip properties-correcting agent W 166 (PPG600) 0.3 part; After dropwising, slowly be warmed up to 62 ℃.The variation of reaction trackings-NCO massfraction, near theoretical value n (NCO)/0.001 part of modified epoxy acrylic ester that n (OH) be 1.3 o'clock cool to 50 ℃, 6.5 parts of dimethylol propionic acids of adding and steps A) makes and catalyzer dibutyl tin laurate; Slowly be warmed up to 78 ℃, reaction 15min is cooled to 50 ℃ after the dimethylol propionic acid small-particle disappears; Add 0.02 part of stopper p methoxy phenol, mix 6 parts of dropwise addition of acrylic acid hydroxyl ethyl esters; Slowly be warmed up to 75 ℃ after being added dropwise to complete, reaction 2h is cooled to 50 ℃; Add 5 parts of neutralizing agent triethylamines; In be about 15min with the time, under control rotating speed 800r/min whipped state, drip 60 parts of dilutions of deionized water at leisure, obtain epoxy acrylate modified waterborne polyurethane emulsion;
C). preparation epoxy acrylate modified aqueous polyurethane coating
add by step B in the reactor drum that has whisking appliance) the epoxy acrylate modified aqueous polyurethane emulsion that makes; Open and stir; Under control rotating speed 260r/min whipped state, add 0.05 part of initiator potassium persulfate, auxiliary agent and water-based paint (with embodiment 1) by weight successively; After stirring 30min is uniformly dispersed; Filter discharging; Promptly obtain finished product epoxy acrylate modified aqueous polyurethane coating, wherein said auxiliary agent is: 1 part of 0.2 part of 3 parts of solubility promoter Flow425 (the high reagent of German enlightening), wetting agent dispers 750w (Germany wins the wound chemistry), 0.1 part of flow agent byk-354 (German Bi Ke chemistry), 0.5 part of scratch resistance CERAFLOUR 996 (German Bi Ke chemistry), 2 parts of dispersion agent Rewopal M 365 (Germany wins the wound chemistry), 0.2 part of skimmer byk-054 (German Bi Ke chemistry), matting agent CERAFLOUR 929 (German Bi Ke chemistry) and 1.8 parts of rheological agent byk-E-420 (German Bi Ke chemistry).
have the excellent technique effect shown in the following table by the epoxy acrylate modified aqueous polyurethane coating that the foregoing description 1-5 obtains through detection.
Figure 2012100608592100002DEST_PATH_IMAGE001

Claims (10)

1. A kind of method for preparing the epoxy acrylate modified aqueous polyurethane coating is characterized in that may further comprise the steps:
A) modified epoxy acrylic ester is synthetic
In four-hole boiling flask 1, add by weight epoxy resin 6-8 part, properties-correcting agent 0.2-0.4 part and catalyzer 0.002-0.003 part, be heated to 75-85 ℃, add stopper 0.01-0.04 part; The mixing solutions of dropwise addition of acrylic acid class monomer 2-3 part and catalyzer 0.001-0.003 part; In 30-60min, drip, then be warmed up to 85~90 ℃, every separated 60min sampling detecting acid number 1 time; When acid number during less than 5mgKOH/g, cooling obtains the epoxy acrylate of modification;
B) preparation epoxy acrylate modified waterborne polyurethane emulsion
By weight, in the four-hole boiling flask that whisking appliance, TM, prolong and nitrogen conduit are housed 2, add methyl-2,4-vulcabond 4-6 part; Drip properties-correcting agent 0.5-0.6 part at normal temperatures and under protection of nitrogen gas, be warming up to 60~65 ℃ after dropwising, and the variation of tracking-NCO massfraction; When near theoretical value n (NCO)/ modified epoxy acrylic ester and catalyzer 0.001-0.003 part that n (cool to 50 ℃ when OH) being 1.3~1.4, add dimethylol propionic acid 4-6 part and steps A) makes, slowly be warmed up to 75~80 ℃; After the dimethylol propionic acid small-particle disappears, be cooled to 50 ℃, add stopper 0.01-0.06 part, mixing; Dropwise addition of acrylic acid class monomer 6-11 part slowly is warmed up to 70~75 ℃ after being added dropwise to complete, be cooled to 50 ℃; Add neutralizing agent 3-8 part; In with the time be 12-18min, drip the dilution of deionized water 45-65 part at control rotating speed 750-850r/min whipped state, obtain epoxy acrylate modified waterborne polyurethane emulsion;
C) the epoxy acrylate modified aqueous polyurethane coating of preparation finished product
add step B in having the reactor drum of whisking appliance) the epoxy acrylate modified aqueous polyurethane emulsion that obtains; Open and stir; Under control rotating speed 200~300r/min whipped state, add initiator 0.05-0.1 part, auxiliary agent and water-based paint successively; After stirring 25-35min, filter discharging, promptly obtain the epoxy acrylate modified aqueous polyurethane coating.
2. method for preparing the epoxy acrylate modified aqueous polyurethane coating according to claim 1 is characterized in that described acrylic monomer is more than one in vinylformic acid, Bing Xisuandingzhi, Hydroxyethyl acrylate and the TEB 3K.
3. method for preparing the epoxy acrylate modified aqueous polyurethane coating according to claim 1 is characterized in that described stopper is a p methoxy phenol.
4. method for preparing the epoxy acrylate modified aqueous polyurethane coating according to claim 1 is characterized in that described initiator is Potassium Persulphate or ammonium persulphate.
5. method for preparing the epoxy acrylate modified aqueous polyurethane coating according to claim 1 is characterized in that described properties-correcting agent is W 166 (PPG600), W 166 (PPG1000) or W 166 (PPG2000).
6. method for preparing the epoxy acrylate modified aqueous polyurethane coating according to claim 1 is characterized in that described catalyzer is a dibutyl tin laurate.
7. method for preparing the epoxy acrylate modified aqueous polyurethane coating according to claim 1 is characterized in that described epoxy resin is E-51 or E-44.
8. method for preparing the epoxy acrylate modified aqueous polyurethane coating according to claim 1 is characterized in that described neutralizing agent is a triethylamine.
9. method for preparing the epoxy acrylate modified aqueous polyurethane coating according to claim 1 is characterized in that described auxiliary agent is more than one in solubility promoter, wetting agent, flow agent, scratch resistance, dispersion agent, skimmer, matting agent and the rheological agent.
10. The method for preparing the epoxy acrylate modified aqueous polyurethane coating according to claim 1 is characterized in that described water-based paint is red iron oxide, iron mica, Soxylat A 25-7 carbon black or disperses copper phthalcyanine
CN2012100608592A 2012-03-09 2012-03-09 Method for preparing epoxy acrylate modified waterborne polyurethane coating Pending CN102585693A (en)

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CN109957086A (en) * 2017-12-14 2019-07-02 惠州市长润发涂料有限公司 A kind of synthetic method of the polyurethane acrylate resin of high-performance and low-cost
CN110698642A (en) * 2019-09-18 2020-01-17 江南大学 Polyurethane modified epoxy acrylate resin and preparation method thereof
CN113621301A (en) * 2021-08-23 2021-11-09 海南必凯水性新材料有限公司 Environment-friendly water-based paint, and preparation method and application thereof
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CN103450446B (en) * 2013-08-26 2016-02-03 江苏高博智融科技有限公司 A kind of synthetic method of modified bisphenol A epoxy acrylate
CN103450446A (en) * 2013-08-26 2013-12-18 无锡市金盛助剂厂 Synthesis method of modified bisphenol A epoxy acrylate
CN104610871A (en) * 2014-12-19 2015-05-13 长飞光纤光缆股份有限公司 Radiation curing coating
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CN106905504B (en) * 2017-03-22 2020-03-31 中山市千佑化学材料有限公司 Water-based ultraviolet-curing polyurethane resin and preparation method and application thereof
CN106905504A (en) * 2017-03-22 2017-06-30 中山市千佑化学材料有限公司 UV-curable waterborne polyurethane resin and its preparation method and application
CN109957086A (en) * 2017-12-14 2019-07-02 惠州市长润发涂料有限公司 A kind of synthetic method of the polyurethane acrylate resin of high-performance and low-cost
CN110698642A (en) * 2019-09-18 2020-01-17 江南大学 Polyurethane modified epoxy acrylate resin and preparation method thereof
CN113621301A (en) * 2021-08-23 2021-11-09 海南必凯水性新材料有限公司 Environment-friendly water-based paint, and preparation method and application thereof
CN114410174A (en) * 2022-02-24 2022-04-29 郑州中科新兴产业技术研究院 High-performance water-based acrylic polyurethane coating and preparation method thereof
CN114410174B (en) * 2022-02-24 2023-09-29 郑州中科新兴产业技术研究院 High-performance aqueous acrylic polyurethane coating and preparation method thereof
CN116574440A (en) * 2023-04-26 2023-08-11 广州市百庄复合材料有限公司 Water-based protective agent and preparation method thereof
CN116574440B (en) * 2023-04-26 2024-01-19 广州市百庄复合材料有限公司 Water-based protective agent and preparation method thereof

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Application publication date: 20120718