CN112375208A - High-throwing-power toughened cathode electrophoresis resin and preparation method thereof, and electrophoresis emulsion and preparation method thereof - Google Patents
High-throwing-power toughened cathode electrophoresis resin and preparation method thereof, and electrophoresis emulsion and preparation method thereof Download PDFInfo
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- CN112375208A CN112375208A CN202011357441.9A CN202011357441A CN112375208A CN 112375208 A CN112375208 A CN 112375208A CN 202011357441 A CN202011357441 A CN 202011357441A CN 112375208 A CN112375208 A CN 112375208A
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- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 238000001962 electrophoresis Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000839 emulsion Substances 0.000 title claims abstract description 25
- 238000004945 emulsification Methods 0.000 title description 2
- 239000004593 Epoxy Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 28
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229940043237 diethanolamine Drugs 0.000 claims abstract description 21
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 14
- 150000002513 isocyanates Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 239000000159 acid neutralizing agent Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000007921 spray Substances 0.000 abstract description 3
- 229920006317 cationic polymer Polymers 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- DDNCQMVWWZOMLN-IRLDBZIGSA-N Vinpocetine Chemical compound C1=CC=C2C(CCN3CCC4)=C5[C@@H]3[C@]4(CC)C=C(C(=O)OCC)N5C2=C1 DDNCQMVWWZOMLN-IRLDBZIGSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229960000744 vinpocetine Drugs 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
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- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
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- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
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Abstract
The invention provides a high throwing power toughening cathode electrophoresis resin and a preparation method thereof, and an electrophoresis emulsion and a preparation method thereof, wherein epoxy resin E-51, bisphenol A, diethanolamine and methyl isobutyl ketone are mixed, heated for reaction, and then added with an epoxy diluent 207 for reaction; then adding methyl isobutyl ketone, controlling the temperature, adding diethanol amine, heating for reaction, finally adding methyl isobutyl ketone, mixing and stirring uniformly to obtain the high-throwing-power toughened cathode electrophoresis resin; the throwing power is improved by improving the solvent content, increasing the molecular weight of the epoxy resin and reducing the MEQ value; the cathodic electrophoresis emulsion and the bath solution are prepared by taking the cationic polymer as raw materials, the obtained cathodic electrophoresis emulsion is stable in storage, and a paint film of a sample plate prepared by bath solution electrophoresis has better salt spray resistance, sharp edge corrosion resistance and impact toughness performance.
Description
Technical Field
The invention belongs to the technical field of electrophoretic paint preparation, and particularly relates to a high-throwing-power toughened cathode electrophoretic resin and a preparation method thereof, and an electrophoretic emulsion and a preparation method thereof.
Background
As a high-grade consumer product in modern society, the automobile coating needs to meet the high-quality requirement of consumers, so that the requirement on the corrosion resistance of automobiles is very high, and the electrophoretic coating has been widely applied as the primer of the automobile body since 60 years. After the salt spray performance is met, the thickness of the inner film of the automobile body is increased and is gradually emphasized. Through promoting wet film resistance, reduce solvent content, increase epoxy main resin molecular weight, reduce the MEQ value, can promote the throwing power of electrophoresis tank liquor by a wide margin. By applying the new method for detecting the throwing power of the four-box method, the throwing power of a new generation of high throwing power toughened product is improved from 25% to about 63%, so that the requirements of electrophoresis lines of a host factory on the thickness and the throwing power of an inner film of a vehicle body are met, and the toughness problem after a coating film is thinned is solved.
At present, in the passenger vehicle industry, domestic autonomous enterprises in China have acquired the qualification of suppliers and are applied in the market. However, due to throwing power, impact toughness and low-temperature baking performance, an autonomous electrophoretic coating enterprise has not made a great breakthrough in the passenger vehicle industry, and the autonomous high-throwing-power toughened product is believed to have a larger market application prospect.
Disclosure of Invention
The invention aims to provide a high-throwing-power toughened cathode electrophoretic resin and a preparation method thereof, which improve the throwing power by improving the solvent content, increasing the molecular weight of epoxy resin and reducing the MEQ value.
The invention also aims to provide an electrophoretic emulsion and a preparation method thereof, which are prepared by using the high throwing power toughened cathode electrophoretic resin.
The specific technical scheme of the invention is as follows:
a preparation method of high throwing power toughening cathode electrophoresis resin is characterized in that a matrix epoxy resin E51 is prepared into amine modified resin, and epoxy reactive diluent is added to increase the molecular flexibility of an epoxy chain, so that the toughness of the epoxy resin and a coating is improved, and the preparation method specifically comprises the following steps:
1) mixing epoxy resin E-51, bisphenol A, diethanolamine and methyl isobutyl ketone, heating to perform epoxy chain extension for 1 step reaction, adding epoxy diluent 207, and continuing chain extension for 2 steps reaction;
2) adding methyl isobutyl ketone, cooling, adding diethanol amine, and heating for reaction;
3) and adding methyl isobutyl ketone, and uniformly mixing and stirring to obtain the cathode main electrophoretic resin.
The step 1 of epoxy chain extension reaction in the step 1) is carried out for 1-1.5 hours at the temperature of 120 +/-5 ℃;
the 2-step reaction of continuing the epoxy chain extension in the step 1) refers to a reaction at 120 +/-5 ℃ for 2-2.5 h.
Preferably, in the step 1), heating to perform epoxy chain extension for 1 step, and reacting for 1h at 120 ℃; in the epoxy chain extension reaction of step 1, performing chain extension addition on epoxy resin and bisphenol A, after the reaction is carried out for 1 hour, adding an epoxy diluent 207, continuing the chain extension reaction of step 2, and reacting for 2 hours at the temperature of 120 ℃; the detected epoxy value is qualified, and the detected epoxy value range is 1.31-1.45.
In the step 1), the mass ratio of the epoxy resin E-51, the bisphenol A, the diethanolamine, the methyl isobutyl ketone and the epoxy diluent 207 is 30-45: 10-20: 0.3-0.5: 1-3: 5-20 parts of;
the mass ratio of the diethanolamine in the step 1) to the diethanolamine in the step 2) is 1: 15-26.
The epoxy equivalent of the epoxy resin E-51 in the step 1) is 188-192, and the epoxy resin E-51 is vinpocetine epoxy resin BE-188 EL; the epoxy diluent 207 is polypropylene glycol glycidyl ether.
In the step 2), adding methyl isobutyl ketone, and cooling to 90 +/-5 ℃; adding diethanolamine;
the heating reaction in the step 2) refers to heating to 120-140 ℃ for 2-3 h.
And 2) carrying out amine modification, detecting the epoxy value reaction end point, and detecting the range of the epoxy value to be 1.05-1.17.
And 3) adding a solvent, diluting, adjusting the viscosity, discharging, and detecting the amine value range of 54-66.
The mass ratio of the methyl isobutyl ketone in the step 1), the step 2) and the step 3) is 1-3: 10-15: 10-15.
The high-throwing-power toughened cathode electrophoresis resin provided by the invention is prepared by the method, and the solid content of the resin is 70-80%.
The invention provides an electrophoretic emulsion, which takes the high throwing power toughened cathode electrophoretic resin as a raw material.
The electrophoresis emulsion comprises the following raw materials in percentage by weight:
the balance of deionized water.
The dispersant is polypropylene glycol; the acid neutralizer is formic acid or acetic acid.
The nonionic surfactant is OP-10.
The preparation method of the isocyanate modified resin comprises the following steps:
mixing isocyanate and methyl isobutyl ketone, heating to 80-85 ℃, starting to dropwise add ethylene glycol butyl ether, sampling and detecting NCO to be less than or equal to 90.0, adding propylene glycol, heating to 120 ℃, reacting at constant temperature, detecting NCO to be less than or equal to 1.0, cooling, discharging, and obtaining the isocyanate resin with the solid content of 85%.
The isocyanate model is Bayer 44V20 MDI.
The weight of the isocyanate, the methyl isobutyl ketone, the ethylene glycol butyl ether and the propylene glycol is 50-55: 10-15: 15-21: 14-19.
Dropwise adding ethylene glycol butyl ether for 1-2 hours;
adding propylene glycol, heating to 120 +/-5 ℃, and reacting at constant temperature for 1-3 h;
the preparation method of the electrophoresis emulsion provided by the invention comprises the following steps:
a) mixing the high throwing power toughened cathodic electrophoretic resin, the isocyanic acid modified resin and the dispersing agent according to the formula amount, adding the acid neutralizing agent according to the formula amount after uniformly stirring, adding the nonionic surfactant according to the formula amount, and uniformly stirring and mixing;
b) and then, dropwise adding deionized water into the system, and simultaneously carrying out high-speed dispersion to obtain the electrophoretic emulsion.
The step a) of uniformly stirring means uniformly stirring for 20-30min at 40-60 ℃;
adding an acid neutralizer in the step a), and stirring for 15-20 min;
dropwise adding deionized water in the step b), and controlling the dropwise adding time to be 25-35 min;
the high-speed dispersion rotating speed in the step b) is 700-1400 r/min.
In the preparation method of the high throwing power toughened cathode electrophoresis main resin, firstly, under the catalytic action of trace diethanolamine, ring opening of epoxy resin E51 is carried out to carry out chain extension reaction with bisphenol A, active epoxy diluent is added after one stage of the chain extension reaction, the toughness of the epoxy resin is increased, the molecular weight is increased, and finally, diethanolamine and epoxy group at the end of a molecular chain are added to carry out ring opening for modification, so that the main resin capable of being quaternized is obtained.
The prepared cathode electrophoresis main resin is matched with isocyanate modified resin (cross-linked cured resin) to serve as matrix resin, and a nonionic surfactant and a dispersing agent are added, so that the ionization of the cathode electrophoresis main resin quaternary ammonium salt is realized under the neutralization action of an acid neutralizing agent, and the isocyanate modified resin is wrapped to form micelle particles. And then shearing and emulsifying in deionized water to obtain uniform and stable cathode electrophoresis emulsion. The paint film of the sample plate obtained by bath solution electrophoresis has better salt spray resistance, sharp edge corrosion resistance and impact toughness performance;
compared with the prior art, the invention has the following advantages: the cathode electrophoresis main resin prepared by the preparation method is used as one of raw materials of the cathode electrophoresis emulsion to prepare electrophoresis tank liquid, a standard phosphatized plate is used for carrying out four throwing power tests to prepare the plate, the throwing power is greatly improved, and meanwhile, the active epoxy diluent is added to increase the molecular weight of the main resin, so that the good impact toughness and the cup convex performance of an electrophoresis coating are ensured.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A preparation method of a high throwing power toughened cathode electrophoresis resin comprises the following steps:
1) mixing 35 parts of epoxy resin E-51, 19 parts of bisphenol A, 0.3 part of diethanolamine and 3 parts of methyl isobutyl ketone, reacting for 1 hour at 120 ℃, continuously adding 12 parts of epoxy diluent 207 monomer, reacting for 2.0 hours at 120 ℃, and sampling to test the epoxy value of the reaction system, wherein the epoxy value is 1.42; the epoxy equivalent of the used epoxy resin E-51 is 188-192, and the epoxy resin E-51 is vinpocetine epoxy resin BE-188 EL;
2) adding 10 parts of methyl isobutyl ketone, controlling the reaction temperature to 90 ℃, adding 5 parts of diethanol amine, heating to 140 ℃, and reacting for 3 hours; detecting the epoxy value to be 1.15;
3) adding 15 parts of methyl isobutyl ketone, mixing and stirring uniformly, cooling and discharging to obtain the high-throwing-power toughened cathode electrophoresis resin CED-101.
The cathodic electrophoretic host resin prepared in this example had a solids content of 75% and an amine number of 55.
Example 2
A preparation method of a high throwing power toughened cathode electrophoresis resin comprises the following steps:
1) 32 parts of epoxy resin E-51, 19 parts of bisphenol A, 0.3 part of diethanolamine and 3 parts of methyl isobutyl ketone are mixed and reacted for 1 hour at 120 ℃, 15 parts of epoxy diluent 207 monomer is continuously added and reacted for 2.0 hours at 120 ℃, and then a sample is taken to test the epoxy value of the reaction system, wherein the epoxy value is 1.35.
2) Adding 10 parts of methyl isobutyl ketone, controlling the reaction temperature to 90 ℃, adding 7 parts of diethanol amine, heating to 140 ℃, and reacting for 3 hours; the epoxy value was measured at 1.08.
3) Adding 15 parts of methyl isobutyl ketone, mixing and stirring uniformly, cooling and discharging to obtain the high-throwing-power toughened cathode electrophoresis resin CED-201.
The high throwing power toughened cathodic electrophoretic resin prepared in the example has a solid content of 75% and an amine value of 63.
Comparative example 1
A preparation method of cathode electrophoresis resin comprises the following steps:
1) mixing 44 parts of epoxy resin E-51, 19 parts of bisphenol A, 0.3 part of diethanolamine and 2 parts of methyl isobutyl ketone, reacting for 3 hours at 120 ℃, and sampling to test the epoxy value of a reaction system, wherein the epoxy value is 1.31;
2) adding 10 parts of methyl isobutyl ketone, controlling the reaction temperature to 90 ℃, adding 8 parts of diethanol amine, heating to 140 ℃, and reacting for 3 hours; the epoxy value was determined to be 1.23.
3) Adding 15 parts of methyl isobutyl ketone, mixing and stirring uniformly, cooling and discharging to obtain the cathode electrophoresis resin ED-301 with the solid content of 75% and the amine value of 65;
the cathodic electrophoretic resins prepared in the above examples and comparative examples were prepared into electrophoretic emulsions according to the weight percentages in table 1.
TABLE 1 electrophoretic emulsion formulation
The preparation method of the electrophoresis emulsion comprises the following steps:
a) mixing the main resin, the isocyanate modified resin and the dispersing agent according to the formula amount shown in the table 1, uniformly stirring for 30min at 40 ℃, adding the acid neutralizing agent according to the formula amount, uniformly stirring for 15min, adding the surfactant according to the formula amount, and uniformly stirring and mixing;
b) and then, dropwise adding deionized water into the system, controlling the dropwise adding time to be 30min, and simultaneously carrying out high-speed dispersion at 1000r/min to obtain the milky-white cathode electrophoresis emulsion.
The preparation methods of the isocyanate-modified resins used in example 1, example 2 and comparative example 1 were:
mixing isocyanate and methyl isobutyl ketone, heating to 80-85 ℃, beginning to drop ethylene glycol butyl ether for 2 hours, adding propylene glycol at 80 ℃ after the NCO is less than or equal to 90.0 by sampling detection and the value is qualified, heating to 120 ℃, reacting at constant temperature for 2 hours, detecting the NCO is less than or equal to 1.0, cooling to 70 ℃, discharging, and obtaining the isocyanate resin with the solid content of 85 percent. The isocyanate model is Bayer 44V20 MDI. The weight of the isocyanate, the methyl isobutyl ketone, the ethylene glycol butyl ether and the propylene glycol is 50: 10: 21: 19;
mixing the obtained electrophoretic emulsion 1, electrophoretic emulsion 2 and electrophoretic emulsion 3 with color paste and deionized water according to the ratio of 4: mixing the materials according to the mass ratio of 1:5, uniformly stirring, ventilating, curing and stirring for 24 hours to respectively obtain electrophoresis tank liquid 1, electrophoresis tank liquid 2 and electrophoresis tank liquid 3, carrying out electrophoresis plate making in the electrophoresis tank liquid by using a standard phosphorization plate, wherein the electrophoresis process parameters are 250V and 3 minutes, and evaluating the prepared electrophoresis plate, and the results are shown in Table 2.
TABLE 3 electrophoretic Panel Properties
The electrophoresis liquid provided by the invention is prepared, the MEQ value is reduced to improve the throwing power, and the good impact toughness and the cup convex performance of an electrophoresis coating are ensured.
Claims (10)
1. A preparation method of a high throwing power toughened cathode electrophoresis resin is characterized by comprising the following steps:
1) mixing epoxy resin E-51, bisphenol A, diethanolamine and methyl isobutyl ketone, heating to perform epoxy chain extension for 1 step reaction, adding epoxy diluent 207, and continuing chain extension for 2 steps reaction;
2) adding methyl isobutyl ketone, cooling, adding diethanol amine, and heating for reaction;
3) and adding methyl isobutyl ketone, and uniformly mixing and stirring to obtain the cathode main electrophoretic resin.
2. The preparation method of claim 1, wherein the 1-step epoxy chain extension reaction in the step 1) is carried out at 120 ± 5 ℃ for 1-1.5 h; the 2-step reaction of continuing the epoxy chain extension in the step 1) refers to a reaction at 120 +/-5 ℃ for 2-2.5 h.
3. The process according to claim 1 or 2, wherein the mass ratio of the methyl isobutyl ketone in the step 1), the step 2) and the step 3) is 1 to 3: 10-15: 10-15.
4. The preparation method according to claim 1, wherein in the step 1), the mass ratio of the epoxy resin E-51, the bisphenol A, the diethanolamine, the methyl isobutyl ketone and the epoxy diluent 207 is 30-45: 10-20: 0.3-0.5: 1-3: 5-20.
5. The method as claimed in claim 1, wherein the heating reaction in step 2) is carried out at 120-140 ℃ for 2-3 h.
6. The preparation method according to claim 1, wherein the mass ratio of diethanolamine in step 1) to diethanolamine in step 2) is 1: 15-26.
7. The high throwing power toughened cathodic electrophoretic resin prepared by the preparation method of any one of claims 1 to 6, wherein the solid content of the high throwing power toughened cathodic electrophoretic resin is 70 to 80 percent.
8. An electrophoretic emulsion, characterized in that the high throwing power toughened cathodic electrophoretic resin prepared by the preparation method of any one of claims 1 to 6 is used as a raw material, and the electrophoretic emulsion comprises the following raw materials in percentage by mass:
9. the electrophoretic emulsion according to claim 8, wherein the isocyanate-modified resin is prepared by a method comprising:
mixing isocyanate and methyl isobutyl ketone, heating to 80-85 ℃, starting to dropwise add ethylene glycol butyl ether, sampling and detecting NCO to be less than or equal to 90.0, adding propylene glycol, heating to 120 ℃, reacting at constant temperature to detect NCO to be less than or equal to 1.0%, cooling, discharging, and obtaining the isocyanate resin with the solid content of 85%.
10. A method for preparing an electrophoretic emulsion according to claim 8 or 9, comprising the steps of:
a) mixing the high throwing power toughened cathodic electrophoretic resin, the isocyanic acid modified resin and the dispersing agent according to the formula amount, adding the acid neutralizing agent according to the formula amount after uniformly stirring, adding the nonionic surfactant according to the formula amount, and uniformly stirring and mixing;
b) and then, dropwise adding deionized water into the system, and simultaneously carrying out high-speed dispersion to obtain the electrophoretic emulsion.
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