CN103342943A - Method for preparing high-charge-density cathode electrophoretic paint - Google Patents
Method for preparing high-charge-density cathode electrophoretic paint Download PDFInfo
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- CN103342943A CN103342943A CN2013102542043A CN201310254204A CN103342943A CN 103342943 A CN103342943 A CN 103342943A CN 2013102542043 A CN2013102542043 A CN 2013102542043A CN 201310254204 A CN201310254204 A CN 201310254204A CN 103342943 A CN103342943 A CN 103342943A
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Abstract
The invention relates to a method for preparing high-charge-density cathode electrophoretic paint. The method comprises the following steps: by using epoxy resin, carboxyl sealing cation polyurethane resin, a chain extender and an organic amine compound as raw materials, carrying out stepwise polymerization and ring-opening reaction to obtain aminated cation polyurethane modified epoxy resin; blending the resin with a totally-enclosed isocyanate crosslinking agent, and adding organic acid for neutralization after completely blending; and finally emulsifying and dispersing in an aqueous medium to obtain the high-charge-density cathode electrophoretic paint. Two ends of cation resin and a main chain of the epoxy electrophoretic paint have ion groups, and therefore the average charge density of each resin molecular chain is increased, and the throwing power of the paint is increased. The modified epoxy resin molecules contain a lot of carbamic acid ester chains, ester bonds, ether bonds, biuret bonds, allophanate bonds and the like, so that an electrophoretic paint film has good adhesive force, toughness, abrasive resistance and elasticity, high glossiness and good antiseptic property.
Description
[technical field]
The present invention relates to a kind of preparation method of high charge density cathode electrophoresis dope, a kind of specifically possess higher throwing power, can satisfy the preparation method of the cathode electrophoresis dope of complex structure workpiece surface application, wherein all have ionic group on the two ends of resin cation (R.C.) and the main chain.
[background technology]
Since the seventies in 20th century, cathode electrophoresis dope is because the superiority of self, for example: it has the uniform characteristics of each position application of the complex-shaped workpiece of pair set, has obtained increasing application, particularly automobile industry in all conglomeraties and has obtained using widely.In painting dressing automobiles, require electrophoretic paint that there is high coating ability at the automobile inner cavity position, because though electrophoresis coating technique can form a coating film at the workpiece surface of complexity, owing to be easy to generate shielding effect in the electrophoresis process, the feasible became uneven of filming that is coated the workpiece surfaces externally and internally, especially inner surface coating is thin, thereby influences the antiseptic property of whole work-piece.In order to improve the barrier propterty of the barrier propterty of automobile integral body, particularly inner chamber, just must improve the throwing power of coating.The ability that throwing power refers to make in the electrophoretic painting process the surperficial electrophoresis of the coated article that deviates from electrode to coat.Body of a motor car for high protection against corrosion requirement, the electrophoretic paint of high throwing power not only can make the recessed depths, place, slit and conductively-closed place that are coated workpiece obtain the application of uniform film thickness, can also be under the situation that improves the internal surface thickness, reduce the thickness of automobile-exterior face, thereby reduce the consumption of coating, save painting cost.
[summary of the invention]
In order to improve the throwing power of electrophoretic paint, thereby further strengthen the antiseptic power of workpiece behind the electrophoresis, the invention provides a kind of preparation method of high charge density cathode electrophoresis dope, a kind of specifically possess higher throwing power, can satisfy the preparation method of the cathode electrophoresis dope of complex structure workpiece surface application, wherein all have ionic group on the two ends of resin cation (R.C.) and the main chain.
The invention provides a kind of preparation method of high charge density cathode electrophoresis dope to achieve these goals, described method is made up of following steps:
Step 1, progressively polymerization: in reaction vessel, add Resins, epoxy, carboxy blocking cationic polyurethane resin and chainextender successively, add catalyzer after reaction system is warming up to 120 ℃, after finishing, the catalyzer adding is warming up to 140～160 ℃, and 1～5h is reacted in continuation under this temperature, after epoxy equivalent (weight) reached theoretical value, stopped reaction obtained the cation polyurethane modified epoxy;
Step 2, ring-opening reaction: cation polyurethane modified epoxy and organic amine compound are joined in the reaction vessel, be warming up to 100～130 ℃ of afterreaction 1～4h.Wherein, the epoxide group of cation polyurethane modified epoxy and the mol ratio of organic amine compound are 1:0.8～1:1.2, obtain the cation polyurethane modified epoxy after the amination;
Cation polyurethane modified epoxy and totally-enclosed isocyanate crosslinking after step 3, the amination carry out blend, and blend back adding organic acid fully neutralizes; Emulsification disperses to obtain the high charge density cathode electrophoresis dope in aqueous medium at last.
Above-mentioned preparation method also has following prioritization scheme:
Prepare the amount of the required various raw materials of above-mentioned cation polyurethane modified epoxy by carboxy blocking cationic polyurethane resin content (the carboxy blocking cationic polyurethane resin accounts for the per-cent of cation polyurethane modified epoxy total solids quality), the amount of substance of epoxide group (the amount of substance * 2 of Resins, epoxy), the amount of substance of chain extension group (the amount of substance * 2 of carboxy blocking cationic polyurethane resin and chainextender) and the design epoxy equivalent (weight) of cation polyurethane modified epoxy decide.Wherein, the epoxy equivalent (weight) scope of cation polyurethane modified epoxy is: 500～5000; The acid number scope of carboxy blocking cationic polyurethane resin is: 20～300; Carboxy blocking cationic polyurethane resin content range is: 5%～40%; Described catalyzer is triphenylphosphine or N, a kind of in the N-dimethyl benzylamine, and catalyst levels (catalyst quality accounts for the per-cent of Resins, epoxy total mass) scope is: 0.1%～1%; Described modified resin total solids quality is the total mass of Resins, epoxy, carboxy blocking cationic polyurethane resin and chainextender.
Resins, epoxy typically refers to and contains two 1 on each molecule, the aliphatics of 2～epoxide group, alicyclic, aromatic series or heterogeneous ring compound, the epoxy equivalent (weight) of described Resins, epoxy is between 50～2000, specially suitable Resins, epoxy includes but not limited to, any one in bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, polyethyleneglycol diglycidylether and the polypropylene glycol diglycidyl ether or any two kinds and two or more mixtures.
Chainextender is poly carboxylic acid, polyvalent alcohol, polynary mercapto alcohol, polyphenol and the amine with two or more active hydrogens, the molecular weight of described chainextender is between 50～3000, specially suitable chainextender includes but not limited to, any one in di-carboxylic acid, dibasic alcohol, the pure and mild dihydric phenolic compounds of binary mercapto or any two kinds and two or more mixtures.
The carboxy blocking cationic polyurethane resin is to be raw material with vulcabond, polymer polyatomic alcohol, hydrophilic chain extender, general chainextender and end-capping reagent, obtains the carboxy blocking cationic polyurethane resin through pre-polymerization and end capping.The preparation process of carboxy blocking cationic polyurethane resin is: add vulcabond and polymer polyatomic alcohol in reaction vessel, be warming up to 50～80 ℃ of afterreaction 30～60min; Then general chainextender is joined in the reaction system, behind reaction 30～60min under 50～80 ℃; Then hydrophilic chain extender is joined in the reaction system, react isocyanate group content in 40～60min post analysis prepolymer down at 50～80 ℃; After isocyanate group content reaches theoretical value, wherein, the isocyanate content theoretical value is 5%～30%, at last end-capping reagent is joined in the reaction system, behind reaction 30～60min under 50～80 ℃, termination reaction obtains main chain and contains ether, urethano and hydrophilic radical segment, and two ends are the carboxy blocking cationic polyurethane resin of carboxy blocking.Wherein, the mol ratio of hydroxyl summation is in isocyanate group and polymer polyatomic alcohol in the described vulcabond, hydrophilic chain extender and the general chainextender: 10:1～2:1, the mol ratio of residual isocyanate base is in described end-capping reagent and the prepolymer: 1.2:1～1:1, and the content range of described hydrophilic radical is: 1%～10%; The quality that described hydrophilic radical content is hydrophilic chain extender accounts for the per-cent of total solids quality; Described total solids quality is the total mass of vulcabond, polymer polyatomic alcohol, hydrophilic chain extender, general chainextender and end-capping reagent.
In the carboxy blocking cationic polyurethane resin process:
A) vulcabond is any one or any two kinds and the two or more mixture in tolylene diisocyanate, '-diphenylmethane diisocyanate, polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride isocyanic ester, trimethyl hexamethylene diisocyanate and the hydrogenated tolylene diisocyanate.
B) polymer polyatomic alcohol is polyether glycol, in the pure and mild polycarbonate polyol of polyester polyols any one or any two kinds and two or more mixtures, the molecular weight of described polymer polyatomic alcohol is between 100～3000, wherein: (1) described polyether glycol is the polytetrahydrofuran polyvalent alcohol, the polyoxyethylene polyvalent alcohol, in the polyoxytrimethylene polyvalent alcohol any one or any two kinds and two or more mixtures, or tetrahydrofuran (THF), ethylene oxide, propylene oxide is a kind of or any two kinds and two or more mixtures in both polyol arbitrarily, or tetrahydrofuran (THF), ethylene oxide, propylene oxide three polyol; (2) described polyester polyol is any one or any two kinds and the two or more mixture in poly-hexanodioic acid hexylene glycol ester, poly adipate succinic acid ester, polyethylene glycol adipate, polyneopentyl glycol adipate, the poly-phthalic acid hexylene glycol ester, or the polyester polyol that is formed by diprotic acid and dibasic alcohol condensation, or the polyester polyol that is formed by lactone ring opening polymerization; (3) described polycarbonate polyol is the oligopolymer that contains two or more terminal hydroxy group carbonate-containing structures, is to be obtained by transesterify by carbonic diester and dibasic alcohol.
C) hydrophilic chain extender has [R
1R
2R
3S]
+R
4COO
-In the structural formula compound any one or any two kinds and two or more mixtures, wherein R
1And R
4Can be identical group, also can be different groups, R
1And R
4Group is that carbon atom is 2～20 alkyl, R
2And R
3Be different groups, R
2And R
3Be that carbon atom is 2～12 hydroxyl alkyl and in the hydroxyl alkylene any one.
D) general chainextender is any one or any two kinds and the two or more mixture in ethylene glycol, propylene glycol, butyleneglycol, Diethylene Glycol, triethylene glycol, quadrol, propylene diamine, butanediamine and the hexanediamine.
E) end-capping reagent has R
6R
5In the COOH structural formula compound any one or any two kinds and two or more mixtures, wherein R
5Group is that carbon atom is 2～20 alkyl, R
6Group is any one in amino, hydroxyl and the sulfydryl, wherein R
6Group is the direct-connected R of receiving
5On the group, and pass through R
5Group links to each other with carboxyl, and typical end-capping reagent comprises Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, glycine, phenylalanine and L-Ala etc.
Organic amine compound is to have the secondary amine compound of the protected primary amino by forming ketoimine and have HNR
3R
4In the structural formula compound any one or any two kinds and two or more mixtures, wherein R
3And R
4Can be identical group, also can be different groups, R
3And R
4Group is that carbon atom is any one in 2～12 alkyl, hydroxyl alkyl and the hydroxyl alkylene, and typical organic amine compound comprises diethylamine, dipropyl amine, dibutylamine, N-Mono Methyl Ethanol Amine, diethanolamine and diethylenetriamine type ketoimine etc.
Totally-enclosed isocyanate crosslinking is by polyisocyanates and the compound prepared in reaction that contains reactive hydrogen.Wherein, temperature of reaction is 50～90 ℃, and the reaction times is 1～8h, and isocyanate group is 1:1～1:1.5 with the mol ratio that contains the compound of reactive hydrogen in the polyisocyanates.Employed in the preparation process: (1) polyisocyanates is to include but not limited to aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, fat-aromatic diisocyanate, triisocyanate, in tetraisocyanate and the polymeric polyisocyanate any one or any two kinds and two or more mixtures comprise tolylene diisocyanate, '-diphenylmethane diisocyanate, the polymethylene polyphenyl vulcabond, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, the dicyclohexyl methyl hydride isocyanic ester, trimethyl hexamethylene diisocyanate and hydrogenated tolylene diisocyanate etc.; (2) compound that contains reactive hydrogen is any one or any two kinds and the two or more mixture in alcohol, amine, carboxylic acid, oxime and the cyclic amide that contains 1～20 carbon atom, comprises methyl alcohol, ethanol, propyl alcohol, hexalin, phenol, p-cresol, xylenol, chlorophenol, xylidine, aniline, n-Butyl Amine 99, Di-n-Butyl Amine, formic acid, acetic acid, propionic acid, sad, stearic acid, formyl amidoxime, acetoxime, methyl ethyl ketoxime, hexanolactam and pyrrolidone etc.
Organic acid is any one or any two kinds and the two or more mixture in the aliphatics that contains 1～20 carbon atom, alicyclic, aromatic series or the heterocycle monoprotic acid, comprise formic acid, acetic acid, propionic acid, butyric acid, lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid and phenylformic acid etc.
Beneficial effect of the present invention is:
1, the cationic urethane resin of main chain belt is incorporated in the Resins, epoxy by chemical bond goes, make and all have ionic group on the two ends of resin cation (R.C.) in the epoxy electrophoretic paint after the modification and the main chain, thereby increased the mean charge density on the every molecular resin chain, made the throwing power of coating increase;
2, because the introducing of urethane segment, make and contain a large amount of carbamic acid ester chain, ester bond, ehter bond, biuret linkage and allophanic acid ester bond etc. in the Resins, epoxy molecule after the modification, therefore, make the paint film behind the electrophoresis have good sticking power, toughness, wear resistance, elasticity and high-luster, and have excellent antiseptic property.
[embodiment]
In order to be easy to further understand the present invention, the following example has been set forth more specific details, but embodiments of the present invention are not limited thereto.
Embodiment 1
One, the preparation of carboxy blocking cationic polyurethane resin
* R
1And R
4Be methyl, R
2Be hydroxyethyl, R
3Be the 2-hydroxypropyl
* NCO/OH=5:1, hydrophilic radical content: 4.34%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add tolylene diisocyanate and the polyether Glycols of formula ratio successively, be warming up to 70 ℃ of afterreaction 30min; Then add ethylene glycol, continue reaction 30min under the same temperature; Add hydrophilic chain extender then, continuation is analyzed isocyanato content in the prepolymer with standard Di-n-Butyl Amine back titration method react 40min under uniform temp after, when isocyanato content reaches theoretical value 17.38%, add thiohydracrylic acid and carry out end-blocking, obtaining acid number is the carboxy blocking cationic polyurethane resin of 232mgKOH/g.
Two, the preparation * * of the polyurethane modified epoxy resin of amination
* by diethylenetriamine and methyl iso-butyl ketone (MIBK) according to mol ratio 1:2 prepared in reaction, the solid content of final product is: 100%
* EEW=1140, carboxy blocking cationic polyurethane resin content=17.3%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add Resins, epoxy, carboxy blocking cationic polyurethane resin, dihydroxyphenyl propane and first part's methyl iso-butyl ketone (MIBK) of formula ratio successively; Behind reinforced the finishing, start stir and reaction system is warming up to 120 ℃ after insulation, treat that raw material dissolves fully and mixes after, after adding triphenylphosphine temperature is risen to 130 ℃, and under this temperature, continue reaction 3h, when the reaction system epoxy equivalent (weight) reaches theoretical value, stop heating; When system temperature is down to below 90 ℃, N-Mono Methyl Ethanol Amine and ketoimine are joined in the reaction system, be warming up to 120 ℃ again, under this temperature, continue reaction 2h; After reaction finishes reaction system is cooled to 70 ℃, adds the second section methyl iso-butyl ketone (MIBK), obtain final solid content and be the cation polyurethane modified epoxy after 80.0% the amination.
Three, the preparation of totally-enclosed isocyanate crosslinking
The tolylene diisocyanate that in the reaction flask that thermometer, agitator and reflux condensing tube are housed, adds formula ratio, after being warming up to 70 ℃, stirring begins to drip methyl ethyl ketoxime, be no more than 75 ℃ with water-bath cooling and control temperature in the dropping process, dropwising the back continues to react 2h down at 70 ℃, with residue isocyanato content in the standard Di-n-Butyl Amine back titration method analytical reaction system, when residue isocyanato content less than 0.5% the time, add methyl iso-butyl ketone (MIBK) and dilute, obtain final solid content and be 80% totally-enclosed isocyanate crosslinking.
Four, the preparation of high charge density cathode electrophoresis dope
The polyurethane modified epoxy resin and the totally-enclosed isocyanate crosslinking that in the reaction flask of agitator is housed, add the amination of formula ratio, start and stir and reaction system is mixed, adding acetic acid then neutralizes and makes the resin reignition, add successively at last and respectively go on foot required deionized water, the organic solvent in the emulsion is removed in underpressure distillation behind the emulsification 30min, namely gets solid content and be 33.7% high charge density cathode electrophoresis dope.
After the high charge density cathode electrophoresis dope of above-mentioned preparation joined groove slaking 48h, adopt four pieces of box methods that the throwing power of coating is tested, and compare with traditional epoxy cathode electrophoresis dope, correlation parameter sees the following form.
The throwing power contrast of the different coating of table 1
Deposition condition: voltage 220V, 30 ℃ of groove temperature, electrophoresis time 3min
By above-mentioned data as can be seen, the throwing power of the high charge density cathode electrophoresis dope among the embodiment 1 is far superior to the throwing power of traditional epoxy cathode electrophoresis dope.
Embodiment 2
One, the preparation of carboxy blocking cationic polyurethane resin
* R
1Be butyl, R
4Be ethyl, R
2And R
3Be the 2-hydroxypropyl
* NCO/OH=3:1, hydrophilic radical content: 9.14%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add the isophorone diisocyanate of formula ratio and the polyether Glycols of two kinds of different molecular weights successively, be warming up to 80 ℃ of afterreaction 50min; Then add butyleneglycol, continue reaction 30min under the same temperature; Add hydrophilic chain extender then, continuation is analyzed isocyanato content in the prepolymer with standard Di-n-Butyl Amine back titration method react 35min under uniform temp after, when isocyanato content reaches theoretical value 15.62%, add 6-aminocaprolc acid and carry out end-blocking, obtaining acid number is the carboxy blocking cationic polyurethane resin of 140mgKOH/g.
Two, the preparation * * of the polyurethane modified epoxy resin of amination
* EEW=1800, carboxy blocking cationic polyurethane resin content=36.4%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add Resins, epoxy, carboxy blocking cationic polyurethane resin, dihydroxyphenyl propane and first part's methyl iso-butyl ketone (MIBK) of formula ratio successively; Behind reinforced the finishing, start stir and reaction system is warming up to 120 ℃ after insulation, treat that raw material dissolves fully and mixes after, after adding triphenylphosphine temperature is risen to 130 ℃, and under this temperature, continue reaction 3h, when the reaction system epoxy equivalent (weight) reaches theoretical value, stop heating; When system temperature is down to below 90 ℃, N-Mono Methyl Ethanol Amine and diethanolamine are joined in the reaction system, be warming up to 120 ℃ again, under this temperature, continue reaction 2h; After reaction finishes reaction system is cooled to 70 ℃, adds the second section methyl iso-butyl ketone (MIBK), obtain final solid content and be the cation polyurethane modified epoxy after 78.5% the amination.
Three, the preparation of totally-enclosed isocyanate crosslinking
The hexamethylene diisocyanate trimer that in the reaction flask that thermometer, agitator and reflux condensing tube are housed, adds formula ratio, after being warming up to 80 ℃, stirring begins to drip ethylene glycol monobutyl ether, be no more than 85 ℃ with water-bath cooling and control temperature in the dropping process, dropwising the back continues to react 4h down at 80 ℃, with residue isocyanato content in the standard Di-n-Butyl Amine back titration method analytical reaction system, when residue isocyanato content less than 0.5% the time, add methyl iso-butyl ketone (MIBK) and dilute, obtain final solid content and be 75% totally-enclosed isocyanate crosslinking.
Four, the preparation of high charge density cathode electrophoresis dope
The polyurethane modified epoxy resin and the totally-enclosed isocyanate crosslinking that in the reaction flask of agitator is housed, add the amination of formula ratio, start and stir and reaction system is mixed, adding 88% lactic acid then neutralizes and makes the resin reignition, add successively at last and respectively go on foot required deionized water, the organic solvent in the emulsion is removed in underpressure distillation behind the emulsification 30min, namely gets solid content and be 34.2% high charge density cathode electrophoresis dope.
Embodiment 3
One, the preparation of carboxy blocking cationic polyurethane resin
* R
1Be ethyl, R
2Be hydroxyethyl, R
3Be 3-propoxy--2-hydroxypropyl, R
4Be butyl
* NCO/OH=2:1, hydrophilic radical content: 3.84%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add diphenylmethanediisocyanate and the polyester diol of formula ratio successively, be warming up to 60 ℃ of afterreaction 30min; Then add hexylene glycol, continue reaction 30min after being warming up to 70 ℃; Add hydrophilic chain extender then, continuation is analyzed isocyanato content in the prepolymer with standard Di-n-Butyl Amine back titration method react 35min under uniform temp after, when isocyanato content reaches theoretical value 7.60%, add 2-sulfydryl butyric acid and carry out end-blocking, obtaining acid number is the carboxy blocking cationic polyurethane resin of 83.4mgKOH/g.
Two, the preparation * * of the polyurethane modified epoxy resin of amination
* by diethylenetriamine and methyl iso-butyl ketone (MIBK) according to mol ratio 1:2 prepared in reaction, the solid content of final product is: 100%
* EEW=900, carboxy blocking cationic polyurethane resin content=24.3%
In the reaction flask that thermometer, agitator and reflux condensing tube are housed, add Resins, epoxy, carboxy blocking cationic polyurethane resin, dihydroxyphenyl propane and first part's methyl iso-butyl ketone (MIBK) of formula ratio successively; Behind reinforced the finishing, start stir and reaction system is warming up to 120 ℃ after insulation, treat that raw material dissolves fully and mixes after, after adding triphenylphosphine temperature is risen to 130 ℃, and under this temperature, continue reaction 3h, when the reaction system epoxy equivalent (weight) reaches theoretical value, stop heating; When system temperature is down to below 90 ℃, diethanolamine and ketoimine are joined in the reaction system, be warming up to 120 ℃ again, under this temperature, continue reaction 2h; After reaction finishes reaction system is cooled to 70 ℃, adds the second section methyl iso-butyl ketone (MIBK), obtain final solid content and be the cation polyurethane modified epoxy after 75% the amination.
Three, the preparation of totally-enclosed isocyanate crosslinking
Thermometer is being housed, the tolylene diisocyanate and the isophorone diisocyanate that add formula ratio in the reaction flask of agitator and reflux condensing tube, after being warming up to 70 ℃, stirring begins to drip methyl ethyl ketoxime, the mixture of hexanolactam and ethylene glycol ether, be no more than 75 ℃ with water-bath cooling and control temperature in the dropping process, dropwising the back continues to react 5h down at 70 ℃, with residue isocyanato content in the standard Di-n-Butyl Amine back titration method analytical reaction system, when residue isocyanato content less than 0.5% the time, add methyl iso-butyl ketone (MIBK) and dilute, obtain final solid content and be 80% totally-enclosed isocyanate crosslinking.
Four, the preparation of high charge density cathode electrophoresis dope
The polyurethane modified epoxy resin and the totally-enclosed isocyanate crosslinking that in the reaction flask of agitator is housed, add the amination of formula ratio, start and stir and reaction system is mixed, add 2 then, the deionized water of 2-dimethylol propionic acid and first part neutralizes and makes the resin reignition, add successively at last and respectively go on foot required deionized water, the organic solvent in the emulsion is removed in underpressure distillation behind the emulsification 30min, namely gets solid content and be 33.74% high charge density cathode electrophoresis dope.
Claims (10)
1. the preparation method of a high charge density cathode electrophoresis dope is characterized in that described method is made up of following steps:
Step 1, in reaction vessel, add Resins, epoxy, carboxy blocking cationic polyurethane resin and chainextender successively, add catalyzer after reaction system is warming up to 120 ℃, wherein, catalyst levels accounts for 0.1%～1% of Resins, epoxy total mass, after finishing, the catalyzer adding is warming up to 140～160 ℃, and under this temperature, continue reaction 1～5h, when epoxy equivalent (weight) reached 500～2000, stopped reaction obtained the cation polyurethane modified epoxy;
Step 2, cation polyurethane modified epoxy and organic amine compound are joined in the reaction vessel, be warming up to 100～130 ℃ of afterreaction 1～4h, wherein, the epoxide group of cation polyurethane modified epoxy and the mol ratio of organic amine compound are 1:0.8～1:1.2, obtain the cation polyurethane modified epoxy after the amination;
Cation polyurethane modified epoxy and totally-enclosed isocyanate crosslinking after step 3, the amination carry out blend, wherein, the mass ratio of the cation polyurethane modified epoxy after the amination and the blend of totally-enclosed isocyanate crosslinking is 2:1～4:1, blend back adding organic acid fully neutralizes, and emulsification disperses to obtain the high charge density cathode electrophoresis dope in aqueous medium at last.
2. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 1 is characterized in that described Resins, epoxy is to contain two 1 on each molecule, the aliphatics of 2-epoxide group, alicyclic, aromatic series or heterogeneous ring compound.
3. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 1, the main chain that it is characterized in that described carboxy blocking cationic polyurethane resin contains ether, urethano and hydrophilic radical segment, two ends are carboxy blocking, and the acid number scope is 20～300; Consumption account for high charge density cathode electrophoresis dope total mass 5%～40%.
4. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 3 is characterized in that also comprising the preparation process of carboxy blocking cationic polyurethane resin:
In reaction vessel, add vulcabond and polymer polyatomic alcohol, the mol ratio of hydroxyl summation is 10:1～2:1 in isocyanate group and polymer polyatomic alcohol in the vulcabond, hydrophilic chain extender and the general chainextender, the mol ratio of residual isocyanate base is 1.2:1～1:1 in described end-capping reagent and the prepolymer, and described hydrophilic radical content range is 1%～10%;
Be warming up to 50～80 ℃ of afterreaction 30～60min; Then general chainextender is joined in the reaction system, behind reaction 30～60min under 50～80 ℃; Then hydrophilic chain extender is joined in the reaction system, react isocyanate group content in 40～60min post analysis prepolymer down at 50～80 ℃; When isocyanate group content reaches 5%～30%, end-capping reagent is joined in the reaction system, behind reaction 30～60min under 50～80 ℃, termination reaction.
5. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 4 is characterized in that described polymer polyatomic alcohol is any one or the multiple mixture in the pure and mild polycarbonate polyol of polyether glycol, polyester polyols of molecular weight between 100～3000.
6. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 4 is characterized in that described hydrophilic chain extender is to have [R
1R
2R
3S]+R
4The mixture of one or more in COO-structural formula compound, R
1And R
4Represent C respectively
2～C
20Alkyl, R
2And R
3Be different groups, R2 and R3 represent C respectively
2～C
12Hydroxyl alkyl or hydroxyl alkylene.
7. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 4 is characterized in that described end-capping reagent is to have R
6R
5The mixture of one or more in the COOH structural formula compound, wherein R
5Expression C
2～C
20Alkyl, R
6Expression amino, hydroxyl or sulfydryl, wherein R
6Group is the direct-connected R of receiving
5On the group, and pass through R
5Group links to each other with carboxyl.
8. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 1 is characterized in that described organic amine compound has the secondary amine compound of the protected primary amino by forming ketoimine and has HNR
3R
4The mixture of one or more in the structural formula compound, wherein R
3And R
4Be C
2～C
12Alkyl, hydroxyl alkyl or hydroxyl alkylene.
9. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 1 is characterized in that also comprising the preparation process of totally-enclosed isocyanate crosslinking:
By polyisocyanates and the compound prepared in reaction that contains reactive hydrogen, isocyanate group is 1:1～1:1.5 with the mol ratio that contains the compound of reactive hydrogen in the polyisocyanates, and temperature of reaction is 50～90 ℃, and the reaction times is 1～8h.
10. the preparation method of high charge density cathode electrophoresis dope as claimed in claim 9 is characterized in that the described compound that contains reactive hydrogen is alcohol, amine, carboxylic acid, oxime or the cyclic amide that contains 1～20 carbon atom.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310254204.3A CN103342943B (en) | 2013-06-24 | 2013-06-24 | Method for preparing high-charge-density cathode electrophoretic paint |
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|---|---|---|---|
| CN201310254204.3A CN103342943B (en) | 2013-06-24 | 2013-06-24 | Method for preparing high-charge-density cathode electrophoretic paint |
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| Publication Number | Publication Date |
|---|---|
| CN103342943A true CN103342943A (en) | 2013-10-09 |
| CN103342943B CN103342943B (en) | 2015-04-29 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104371496A (en) * | 2014-11-07 | 2015-02-25 | 广德瑞邦涂料有限公司 | Cathodic water-soluble electrophoretic paint emulsion and preparation method thereof |
| CN104945590A (en) * | 2015-05-15 | 2015-09-30 | 武汉科利尔新材料有限公司 | Hydroxyl-terminal modified polyurethane resin, electrophoretic coating composition thereof and preparation methods of hydroxyl-terminal modified polyurethane resin and electrophoretic coating composition |
| CN105378009A (en) * | 2013-05-16 | 2016-03-02 | 株式会社Kcc | Method for preparing urethane hardener for electrodeposition paint, cationic electrodeposition resin composition for electrodeposition paint containing same, and electrodeposition paint composition |
| CN109384936A (en) * | 2018-09-26 | 2019-02-26 | 青岛科技大学 | Carbon nanotube is grafted hydroxyl-terminated polyurethane electrophoresis resin, cathode polyurethane electrophoretic paint and preparation method thereof |
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| JP2006111765A (en) * | 2004-10-15 | 2006-04-27 | Kansai Paint Co Ltd | Anionic electrodeposition coating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105378009A (en) * | 2013-05-16 | 2016-03-02 | 株式会社Kcc | Method for preparing urethane hardener for electrodeposition paint, cationic electrodeposition resin composition for electrodeposition paint containing same, and electrodeposition paint composition |
| CN104371496A (en) * | 2014-11-07 | 2015-02-25 | 广德瑞邦涂料有限公司 | Cathodic water-soluble electrophoretic paint emulsion and preparation method thereof |
| CN104945590A (en) * | 2015-05-15 | 2015-09-30 | 武汉科利尔新材料有限公司 | Hydroxyl-terminal modified polyurethane resin, electrophoretic coating composition thereof and preparation methods of hydroxyl-terminal modified polyurethane resin and electrophoretic coating composition |
| CN104945590B (en) * | 2015-05-15 | 2018-11-16 | 武汉科利尔新材料有限公司 | Terminal hydroxy group modified polyurethane resin and its cataphoresis paint composition and preparation method |
| CN109384936A (en) * | 2018-09-26 | 2019-02-26 | 青岛科技大学 | Carbon nanotube is grafted hydroxyl-terminated polyurethane electrophoresis resin, cathode polyurethane electrophoretic paint and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN103342943B (en) | 2015-04-29 |
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Address after: No.158, Huiping Road, Nanxiang Town, Jiading District, Shanghai, 201802 Patentee after: HLS COATING (SHANGHAI) Co.,Ltd. Patentee after: HAOLISEN CHEMICAL TECHNOLOGY (JIANGSU) Co.,Ltd. Address before: No.158, Huiping Road, Nanxiang Town, Jiading District, Shanghai, 201802 Patentee before: HLS COATING (SHANGHAI) Co.,Ltd. Patentee before: HAOLISEN CHEMICAL TECHNOLOGY JIANGSU CO.,LTD. |