CN106700028A - Sulfonium salt type dispersion resin for cathodic electrophoretic paint and preparation method of sulfonium salt type dispersion resin - Google Patents
Sulfonium salt type dispersion resin for cathodic electrophoretic paint and preparation method of sulfonium salt type dispersion resin Download PDFInfo
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Abstract
The invention belongs to the technical field of paint, and relates to sulfonium salt type dispersion resin for cathodic electrophoretic paint and a preparation method of the sulfonium salt type dispersion resin. The preparation method of the dispersion resin comprises the following steps of 1), preparing a micromolecular thickener semi-closed isocyanate; 2), preparing a thioether compound semi-closed isocyanate containing reactive hydrogen; 3), preparing an alcohol compound or alcohol ether compound semi-closed isocyanate; 4), preparing the dispersion resin. A sulfur atom in a thioether bond on a side chain of the dispersion resin can form an iron-sulfur bond with an iron base material; further, the binding force between a coating and a metallic base material is improved; the corrosion-resistant capacity and the redissolution-resistant capacity of the coating are improved; meanwhile, the dispersion resin has better leveling property, so the luster of the coating can be improved; in addition, the dispersion resin belongs to water-base dispersion resin; organic solvents are used less; the dispersion resin has a low-VOC (Volatile Organic Compounds) environmentally friendly characteristic. Compared with quaternary ammonium salt type dispersion resign, the dispersion resin has many advantages, and has a wide application prospect.
Description
Technical field
The invention belongs to technical field of coatings, it is related to a kind of corrosion resistance that can improve cathode electrophoresis dope, paint film table
Face gloss and anti-sulfosalt type dispersion resin of dissolubility ability and preparation method thereof again.
Background technology
Electrophoretic coating is typically referred under electric field action, and the main substance in coating is finally baked into deposited on substrates
A kind of water paint of film.By the development of decades, status of the electrophoretic coating in coating industry is more and more important, and this is main
Be attributed to electrophoretic coating and have that utilization efficiency of coatings is high, corrosion resistance strong, good environmental protection the features such as.
Auto industry is one of topmost application field of cathode electrophoresis dope, and the cathode electrophoresis dope for the field leads to
Frequently with epoxy resin as matrix resin, mill base is prepared using the dispersion resin containing quaternary ammonium salt structure.This negative electrode electricity
Swimming coating possesses good corrosion resistance when being processed before Zinc phosphating, 1000 is can reach under the conditions of neutral salt spray test small
When.But, Zinc phosphating pre-treatment it is relatively costly, in the work progress in some low-end applications fields pass through frequently with iron system phosphorus
Change pre-treatment substituted, its have construction it is simple, with low cost the features such as, but the salt spray resistance ability of gained paint film significantly under
Drop, is unfavorable for the protection of base material.When using ferric solid-acid as preceding treatment, traditional quaternary dispersion resin it is corrosion-resistant
Scarce capacity.Due to there is substantial amounts of ammonium salt in dispersion resin, the easy loss of gloss of paint film, xanthochromia in high-temperature baking.Quaternary
Mill base prepared by dispersion resin is returned slightly after precipitating, easily, and the stability of construction is have impact on to a certain extent.
In terms of the decay resistance of electrophoretic coating is improved, forefathers are made that substantial amounts of work.Li Xiangtao uses zirconium film
Technology improves paint film with the adhesion and decay resistance of base material (referring to Li Xiangtao, before cathode electro-coating as pre-treatment
The research [D] for the treatment of, Dalian Polytechnic University's master thesis, 2013), but zirconium pre-treatment is still than ferric solid-acid cost
It is high.Nie Ren states once added the epoxy resin of high equivalent weight in the electrodeposited paint film using ferric solid-acid as preceding treatment, improve paint
The degree of cross linking of film, improves decay resistance of the electrodeposited paint film in ferric solid-acid (referring to Nie Ren states, SGMW to a certain extent
Vehicle corrosion resistance and vehicle body Anti-corrosive process for oil [D], Jilin University's master thesis, 2011), but high equivalent weight asphalt mixtures modified by epoxy resin
Fat brings the problem in terms of levelling again, causes the degraded appearance of paint film.
The content of the invention
For above-mentioned situation, disperseed with sulfosalt type it is an object of the invention to provide a kind of new cathode electrophoresis dope
Resin and preparation method thereof.The dispersion resin is a kind of cation dispersion resin, by the semi-enclosed isocyanic acid of small molecule thickener
Ester, the semi-enclosed isocyanates of the thio-ether type compounds containing active hydrogen, alcohol compound or alcohol ethers compound are semi-enclosed different
Cyanate and epoxy resin reaction prepare matrix resin, then using the thio-ether type compounds and aforementioned body being acidified through Bronsted acid
Resin reaction is obtained, wherein：Alcohol compound or the semi-enclosed isocyanates of alcohol ethers compound are by alcohol compound or alcohol ether
Class compound is obtained with isocyanate ester compound reaction；The semi-enclosed isocyanates of thio-ether type compounds containing active hydrogen is by containing
The thio-ether type compounds of active hydrogen are obtained with isocyanate ester compound reaction；The semi-enclosed isocyanates of small molecule thickener by
Polyether compound or polyethylene glycols compound react with isocyanate ester compound, then again with alcohol compound and alcohol ether
The reaction of class compound is obtained.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
A kind of cathode electrophoresis dope preparation method of sulfosalt type dispersion resin, it comprises the following steps：
1) under inert gas shielding, to adding isocyanic acid in the reaction vessel with agitating device and cooling back installation
Ester type compound, the rotating speed for controlling agitating device is 300~600rpm；Be added dropwise polyethers (also known as PPG) class compound or
Polyethylene glycols compound, while ON cycle cooling device, 1~4 hour is incubated in 20~40 DEG C；Be added dropwise alcohol compound or
Alcohol ethers compound, 1~4 hour is incubated in 20~40 DEG C；Methyl iso-butyl ketone (MIBK) is added, after stirring, small molecule increasing is obtained
Thick dose of semi-enclosed isocyanates, it is standby；
Wherein：Rubbing between the isocyanate ester compound and the polyether compound or polyethylene glycols compound
You are than being 2~3:1；Mol ratio between the isocyanate ester compound and the alcohol compound or alcohol ethers compound is
1.5~2:1；
2) under inert gas shielding, to adding isocyanic acid in the reaction vessel with agitating device and cooling back installation
Ester type compound, the rotating speed for controlling agitating device is 300~600rpm；The thio-ether type compounds containing active hydrogen are added dropwise, in 20~
40 DEG C are incubated 1~4 hour；Methyl iso-butyl ketone (MIBK) is added, after stirring, the thio-ether type compounds containing active hydrogen is obtained semiclosed
Isocyanates, it is standby；
Wherein：Mol ratio between the isocyanate ester compound and the thio-ether type compounds containing active hydrogen is
0.5~1:1；
3) under inert gas shielding, to adding isocyanic acid in the reaction vessel with agitating device and cooling back installation
Ester type compound, the rotating speed for controlling agitating device is 300~600rpm；Alcohol compound or alcohol ethers compound is added dropwise, in 20
~40 DEG C are incubated 1~4 hour；Methyl iso-butyl ketone (MIBK) is added, after stirring, alcohol compound or alcohol ethers compound half is obtained
The isocyanates of closing, it is standby；
Wherein：Mol ratio between the isocyanate ester compound and the alcohol compound or alcohol ethers compound is
0.5~1:1；
4) under inert gas shielding, in the reaction vessel with heater and agitating device add epoxy resin,
Bisphenol-A, nonyl phenol and dimethylbenzene, are heated to 100~110 DEG C, and the rotating speed for controlling agitating device is 300~600rpm；Add first
Base triphenyl phosphonium iodide catalyst, 1~4 hour is incubated in 130~140 DEG C, is cooled to 100~110 DEG C, is incubated 1~2 hour；
Step 1 is added dropwise) in the semi-enclosed isocyanates of small molecule thickener, the step 2 that obtain) in the thioether class containing active hydrogen that obtains
The semi-enclosed isocyanates of compound and step 3) in the alcohol compound or the semi-enclosed isocyanic acid of alcohol ethers compound that obtain
Ester, 60~65 DEG C are cooled to after being incubated 1~3 hour in 100~110 DEG C；Thio-ether type compounds, Bronsted acid and water are added, in 65
~75 DEG C are incubated 4~8 hours, add water dilution, after being well mixed, obtain cathode electrophoresis dope sulfosalt type dispersion resin；
Wherein：The step 1) between the semi-enclosed isocyanates of small molecule thickener that obtains and the epoxy resin
Mass ratio be 5~15:100；The step 2) in the semi-enclosed isocyanates of the thio-ether type compounds containing active hydrogen that obtains
It is 10~20 with the mass ratio between the epoxy resin:100；The step 3) in the alcohol compound that obtains or alcohol ethers
Mass ratio between the semi-enclosed isocyanates of compound and the epoxy resin is 20~30:100.
Preferably, in above-mentioned preparation method, the inert gas includes nitrogen, helium, neon and argon gas, preferably nitrogen
Gas.
Preferably, in above-mentioned preparation method, the isocyanate ester compound include toluene di-isocyanate(TDI) (including 2,
4- toluene di-isocyanate(TDI)s and 2,6- toluene di-isocyanate(TDI), preferably 2,4- toluene di-isocyanate(TDI)s), the isocyanide of diphenyl methane two
Acid esters (including 4,4 '-methyl diphenylene diisocyanate, 2,4 '-methyl diphenylene diisocyanate and 2,2 '-diphenyl methane
Diisocyanate, preferably 4,4 '-methyl diphenylene diisocyanate), (including 1,3- benzene two is sub- for XDI
Methyl diisocyanate and Isosorbide-5-Nitrae-XDI, preferably 1,3- XDIs), six methylenes
Group diisocyanate, IPDI and dicyclohexyl methyl hydride diisocyanate (including 4,4 '-dicyclohexyl methyl hydride
Diisocyanate, 2,4 '-dicyclohexyl methyl hydride diisocyanate and 2,2 '-dicyclohexyl methyl hydride diisocyanate, preferably 4,4 '-
Dicyclohexyl methyl hydride diisocyanate), preferred toluene di-isocyanate(TDI).
Preferably, in above-mentioned preparation method, the mean molecule quantity of the polyether compound is 200~2000.
Preferably, in above-mentioned preparation method, the mean molecule quantity of the polyethylene glycols compound is 200~2000.
Preferably, in above-mentioned preparation method, the alcohol compound includes isopropanol, n-butanol, the tert-butyl alcohol, Zhong Ding
Alcohol, n-amyl alcohol, tert-pentyl alcohol and isooctanol, preferably isooctanol.
Preferably, in above-mentioned preparation method, the alcohol ethers compound (is passed through by glycol compound and alcohol compound
Compound obtained in etherification reaction) include ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propandiol butyl ether and diethyl two
Alcohol butyl ether, preferably propandiol butyl ether.
Preferably, in above-mentioned preparation method, the thioether class closure containing active hydrogen includes methylthio phenyl methyl alcohol (bag
Include 4- methylthio phenyls methyl alcohol, 3- methylthio phenyls methyl alcohol and 2- methylthio phenyl methyl alcohol, preferably 4- methylthio phenyls methyl alcohol), methylthio phenyl
Phenol (including 4- methylthiophenols, 3- methylthiophenols and 2- methylthiophenols, preferably 4- methylthiophenols), 3- methyl mercaptos -1-
Hexanol, 2- ethylthioethanols, 3- ethylmercapto groups propyl alcohol, thiodiglycol, 4,4'- dihydroxy diphenyl sulfide and 2- Mercaptoethyls,
It is preferred that 2- ethylthioethanols.
Preferably, in above-mentioned preparation method, the epoxy resin includes bisphenol A type epoxy resin and bisphenol F type epoxy
Resin, preferably bisphenol A type epoxy resin；The epoxide equivalent (EEW) of the epoxy resin be 200~5000, preferably 500~
2000。
Preferably, in above-mentioned preparation method, the thio-ether type compounds include diethyl thioether, dipropyl thioether, two
Butyl thioether, diphenyl sulfide, thiodiglycol, methylthio phenyl methyl alcohol (including 4- methylthio phenyls methyl alcohol, 3- methylthio phenyls methyl alcohol and 2-
Methylthio phenyl methyl alcohol, preferably 4- methylthio phenyls methyl alcohol), methylthiophenol (including 4- methylthiophenols, 3- methylthiophenols and 2-
Methylthiophenol, preferably 4- methylthiophenols), methylthio-benzoic acid (including 4- methylthio-benzoic acids, 3- methylthio-benzoic acids and
2- methylthio-benzoic acids, preferably 4- methylthio-benzoic acids), methylthio phenyl acetic acid (including 4- methylthio phenyls acetic acid, 3- methylthio phenyls
Acetic acid and 2- methylthio phenyl acetic acid, preferably 4- methylthio phenyls acetic acid), 3 methyl mercapto 1 hexanol, 2- ethylthioethanols, 3- second sulphur
Base propyl alcohol, 4,4'- dihydroxy diphenyl sulfide and 2- Mercaptoethyls, preferably thiodiglycol.
Preferably, the Bronsted acid includes formic acid, glacial acetic acid, sulfamic acid, nitric acid, lactic acid and 2,2- dihydroxymethyl third
Acid, preferably glacial acetic acid.
Preferably, the water is deionized water.
The cathode electrophoresis dope sulfosalt type dispersion resin prepared by above-mentioned preparation method.In the dispersion resin structure
Sulphur atom can with iron ion formed iron sulfide linkage, improve the active force between coating and base material, and then improve coating
Corrosion resistance and anti-dissolubility ability again；Meanwhile, the dispersion resin has more preferable levelability, improves the gloss of coating surface
And outward appearance.
Compared with prior art, using above-mentioned technical proposal the invention has the advantages that：
(1) sulfosalt type dispersion resin of the invention forms iron sulphur using the sulphur atom of the thioether bond in structure with iron ion
Key, improves the adhesion of coating and base material, and then improves the corrosion resistance and anti-dissolubility ability again of coating；
(2) solution viscosity of the less sulfosalt type resin of mean molecule quantity is relatively low, and sedimentation is also easy to produce when preparing mill base,
Method of the present invention using small molecule association thickener is grafted so that the resistance to settling of sulfosalt type dispersion resin can be obtained greatly
Big lifting；
(3) mean molecule quantity of sulfosalt type dispersion resin of the invention is less than common quaternary ammonium salt dispersion resin, possesses more
Low glass transition temperature, levelability more preferably, can improve the gloss of coating surface, improve appearance attribute；
(4) the thioether key section in sulfosalt type dispersion resin structure of the invention instead of quaternary dispersion resin knot
Ether-oxygen bond in structure, improves the ability of high temperature resistant and color-changing；
(5) sulfosalt type dispersion resin of the invention be water-base resin, less use organic solvent, with VOC content it is low,
The features such as good environmental protection；
(6) preparation method of the invention has that process is simple, reaction temperature are low, processing cost is low, be easy to large-scale operation
The advantages of.
Brief description of the drawings
Fig. 1 is the synthetic route chart of the semi-enclosed isocyanates of small molecular thickener of embodiment 2.
Fig. 2 is the synthetic route chart of the semi-enclosed isocyanates of thio-ether type compounds containing active hydrogen in embodiment 2.
Fig. 3 is the synthetic route chart of alcohol compound or the semi-enclosed isocyanates of alcohol ethers compound in embodiment 2.
Fig. 4 is the synthetic route chart of cathode electrophoresis dope sulfosalt type dispersion resin in embodiment 2.
Specific embodiment
Further description is made to technical scheme below with reference to the drawings and specific embodiments.It should be understood that
, the following example is merely to illustrate the present invention, and not limits the scope of the invention in any form.In addition, removing
No special illustrates that instrument, material, reagent used in the following example etc. can be obtained by routine business means.
Embodiment 1：Prepare cathode electrophoresis dope component A --- emulsion.
Preparation method refers to the method described in US8486538B2, US4419467, US3984299.
Prepare following each component in parts by weight：816 parts of epoxy resin, 828,2 parts of methyl triphenyl phosphonium iodide catalysis
Agent, 384 parts of bisphenol-As, 60 parts of dimethylbenzene, 847 parts of blocked isocyanate crosslinking agents are (by toluene di-isocyanate(TDI) and isooctanol and three
Hydroxymethyl-propane reaction is obtained, and isooctanol is 7 with the mol ratio of trimethylolpropane:3, solid point 85%), 45 parts of N- methyl lists
Monoethanolamine, 144 parts of ketimides (be obtained through dehydration by diethylenetriamines and methyl iso-butyl ketone (MIBK), solid point 85%), 120
Part propylene glycol n-butyl ether, 60 parts of propane diols phenylates, 24 parts of glacial acetic acid, 3500 parts of deionized waters.
Under nitrogen protection, to input epoxy resin 828, bisphenol-A in the reactor with heater and agitating device
And dimethylbenzene, control rotating speed for 400rpm, it is heated to 100 DEG C or so；After all melting and be well mixed, methyl triphen is added
Base phosphonium iodide catalyst, 2 hours are incubated in 140 DEG C；When test epoxide equivalent is 1100~1150,100 DEG C or so are cooled to；Plus
Enter propylene glycol n-butyl ether and propane diols phenylate, be subsequently added (2-hydroxyethyl)methylamine), 1 hour is incubated in 100 DEG C；Add ketone sub-
Amine, 2 hours are incubated in 110 DEG C；Blocked isocyanate crosslinking agent is added, is stirred 0.5 hour in 120 DEG C of constant temperature；It is cooled to 90 DEG C
Hereinafter, glacial acetic acid is added, 0.5 hour is incubated in 80 DEG C, obtain pre-dispersed resin；To adding deionization in another reaction vessel
Water, adds above-mentioned pre-dispersed resin under stirring, controls rotating speed for 1200rpm, after being uniformly dispersed, obtains emulsion, standby.
Embodiment 2：Prepare sulfosalt type dispersion resin.
(1) following each component in parts by weight are prepared：174 parts of 2,4 toluene diisocyanate (molecular weight 174g/
Mol), 200 parts of polyethers 204 (mean molecule quantity 400g/mol), 90 parts of methyl iso-butyl ketone (MIBK)s, 130 parts of isooctanol (molecular weight
130g/mol)；
As shown in figure 1, under nitrogen protection, being added in the four-hole bottle with agitator, recirculated cooling water and head tank
2,4- toluene di-isocyanate(TDI)s, it is 400rpm to control rotating speed；Polyethers 204 is added dropwise, while opening cooling circulating water, is added dropwise within 3 hours
Finish, 2 hours are incubated in 30 DEG C；Isooctanol is added dropwise, 2 hours completion of dropping are incubated 3 hours in 30 DEG C；Add methyl-isobutyl
Ketone, after stirring, obtains the semi-enclosed isocyanates of small molecule thickener (component X in Fig. 1 and Fig. 4), standby.
(2) following each component in parts by weight are prepared：174 parts of 2,4 toluene diisocyanate (molecular weight 174g/
Mol), 107 parts of 2- ethylthioethanols (molecular weight 107g/mol), 15 parts of methyl iso-butyl ketone (MIBK)s；
As shown in Fig. 2 under nitrogen protection, being added in the four-hole bottle with agitator, recirculated cooling water and head tank
2,4- toluene di-isocyanate(TDI)s, it is 400rpm to control rotating speed；2- ethylthioethanols are added dropwise and (originate from Maoming City Maoming Yunlong
Industrial development Co., Ltd, purity is 99wt%), while opening cooling circulating water, 2 hours completion of dropping are small in 30 DEG C of insulations 2
When；Methyl iso-butyl ketone (MIBK) is added, after stirring, the semi-enclosed isocyanates (Fig. 2 of thio-ether type compounds containing active hydrogen is obtained
With the Y components in Fig. 4), it is standby.
(3) following each component in parts by weight are prepared：174 parts of 2,4 toluene diisocyanate (molecular weight 174g/
Mol), 130 parts of isooctanol (molecular weight 130g/mol), 38 parts of methyl iso-butyl ketone (MIBK)s；
As shown in figure 3, under nitrogen protection, being added in the four-hole bottle with agitator, recirculated cooling water and head tank
2,4- toluene di-isocyanate(TDI)s, it is 400rpm to control rotating speed；Isooctanol is added dropwise, while opening cooling circulating water, drips within 2 hours
Finish, 2 hours are incubated in 30 DEG C；Methyl iso-butyl ketone (MIBK) is added, after stirring, alcohol compound or alcohol ethers compound half is obtained
The isocyanates (Z component in Fig. 3 and Fig. 4) of closing, it is standby.
(4) following each component in parts by weight are prepared：443 parts of epoxy resin, 828,2 parts of methyl triphenyl phosphonium iodides
Semiclosed isocyanates, 68 prepared in catalyst, 157 parts of bisphenol-As, 44 parts of nonyl phenols, 20 parts of dimethylbenzene, 35 parts of steps (1)
Semiclosed isocyanates, the 147 parts of sulphur two prepared in the semiclosed isocyanates, the 100 parts of steps (3) that are prepared in part step (2)
Glycol, 48 parts of glacial acetic acid, 20 parts of deionized waters (1), 344 parts of propandiol butyl ethers, 200 parts of deionized waters (2)；
As shown in figure 4, being added in the four-hole bottle with vacuum extractor, agitating device, recirculated cooling water and head tank
Epoxy resin 828, bisphenol-A, nonyl phenol and dimethylbenzene, are heated to 100 DEG C or so, and it is 400rpm to control rotating speed；Treat whole thawings
And after being well mixed, methyl triphenyl phosphonium iodide catalyst is added, and 2 hours are incubated in 140 DEG C, it is cooled to 100 DEG C or so, insulation
1 hour；The three kinds of semi-enclosed isocyanates (component X, Y components and Z component) prepared in step (1) to (3) are added, in 110
DEG C insulation 2 hours after be cooled to 65 DEG C or so；The nco value determined in product is less than 5 ‰, judges that grafting is complete；Add sulphur
Diethylene glycol (DEG) (originating from Maoming City Maoming Yunlong Industrial Development Co., Ltd., purity is 99wt%), glacial acetic acid and deionization
Water (1), 4 hours are incubated in 70 DEG C, add deionized water (2) dilution, after being well mixed, obtain cathode electrophoresis dope sulfosalt
Type dispersion resin.The acid number for determining final product is 1~3mgKOH/g, judges that reaction is complete, obtains being expected product.
Embodiment 3：Prepare cathode electrophoresis dope B component --- mill base.
Prepare following each component in parts by weight：Sulfosalt type dispersion resin, 460 prepared in 314 parts of embodiments 2
Part deionized water, 260 parts of china clay, 40 parts of carbon blacks, 8 parts of bismuth oxides and 1 part of Surfynol104E types wetting agent (originate from U.S.'s air
Chemical products Co., Ltd)；
To deionized water is added in the reaction vessel with high-speed stirring apparatus, it is 1200rpm or so to control rotating speed；Add
Sulfosalt type dispersion resin is simultaneously uniformly dispersed；Add china clay, carbon black, bismuth oxide and Surfynol 104E types wetting agents and mix
Uniformly；Ground using high-speed grinder, it is 3000rpm or so to control rotating speed, is ground 2 hours, until fineness is less than 20 microns, is obtained
It is standby to mill base.
Embodiment 4：Prepare cathode electrophoresis dope working solution.
Prepare following each component in parts by weight：Made in the emulsion, the 67 parts of embodiments 3 that are prepared in 400 parts of embodiments 1
Standby mill base, 500 parts of deionized waters；
By in deionized water addition emulsion, mill base is stirring evenly and then adding into, is well mixed post curing 4 hours, then carried out
Electrophoresis operation, design parameter is as follows：Construction voltage is 140V, and electrophoresis time is 2 minutes, and baking temperature is 140 DEG C.
Embodiment 5：The performance test of cathode electrophoresis dope.
Under identical operating conditions, the negative electrode that will be prepared by sulfosalt type dispersion resin and quaternary dispersion resin respectively
Electrophoretic coating carries out the performance comparison in terms of salt spray resistance, anti-dissolubility ability again and gloss, and wherein salt spray resistance test is pressed
According to《The measure of the resistance to neutral salt spray performance of GB/T 1771-2007 paint and varnish》Described in method carry out, resist dissolubility ability again
Test according to《HG/T 3952-2007 cathode electrophoresis dopes》Described in method carry out, measurement of luster according to《GB/T 9754-
20 °, the 60 ° and 85 ° measure of bright luster of colored paint paint film of 2007 paint and varnish without metallic pigments》Described in method
Carry out, its result is as shown in table 1.
The performance test results of the cathode electrophoresis dope that table 1. is prepared by different dispersion resins
As shown in Table 1, using sulfosalt type dispersion resin of the invention, it is possible to increase the corrosion resistance of coating and it is anti-again
Dissolubility ability；In addition, sulfosalt type dispersion resin of the invention possesses lower glass transition temperature, levelability is more preferable, energy
The gloss of coating surface is enough improved, improves appearance attribute.
Claims (9)
1. a kind of cathode electrophoresis dope preparation method of sulfosalt type dispersion resin, it comprises the following steps：
1) under inert gas shielding, to adding isocyanates in the reaction vessel with agitating device and cooling back installation
Compound, the rotating speed for controlling agitating device is 300~600rpm；Polyether compound or polyethylene glycols compound is added dropwise, together
When ON cycle cooling device, in 20~40 DEG C be incubated 1~4 hour；Alcohol compound or alcohol ethers compound is added dropwise, in 20~
40 DEG C are incubated 1~4 hour；Methyl iso-butyl ketone (MIBK) is added, after stirring, the semi-enclosed isocyanic acid of small molecule thickener is obtained
Ester, it is standby；
Wherein：Mol ratio between the isocyanate ester compound and the polyether compound or polyethylene glycols compound
It is 2~3:1；Mol ratio between the isocyanate ester compound and the alcohol compound or alcohol ethers compound is 1.5
~2:1；
2) under inert gas shielding, to adding isocyanates in the reaction vessel with agitating device and cooling back installation
Compound, the rotating speed for controlling agitating device is 300~600rpm；The thio-ether type compounds containing active hydrogen are added dropwise, in 20~40 DEG C
Insulation 1~4 hour；Methyl iso-butyl ketone (MIBK) is added, after stirring, the thio-ether type compounds containing active hydrogen is obtained semi-enclosed different
Cyanate, it is standby；
Wherein：Mol ratio between the isocyanate ester compound and the thio-ether type compounds containing active hydrogen for 0.5~
1:1；
3) under inert gas shielding, to adding isocyanates in the reaction vessel with agitating device and cooling back installation
Compound, the rotating speed for controlling agitating device is 300~600rpm；Alcohol compound or alcohol ethers compound is added dropwise, in 20~40
DEG C insulation 1~4 hour；Methyl iso-butyl ketone (MIBK) is added, after stirring, alcohol compound is obtained or alcohol ethers compound is semiclosed
Isocyanates, it is standby；
Wherein：Mol ratio between the isocyanate ester compound and the alcohol compound or alcohol ethers compound is 0.5
~1:1；
4) under inert gas shielding, to addition epoxy resin, bis-phenol in the reaction vessel with heater and agitating device
A, nonyl phenol and dimethylbenzene, are heated to 100~110 DEG C, and the rotating speed for controlling agitating device is 300~600rpm；Add methyl three
Phenyl phosphonium iodide catalyst, 1~4 hour is incubated in 130~140 DEG C, is cooled to 100~110 DEG C, is incubated 1~2 hour；It is added dropwise
Step 1) in the semi-enclosed isocyanates of small molecule thickener, the step 2 that obtain) in the thioether class chemical combination containing active hydrogen that obtains
The semi-enclosed isocyanates of thing and step 3) in the alcohol compound or the semi-enclosed isocyanates of alcohol ethers compound that obtain, in
100~110 DEG C insulation 1~3 hour after be cooled to 60~65 DEG C；Thio-ether type compounds, Bronsted acid and water are added, in 65~75 DEG C
Insulation 4~8 hours, adds water dilution, after being well mixed, obtains cathode electrophoresis dope sulfosalt type dispersion resin；
Wherein：The step 1) in matter between the semi-enclosed isocyanates of small molecule thickener that obtains and the epoxy resin
Amount is than being 5~15:100；The step 2) in the semi-enclosed isocyanates of the thio-ether type compounds containing active hydrogen that obtains and institute
It is 10~20 to state the mass ratio between epoxy resin:100；The step 3) in the alcohol compound that obtains or alcohol ethers compound
Mass ratio between semi-enclosed isocyanates and the epoxy resin is 20~30:100.
2. preparation method according to claim 1, it is characterised in that：
The inert gas includes nitrogen, helium, neon and argon gas.
3. preparation method according to claim 1, it is characterised in that：
The isocyanate ester compound includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, phenylenedimethylidyne two
Isocyanates, hexamethylene diisocyanate, IPDI and dicyclohexyl methyl hydride diisocyanate.
4. preparation method according to claim 1, it is characterised in that：
The mean molecule quantity of the polyether compound is 200~2000；
The mean molecule quantity of the polyethylene glycols compound is 200~2000.
5. preparation method according to claim 1, it is characterised in that：
The alcohol compound includes isopropanol, n-butanol, the tert-butyl alcohol, sec-butyl alcohol, n-amyl alcohol, tert-pentyl alcohol and isooctanol；
The alcohol ethers compound includes ethylene glycol ethyl ether, butyl glycol ether, propylene glycol monomethyl ether, propandiol butyl ether and diethylene glycol
Butyl ether.
6. preparation method according to claim 1, it is characterised in that：
The thioether class closure containing active hydrogen includes methylthio phenyl methyl alcohol, methylthiophenol, 3 methyl mercapto 1 hexanol, 2-
Ethylthioethanol, 3- ethylmercapto groups propyl alcohol, thiodiglycol, 4,4'- dihydroxy diphenyl sulfide and 2- Mercaptoethyls.
7. preparation method according to claim 1, it is characterised in that：
The epoxy resin includes bisphenol A type epoxy resin and bisphenol f type epoxy resin, and its epoxide equivalent is 200~5000.
8. preparation method according to claim 1, it is characterised in that：
The thio-ether type compounds include diethyl thioether, dipropyl thioether, butyl sulfide, diphenyl sulfide, thiodiglycol, first
Sulfenyl phenmethylol, methylthiophenol, methylthio-benzoic acid, methylthio phenyl acetic acid, 3 methyl mercapto 1 hexanol, 2- ethylthioethanols,
3- ethylmercapto groups propyl alcohol, 4,4'- dihydroxy diphenyl sulfide and 2- Mercaptoethyls；
The Bronsted acid includes formic acid, glacial acetic acid, sulfamic acid, nitric acid, lactic acid and 2,2- dihydromethyl propionic acids；
The water is deionized water.
9. a kind of cathode electrophoresis dope sulfosalt type dispersion resin, it passes through according to any one of claim 1 to 8
It is prepared by preparation method.
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| CN108690460A (en) * | 2018-04-03 | 2018-10-23 | 河北晨阳工贸集团有限公司 | A kind of cathode electrophoresis dope and preparation method thereof |
| CN108976981A (en) * | 2018-06-11 | 2018-12-11 | 中海油常州涂料化工研究院有限公司 | A kind of cathode electrophoresis dope lotion and preparation method thereof, cathode electrophoresis dope and preparation method thereof |
| CN111393683A (en) * | 2020-04-20 | 2020-07-10 | 广东科德环保科技股份有限公司 | Modified cationic microgel and preparation method and application thereof |
| CN114874413A (en) * | 2022-02-25 | 2022-08-09 | 上海金力泰化工股份有限公司 | Dispersion resin for cathode electrophoretic coating matched with film pretreatment and preparation method and application thereof |
| CN117551381A (en) * | 2023-11-10 | 2024-02-13 | 珠海东胜科技有限公司 | Heat-insulating glass coating and preparation method thereof |
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