CN1710002A - Water-based polyurethane resin and its electrophoretic paint composition and preparing method - Google Patents
Water-based polyurethane resin and its electrophoretic paint composition and preparing method Download PDFInfo
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- CN1710002A CN1710002A CN 200510018926 CN200510018926A CN1710002A CN 1710002 A CN1710002 A CN 1710002A CN 200510018926 CN200510018926 CN 200510018926 CN 200510018926 A CN200510018926 A CN 200510018926A CN 1710002 A CN1710002 A CN 1710002A
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Abstract
The invention relates to a kind of polyurethane electrophoresis lacquer and its producing method, especially a kind of aqueous polyurethane resin and its producing method and electrophoresis lacquer compound with resin as main raw materials and its producing method. It adopts polyester polyol, HDI, modified epoxy resin, DMPA, and 2-hydroxyethyl methacrylate as raw material, and is produced through chemical reaction. Add initiator into aqueous polyurethane resin to produce electrophoresis lacquer. The artificial perspiration resistance of the polyurethane electrophoresis lacquer produced by the method can get over 24 hours. Besides its luminous fullness is over 90, hardness is over 4H, and water resistance is over 72 hours.
Description
Technical field
The present invention relates to a kind of urethane electrocoating paint and manufacture method thereof, a kind of especially waterbased urethane resin and preparation method thereof and be cataphoresis paint composition of main raw material and preparation method thereof with this resin.
Background technology:
At present the polyurethane resin coating that uses has solvent-borne type and water base two kinds.Solvent-borne type includes free tolylene diisocyanate (TDI) and a large amount of organic solvents.They cause very big harm to the healthy of human body and human living survival environment, are also relating to big danger.Along with the restriction of growing environmental regulation, the water-based resin that solvent type polyurethane resin is developed rapidly gradually substitutes, and this technology is subjected to people's growing interest at present.The more preparation that concentrates on the anionic polyurethane resin of bibliographical information that the preparation of water-based polyurethane resin is present, cationic water-based polyurethane resin synthetic document seldom.Water-based polyurethane resin is because molecular weight is little, and degree of crosslinking makes inadequately that the hardness of polyurethane coating is lower, water tolerance, chemical resistance are unsatisfactory.
(No.sho63 (1988)-69882 adopts and contains hydroxy acid base or sulfonic polyvalent alcohol and prepare the negatively charged ion water-based polyurethane resin of self-emulsifying as the wetting ability chainextender day disclosure (examination) patent, and the hardness of polyurethane coating prepared therefrom is lower, water tolerance, chemical resistance are still unsatisfactory.。
(9 (1997)-157625 of No.Hei propose to adopt dimethylol propionic acid as the wetting ability chainextender to the day disclosure (examination) patent.The performed polymer of at first preparing wetting ability NCO functional group dead-end then in containing the water of a small amount of diamine emulsification disperse to prepare the water base numerical value of anionic polyurethane urea, performance makes moderate progress than waterbased urethane, but its over-all properties is still undesirable.
Summary of the invention:
Technical problem to be solved by this invention is: a kind of preparation method with water-based polyurethane resin and this water-based polyurethane resin of novel molecular structure is provided.
Another object of the present invention is that a kind of preparation method who contains the cataphoresis paint composition and the electrocoating paint thereof of above-mentioned waterbased urethane also is provided.
Technical scheme of the present invention is achieved in that a kind of water-based polyurethane resin, and its structural formula is as follows:
Wherein, R
1, R
2, R
3For being alkyl, molecular weight is 3000-6000, preferred 5000.
Preparation method of the present invention comprises that the following step poly-:
(1) polyvalent alcohol and cyanate carry out polyreaction a few hours;
(2) then in the presence of solvent, add hydrophilizing agent stoichiometric number hour;
(3) add chainextender again and carry out chain extending reaction a few hours;
(4) add end-capping reagent stoichiometric number hour;
(5) add at last in and the salt forming agent stoichiometric number hour be prepared from water-based polyurethane resin;
Wherein each proportion of raw materials is (a weight fraction per-cent):
Polyvalent alcohol 23-30
Cyanate 25-36
Hydrophilizing agent 6.5-10.0
Chainextender 26-36
End-capping reagent 3.0-6.9
In and salt forming agent 5-7
Wherein, described polyvalent alcohol is that molecular weight is the 500-2000 polyester polyol, and preferred molecular weight is 1000 polyester polyol, the too high polyester polyol of molecular weight is as 4500,6000, and possible cleanliness factor is bigger, and the hard segment content of urethane is less, the hardness of paint film is lower, and mechanical property is relatively poor; It is not enough that molecular weight is crossed low snappiness less than 100.Except that using polyester polyol, also can use the polyether glycol of molecular weight as 1000-2000 as the raw material.
Described cyanate is a polyisocyanates, it is not limited to any specific a kind of, preferential employing is different Buddhist diketone vulcabond (1PDI) in the invention, the 1-6-hexamethylene-diisocyanate, 2-4-or 2, the 6-aliphatic diisocyanate also can use aromatic diisocyanate simultaneously, as methyl vulcabond and composition thereof 2,4-or 4,4-diphenylmethanediisocyanate or its mixture, also available aromatic series triisocyanate, as triphenyl methane-4,4,4-triisocyanate, 1,3,5-triisocyanate base benzene and 2,4,6-three isocyanato toluene etc.
Because the increase of chainextender reaction system viscosity is very fast, system need add a small amount of organic solvent and reduce viscosity, organic solvent should have the hydrophilic characteristics of isocyanate group inertia, it both can be low boiling point solvent, as acetone, butanone, tetrahydrofuran (THF), also can be middle high boiling solvent as 1,4-dioxane, N-Methyl pyrrolidone, two are gripped one or more in the alkane, preferred 1, the 4-dioxane is as organic solvent.
Described hydrophilizing agent is one or more of dimethylol propionic acid, dimethylolpropionic acid.The micromolecular amount that hydrophilizing agent contains tertiary N atom should be controlled within 15% ~ 20% the scope of total isocyanide ester group, because resin of the present invention is to use the electrophoresis process film forming, the specific conductivity of considering resin is necessary, the film thickness of the too high metallic surface of specific conductivity, luminance brightness, film outward appearance are very poor, can guarantee under the dispersive situation that the minimum of strict control hydrophilizing agent is essential.
Chainextender of the present invention is small molecular weight polyvalent alcohol such as ethylene glycol, propylene glycol, 1, and the 4-butyleneglycol, 1,3 butylene glycol, 1, ammediol, neopentyl glycol, glycol ether, triglycol, 1,4-dihydroxyl-2-butylene, bishydroxyethyl terephthalate, the lower molecular weight trivalent alcohol is as glycerine and have a low molecular weight polyols that is no less than four hydroxyls, as tetramethylol methane, D-mannitol and Xylitol; Perhaps small molecules diamine, as quadrol, propylene diamine 1,6-hexanediamine hydrazine and have the low molecular weight amine that is no less than three amino is as diethylenetriamine, Triethylenetetramine (TETA), tetren, penten and 2,2 '-diamino diethylamine.As the low molecular weight polyols of chainextender and low molecular weight polyamine can be used separately or two kinds three kinds mix and use.Wherein low molecular weight diol (1, the 4-butyleneglycol) and lower molecular weight trivalent alcohol (glycerine) all are preferred.
Except that above-mentioned traditional small molecule chain extender used, the also preferred a kind of novel chainextender of the present invention was used for reaction process, and this chainextender is the Resins, epoxy of methacrylic acid modification, the acrylic acid modified Resorcinol Resins, epoxy of preferable methyl.There is activity hydroxy at these chainextender molecule two ends, are still waiting the ethylenic unsaturation propyl moiety of radical polymerization, and altogether ultraviolet ray causes Raolical polymerizable usefulness, further improve the water-fast and resistance to chemical corrosion of urethane and intermetallic bonding and paint film.
Described end-capping reagent further reacts with the end capped performed polymer of above-mentioned isocyanato for (methyl) Hydroxyethyl acrylate.Available in addition Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate substitute hydroxyethyl methylacrylate.Hydroxyethyl methylacrylate contains hardness and the luminance brightness that methyl can improve paint film.Therefore end-capping reagent preferentially adopts hydroxyethyl methylacrylate in the invention.
Catalyzer can also be added during the present invention goes on foot poly-(4), consistent catalysts for polyurethanes can be selected for use, as organic tin, organic plumbous class.
Synthetic can be in water the dispersive cationic polyurethane resin, converting hydrophilic polymer to polyelectrolyte is an essential step.The salify neutralizing agent that the present invention adopts comprises various organic acids, as acetic acid, lactic acid and mineral acid etc.In preferred and salt forming agent be can evaporable acetic acid after the film forming.After reaction finishes, under reduced pressure remove organic solvent, reduce the harm of solvent HUMAN HEALTH and environment.
Temperature of reaction in the described step (1) is 40-150 ℃, and the reaction times is 0.5-5 hour, and preferable reaction temperature is 60-90 ℃, and the reaction times is 1.5-3 hour, and most preferably temperature of reaction is 75 ℃, and the reaction times is 2 hours.
Temperature of reaction in the step (2) is 40-120 ℃, and the reaction times is 0.5-8 hour, and preferable reaction temperature is 60-80 ℃, and the reaction times is 2-5 hour, and most preferably temperature of reaction is 75 ℃, and the reaction times is 2 hours
Temperature of reaction in the step (3) is 40-120 ℃, and the reaction times is 0.5-8 hour, and preferable reaction temperature is 60-80 ℃, and the reaction times is 2-5 hour, and most preferably temperature of reaction is 75 ℃, and the reaction times is 2 hours.
Temperature of reaction in the step (4) is 40-150 ℃, and the reaction times is 0.5-6 hour, and preferable reaction temperature is 50-90 ℃, and the reaction times is 2-4 hour, and most preferably temperature of reaction is 70 ℃, and the reaction times is 3 hours.
Temperature of reaction in the step (5) is 10-80 ℃, and the reaction times is 0.5-2 hour, and preferable reaction temperature is 30-60 ℃, and the reaction times is 0.5-1 hour, and most preferably temperature of reaction is 40 ℃, and the reaction times is 0.5 hour.
Utilize water-based polyurethane resin of the present invention can be prepared into a kind of cataphoresis paint composition, its proportion of raw materials is (a weight fraction per-cent):
The water-based polyurethane resin of claim 1: 80-90
Light trigger: 10-20
Wherein light trigger is one or more in Benzoin ethyl ether, methyl ether, the benzophenone.
In this cataphoresis paint composition, can add mill base 3-9, defoamer 0.1-0.5%
The aqueous based dispersions of urethane resin of the present invention can add the initiator of UV-light in the resin by water decomposition after reaction is finished, light trigger is aggregated in the micelle that thing is coated on polymkeric substance.When its be coated be contained in the body surface film forming after under the effect in UV-light, Raolical polymerizable takes place cause that secondary crosslinking improves every performance index of paint film.
The aqueous based dispersions of water-based polyurethane resin of the present invention both can be used as electrophoretic painting, also can be used as water base ultraviolet light polymerization varnish and was used for metal and nonmetallic application.
Contain the cohesive strength that epoxy construction has improved resin and metal in the molecular structure of the urethane resin of the present invention's narration, contain a large amount of alkene double-basis unsaturated chains, by improving water tolerance, chemical resistance, the thermostability of paint film after the reaction of radical polymerization secondary crosslinking greatly, in use do not need to add emulsifying agent, do not need 24 hours mechanical stirring.Waterbased urethane electrocoating paint artificial perspiration resistance with this method preparation reached more than 24 hours, and bright fullness ratio is greater than 90, and hardness is greater than 4H, and water tolerance is greater than more than 72 hours.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Fig. 2 is the chemical equation of each step of the present invention
Embodiment:
Fig. 1, Fig. 2 have clearly illustrated concrete preparation method of the present invention and step, below by embodiment the raw materials used and processing parameter of the present invention are described.
Embodiment 1: get molecular weight and be 5000 polyester polyol 23g, reacted 2 hours down at 75 ℃ with different Buddhist vulcabond (1PDI) 36g, then solvent two grip alkane in the presence of, reacted 2 hours down at 75 ℃ with dimethylol propionic acid 10g, again with methacrylic acid modification Resorcinol Resins, epoxy 16g, glycerine 8g, 1,4-butyleneglycol 8g is at 75 ℃ of following chain extending reactions after 2 hours, under the effect of catalyzer ethyl tin, down carried out end capping 3 hours with hydroxyethyl methylacrylate 5g at 70 ℃, be cooled to 40 ℃ at last, adding acetic acid 6g neutralization reaction was made water-based polyurethane resin in 0.5 hour.
After in above-mentioned water-based polyurethane resin, adding light trigger Benzoin ethyl ether 5g, mill base 3g, defoamer 0.1g again emulsification being sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from the urethane electrocoating paint.
Embodiment 2: get molecular weight and be 3000 polyether glycol 30g, reacted 4 hours down at 40 ℃ with methyl vulcabond 25g, then in the presence of solvent acetone, reacted 1 hour down at 40 ℃ with dimethylolpropionic acid 7g, again with methacrylic acid modification Resorcinol Resins, epoxy 20g, glycerine 10g is at 50 ℃ of following chain extending reactions after 2 hours, under the effect of catalyzer propyl group lead, 50 ℃ down and hydroxyethyl methylacrylate 3g carried out end capping 5 hours, be cooled to 10 ℃ at last, add lactic acid 5g neutralization reaction and made water-based polyurethane resin in 1 hour.
In above-mentioned water-based polyurethane resin, add light trigger methyl ether 5g again, after emulsification is sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from the urethane electrocoating paint.
Embodiment 3: get molecular weight and be 6000 polyether glycol 23g, with 2,4-diphenylmethanediisocyanate 25g reacted 6 hours down at 60 ℃, then in the presence of the solvent butanone, reacted 6 hours down at 60 ℃ with dimethylolpropionic acid 8g, again with methacrylic acid modification Resorcinol Resins, epoxy 18g, propanedioic acid 2g, Xylitol 5g, glycol ether 4g is at 80 ℃ of following chain extending reactions after 2 hours, under the effect of catalyst rings tin alkyl, down carried out end capping 5 hours at 80 ℃, be cooled to 60 ℃ at last and made water-based polyurethane resin in 2 hours with acetic acid 7g neutralization reaction with Hydroxyethyl acrylate 6g.
In above-mentioned water-based polyurethane resin, add light trigger benzophenone 6g again, after emulsification is sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from the urethane electrocoating paint.
Embodiment 4: get molecular weight and be 4000 polyester polyol 28g, reacted 1 hour down at 150 ℃ with methyl vulcabond 30g, then in the presence of solvents tetrahydrofurane, reacted 1 hour down at 120 ℃ with dimethylol propionic acid 6.5g, again with methacrylic acid modification Resorcinol Resins, epoxy 18g, diethylenetriamine 3g, 1,3-butyleneglycol 5g is at 120 ℃ of following chain extending reactions after 0.5 hour, under the effect of the rare basic tin of catalyzer second, down carried out end capping 1 hour at 140 ℃, be cooled to 80 ℃ of adding lactic acid 5g neutralization reactions at last and made water-based polyurethane resin in 2 hours with Rocryl 410 4.5g.
After in above-mentioned water-based polyurethane resin, adding light trigger Benzoin ethyl ether 2g, methyl ether 3g, mill base 3g again emulsification being sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from the urethane electrocoating paint.
Embodiment 5: get molecular weight and be 4000 polyester polyol 25g, with 4,4-ditan two cyanate 25g reacted 3 hours down at 60 ℃, then at solvent 1, under the existence of 4-dioxane, reacted 8 hours down at 80 ℃ with dimethylol propionic acid 7g, again with methacrylic acid modification Resorcinol Resins, epoxy 18g, 1,3-propanedioic acid 13g is at 100 ℃ of following chain extending reactions after 8 hours, under the effect of catalyzer methoxyl group tin, down carried out end capping 5 hours at 90 ℃ with hydroxyethyl methylacrylate 6.9g, be cooled to 50 ℃ of adding hydrochloric acid 5.1g neutralization reactions at last and made water-based polyurethane resin in 1 hour.
After in above-mentioned water-based polyurethane resin, adding light trigger Benzoin ethyl ether 1g, methyl ether 2g, benzophenone 2g, mill base 2g, defoamer 0.5g again emulsification being sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from the urethane electrocoating paint.
Embodiment 6: get molecular weight and be 5000 polyether glycol 23g, reacted 4 hours down at 90 ℃ with different Buddhist diketone vulcabond 25g, then in the presence of the solvent N-Methyl pyrrolidone, reacted 3 hours down at 60 ℃ with dimethylol propionic acid 8g, again with methacrylic acid modification Resorcinol Resins, epoxy 26g, triglycol 3g, tetramethylol methane 6g is at 90 ℃ of following chain extending reactions after 1 hour, at catalyzer 1, under the effect of 3-butadienyl tin, 100 ℃ down with hydroxyethyl methylacrylate 4g end capping 0.5 hour, be cooled to 10 ℃ and acetic acid 5g neutralization reaction at last and made waterbased urethane in 2 hours and set.
After in above-mentioned water-based polyurethane resin, adding light trigger Benzoin ethyl ether 1g, benzophenone 2g, mill base 2g, defoamer 0.5g again emulsification being sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from the urethane electrocoating paint.
Embodiment 7: get molecular weight and be 2000 polyester polyol 25g, with different Buddhist diketone vulcabond 5g, 1-6-hexamethylene-diisocyanate 15g, 4,4-ditan two cyanate 5g reacted 3 hours down at 60 ℃, then at solvent 1,4-dioxane and two is gripped under the existence of alkane, reacted 6 hours down at 80 ℃ with dimethylol propionic acid 7g, again with methacrylic acid modification Resorcinol Resins, epoxy 18g, 1,3-propanedioic acid 13g is at 100 ℃ of following chain extending reactions after 6 hours, under the effect of catalyzer methoxyl group tin, down carried out end capping 5 hours at 90 ℃, be cooled to 50 ℃ of adding hydrochloric acid 5.1g neutralization reactions at last and made water-based polyurethane resin in 1 hour with hydroxyethyl methylacrylate 6.9g.
After in above-mentioned water-based polyurethane resin, adding light trigger Benzoin ethyl ether 1g, methyl ether 2g, benzophenone 2g, mill base 2g, defoamer 0.5g again emulsification being sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from the urethane electrocoating paint.
Embodiment 8: get molecular weight and be 5000 polyester polyol 25g, with different Buddhist diketone vulcabond 5g, 4,4-triisocyanate 15g, 4,4-ditan two cyanate 5g reacted 3 hours down at 60 ℃, then at solvent 1, under the existence of 4-dioxane and acetone, reacted 8 hours down at 80 ℃ with dimethylol propionic acid 7g, again with methacrylic acid modification Resorcinol Resins, epoxy 18g, 1,3-propanedioic acid 13g is at 100 ℃ of following chain extending reactions after 5 hours, under the effect of catalyzer oxyethyl group tin, down carried out end capping 5 hours at 90 ℃ with hydroxyethyl methylacrylate 6.9g, be cooled to 50 ℃ of adding hydrochloric acid 5.1g neutralization reactions at last and made water-based polyurethane resin in 1 hour.
After in above-mentioned water-based polyurethane resin, adding light trigger Benzoin ethyl ether 1g, methyl ether 2g, benzophenone 2g, mill base 2g, defoamer 0.5g again emulsification being sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from the urethane electrocoating paint.
Embodiment 9: get molecular weight and be 4500 polyester polyol 25g, with different Buddhist diketone vulcabond 5g, 1,3,5-triisocyanate base benzene 15g, 4,4-ditan two cyanate 5g reacted 2 hours down at 60 ℃, then at solvent 1, under the existence of 4-dioxane and tetrahydrofuran (THF), reacted 4 hours down at 80 ℃ with dimethylol propionic acid 7g, again with methacrylic acid modification Resorcinol Resins, epoxy 18g, 1,3-propanedioic acid 13g is at 100 ℃ of following chain extending reactions after 4 hours, under the effect of catalyzer methoxyl group tin, down carried out end capping 5 hours at 90 ℃ with hydroxyethyl methylacrylate 6.9g, be cooled to 50 ℃ of adding hydrochloric acid 5.1g neutralization reactions at last and made water-based polyurethane resin in 2 hours.
After in above-mentioned water-based polyurethane resin, adding light trigger Benzoin ethyl ether 4g, mill base 2g, defoamer 0.5g again emulsification being sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from the urethane electrocoating paint.
Embodiment 10: get molecular weight and be 5000 polyester polyol 25g, with different Buddhist diketone vulcabond 15g, 4,4-ditan two cyanate 15g reacted 3 hours down at 60 ℃, then at solvent 1, under the existence of 4-dioxane and N-Methyl pyrrolidone, reacted 3 hours down at 80 ℃ with dimethylol propionic acid 7g, again with methacrylic acid modification Resorcinol Resins, epoxy 18g, 1,3-propanedioic acid 13g is at 100 ℃ of following chain extending reactions after 4 hours, under the effect of catalyzer methoxyl group tin, down carried out end capping 5 hours at 90 ℃ with hydroxyethyl methylacrylate 6.9g, be cooled to 50 ℃ of adding hydrochloric acid 5.1g neutralization reactions at last and made water-based polyurethane resin in 1.5 hours.
After in above-mentioned water-based polyurethane resin, adding light trigger Benzoin ethyl ether 1g, methyl ether 2g, benzophenone 2g, mill base 2g, defoamer 0.5g again emulsification being sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from the urethane electrocoating paint.
Embodiment 11: get molecular weight and be 5500 polyester polyol 25g, with different Buddhist diketone vulcabond 5g, 1,3,5-triisocyanate base benzene 15g, 4,4-ditan two cyanate 5g reacted 3 hours down at 60 ℃, then at solvent 1, under the existence of 4-dioxane and butanone, reacted 2 hours down at 80 ℃ with dimethylolpropionic acid 7g, again with methacrylic acid modification Resorcinol Resins, epoxy 18g, 1,3-propanedioic acid 13g is at 100 ℃ of following chain extending reactions after 2 hours, under the effect of catalyzer methoxyl group tin, down carried out end capping 3 hours at 90 ℃ with hydroxyethyl methylacrylate 6.9g, be cooled to 50 ℃ of adding hydrochloric acid 5.1g neutralization reactions at last and made water-based polyurethane resin in 2 hours.
After in above-mentioned water-based polyurethane resin, adding light trigger Benzoin ethyl ether 4g, mill base 2g, defoamer 0.5g again emulsification being sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from the urethane electrocoating paint.
Claims (10)
1, a kind of water-based polyurethane resin, its structural formula is as follows:
Wherein, R
1, R
2, R
3For being alkyl, molecular weight is 3000-6000.
2, a kind of preparation method of water-based polyurethane resin comprises that the following step poly-:
(1) carries out polyreaction a few hours by polyvalent alcohol and cyanate;
(2) then in the presence of solvent, add hydrophilizing agent stoichiometric number hour;
(3) add chainextender again and carry out chain extending reaction a few hours;
(4) add end-capping reagent stoichiometric number hour;
(5) add at last in and the salt forming agent stoichiometric number hour be prepared into water-based polyurethane resin;
Wherein each proportion of raw materials is (weight percent):
Polyvalent alcohol 23-30
Cyanate 25-36
Hydrophilizing agent 6.5-10.0
Chainextender 26-36
End-capping reagent 3.0-6.9
In and salt forming agent 5-7.
3, the preparation method of a kind of water-based polyurethane resin according to claim 2, wherein said polyvalent alcohol is a kind of in polyester polyol or the polyether glycol, cyanate is the different diketone vulcabond that boils, the 1-6-hexamethylene-diisocyanate, 2-4-or 2, the 6-aliphatic diisocyanate, aromatic diisocyanate, in the aromatic series triisocyanate one or more, solvent is two to grip alkane, acetone, butanone, tetrahydrofuran (THF), 1, the 4-dioxane, in the N-Methyl pyrrolidone one or more, hydrophilizing agent is a dimethylol propionic acid, in the dimethylolpropionic acid one or both, chainextender is a methacrylic acid modified epoxy resin, low molecular polylol, in the low molecule polyamine one or more, end-capping reagent is a hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, a kind of in the Propylene glycol monoacrylate, in and salt forming agent be organic acid
4, the preparation method of a kind of water-based polyurethane resin according to claim 2, wherein said solvent is 1, the 4-dioxane.
5, the preparation method of a kind of water-based polyurethane resin according to claim 2, the molecular weight of wherein said polyvalent alcohol is 1000.
6, the preparation method of a kind of water-based polyurethane resin according to claim 2, the temperature of reaction in the wherein said step (1) is 40-150 ℃, the reaction times is 0.5-5 hour.
Temperature of reaction in the step (2) is 40-120 ℃, and the reaction times is 0.5-8 hour.
Temperature of reaction in the step (3) is 40-120 ℃, and the reaction times is 0.5-8 hour.
Temperature of reaction in the step (4) is 40-150 ℃, and the reaction times is 0.5-6 hour.
Temperature of reaction in the step (5) is 10-80 ℃, and the reaction times is 0.5-2 hour.
7, the preparation method of a kind of water-based polyurethane resin according to claim 2 can add organotin, organic plumbous class catalyzer in the wherein said step (4).
8, according to the preparation method of described any one water-based polyurethane resin of claim 2 to 7, wherein said chainextender is a methacrylic acid modified epoxy resin
9, a kind of cataphoresis paint composition, its proportion of raw materials are (weight percent):
The water-based polyurethane resin of claim 1: 80-90
Light trigger: 10-20
10, a kind of preparation method of waterbased urethane electrocoating paint, it is that light trigger is added in the water-based polyurethane resin of claim 1, after emulsification is sheared in water, treat after the micelle film forming under the effect of UV-light, Raolical polymerizable to take place cause that secondary crosslinking is prepared from.
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