CN111286255A - Ketimine modified epoxy flexible emulsion and preparation method thereof - Google Patents
Ketimine modified epoxy flexible emulsion and preparation method thereof Download PDFInfo
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- CN111286255A CN111286255A CN202010189344.7A CN202010189344A CN111286255A CN 111286255 A CN111286255 A CN 111286255A CN 202010189344 A CN202010189344 A CN 202010189344A CN 111286255 A CN111286255 A CN 111286255A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 51
- 239000004593 Epoxy Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000004658 ketimines Chemical class 0.000 title claims abstract description 15
- 238000004945 emulsification Methods 0.000 title claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 24
- 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 22
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims abstract description 15
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 14
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 diethylenetriamine ketimine Chemical class 0.000 claims abstract description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 8
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 8
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims abstract description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019253 formic acid Nutrition 0.000 claims abstract description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 6
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 239000004014 plasticizer Substances 0.000 claims abstract description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000080 wetting agent Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 31
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 230000001804 emulsifying effect Effects 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 238000005070 sampling Methods 0.000 claims description 9
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- PUSKHXMZPOMNTQ-UHFFFAOYSA-N ethyl 2,1,3-benzoselenadiazole-5-carboxylate Chemical group CCOC(=O)C1=CC=C2N=[Se]=NC2=C1 PUSKHXMZPOMNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 238000005576 amination reaction Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 22
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000001962 electrophoresis Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- NNJPGOLRFBJNIW-HNNXBMFYSA-N (-)-demecolcine Chemical compound C1=C(OC)C(=O)C=C2[C@@H](NC)CCC3=CC(OC)=C(OC)C(OC)=C3C2=C1 NNJPGOLRFBJNIW-HNNXBMFYSA-N 0.000 description 1
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a ketimine modified epoxy flexible emulsion and a preparation method thereof, wherein the flexible emulsion comprises the following raw materials: the flexible emulsion is prepared from epoxy resin, bisphenol A polyoxyethylene ether, xylene formaldehyde resin, dimethylbenzylamine, a cross-linking agent, ethylene glycol butyl ether, propylene glycol phenyl ether, a cross-linking agent, methyl monoethanolamine, diethylenetriamine ketimine, polypropylene glycol ether, a plasticizer, a wetting agent, formic acid, acetic acid and pure water through the steps of epoxy chain extension, amination, neutralization and emulsification.
Description
Technical Field
The invention relates to the technical field of production of cathode electrophoretic coatings, in particular to a ketimine modified epoxy flexible emulsion and a preparation method thereof.
Background
The cathode electrophoretic coating has the advantages of excellent corrosion resistance, high electrophoretic permeability, high coating automation degree, small environmental pollution and the like, so that the cathode electrophoretic coating is widely applied to metal surfaces of automobile industry, household appliances, mechanical products, light industrial products and the like.
The two-component cathode electrophoretic paint comprises emulsion and color paste, wherein the color paste influences the color of the paint, and the emulsion influences the film forming performance of the paint. At present, after electrophoresis processing, workpieces in some automobile parts markets and small hardware markets need to be subjected to processes of bending, stamping, deforming and the like, and after the processes, electrophoresis paint films on processed parts of traditional electrophoretic paints often have the problems of paint film cracking, falling off and the like. If such a problem occurs, only a paint repair treatment can be performed, which has an extremely adverse effect on the appearance and corrosion resistance of the end product. Therefore, it is highly desirable to develop a flexible resin emulsion.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, electrophoresis paint films of workpieces are often cracked and fall off when the electrophoresis paint films of the processing parts are subjected to procedures of bending, stamping, deformation and the like after electrophoresis processing, and provides a ketimine modified epoxy flexible emulsion and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the ketimine modified epoxy flexible emulsion comprises the following raw materials in parts by weight: 9-12 parts of epoxy resin, 2-4 parts of bisphenol A, 3-5 parts of bisphenol A polyoxyethylene ether, 1-2 parts of xylene formaldehyde resin, 0.03-0.07 part of dimethylbenzylamine, 9-12 parts of a cross-linking agent 1, 2-4 parts of a cross-linking agent 2, 10.3-0.5 part of ethylene glycol butyl ether, 1.0-1.5 parts of propylene glycol phenyl ether, 0.3-0.5 part of a cross-linking agent, 0.8-1.2 parts of methyl monoethanolamine, 1.1-1.5 parts of diethylenetriamine ketimine, 0.1-1.3 parts of polypropylene glycol ether, 0.6-1.2 parts of a plasticizer, 0.08-0.12 part of a wetting agent, 0.3-0.5 part of formic acid, 0.3-0.5 part of acetic acid and 55-65 parts of pure water.
The preparation method of the cross-linking agent 1 comprises the following steps:
the method comprises the following steps: mixing and stirring 6-9 parts of methyl ethyl ketone and 8-11 parts of trimethylolpropane uniformly, raising the temperature to 60-70 ℃ at the same time, dissolving the solid material uniformly, and preserving the temperature of the prepared mixed solution at more than 50 ℃ for later use;
step two: adding 38-42 parts of toluene diisocyanate, 3-5 parts of methyl ethyl ketone and 0.01-0.03 part of dibutyltin dilaurate into a reaction kettle, stirring in a nitrogen atmosphere, and heating to 40-50 ℃; then slowly dripping the mixed solution of the methyl ethyl ketone and the trimethylolpropane in the step I at a constant speed, fully stirring, controlling the temperature of the reaction kettle to be 55-60 ℃ during dripping, and preserving heat for 50-70 minutes at the temperature after dripping;
step three: continuously dropwise adding 28-35 parts of ethylene glycol butyl ether, controlling the temperature of the reaction kettle at 65-70 ℃, then keeping the temperature at 73-77 ℃ for 1.5-2.5 hours, and sampling to measure the NCO value;
step four: and after the NCO value is qualified, adding 8-11 parts of ethylene glycol butyl ether, cooling to 58-62 ℃, and preserving heat for later use.
The preparation method of the cross-linking agent 2 comprises the following steps:
the method comprises the following steps: adding 45-52 parts of triurea HI100 and 15-20 parts of methyl isobutyl ketone into a reaction kettle, stirring in a nitrogen atmosphere, and heating to 40-50 ℃; then slowly dripping 28-35 parts of di-n-butylamine at a constant speed, fully stirring, controlling the temperature of the reaction kettle to be 50-60 ℃ during dripping, preserving the temperature at 65-70 ℃ for 1.5-2.5 hours after dripping, and sampling to measure the NCO value;
step two: and after the NCO value is qualified, adding 2-5 parts of n-butyl alcohol, cooling to 58-62 ℃, and preserving heat for later use.
All the raw materials of the ketimine modified epoxy flexible emulsion are obtained by the method, and the preparation of the ketimine modified epoxy flexible emulsion comprises the following steps:
adding epoxy resin, bisphenol A polyoxyethylene ether and xylene formaldehyde resin into a reaction kettle, and adding dimethylbenzylamine for the first time when the temperature is raised to 140-150 ℃ in a nitrogen atmosphere and is stable; continuously heating to 175-185 ℃ and preserving heat for 20-40 minutes, then quickly cooling to 140-150 ℃ and when the temperature is stable, adding dimethylbenzylamine for the second time, preserving heat for 3-5 hours at 140-150 ℃, and detecting the epoxy value;
step two, after the epoxy value reaches a specified value, adding ethylene glycol butyl ether and propylene glycol phenyl ether into a reaction kettle, cooling to 115-125 ℃, quickly adding a crosslinking agent 1 and a crosslinking agent 2, and stirring for 20-40 minutes; continuously cooling to below 105 ℃, quickly adding methyl monoethanolamine and diethylenetriamine ketimine, heating to 115-125 ℃, keeping the temperature for 1-3 hours, and sampling to detect the total amine value;
step three: after the total amine value is qualified, cooling to 70-75 ℃, adding polypropylene glycol ether, a plasticizer and a wetting agent, then continuously cooling to 60-65 ℃, adding formic acid for neutralization, and stirring for 50-70 minutes at the temperature of 65-70 ℃;
step four: and adding the neutralized materials into an emulsifying kettle, controlling the adding flow to be 50-100 Kg/min, and stirring and emulsifying the neutralized materials with acetic acid and pure water in the emulsifying kettle for 0.5-1.5 hours to finish the preparation of the ketimine modified epoxy flexible emulsion.
Preferably, the acetic acid and the pure water are stirred uniformly in advance in the emulsifying kettle, and the temperature is controlled between 20 and 30 ℃.
Preferably, the air pressure in the emulsifying kettle is less than 0.1 MPa.
According to the project, dimethylbenzylamine is added twice, and in the formula design, dimethylbenzylamine is used as a catalyst, the dimethylbenzylamine is added for the first time, then the temperature is raised to 175-185 ℃, the temperature is kept for 20-40 minutes, and the materials are enabled to react rapidly to obtain epoxy resin-bisphenol A and epoxy resin-bisphenol A polyoxyethylene ether molecules; and then cooling to 140-150 ℃, adding dimethylbenzylamine, and carrying out epoxy chain extension to obtain epoxy resin-bisphenol A-epoxy resin-bisphenol A polyoxyethylene ether molecules, so as to avoid forming epoxy resin-bisphenol A-epoxy resin molecules.
After the epoxy value reaches a specified value, adding ethylene glycol butyl ether and propylene glycol phenyl ether into a reaction kettle, cooling to 115-125 ℃, then quickly adding a cross-linking agent, and stirring for 20-40 minutes; and (3) continuously cooling to below 105 ℃, quickly adding methyl monoethanolamine and diethylenetriamine ketimine, heating to 115-125 ℃, and keeping the temperature for 1-3 hours. Because of the volatility of amine, the amine needs to be added quickly, in order to prevent the situation that the addition is unfavorable for temperature control when the temperature is too high, methyl monoethanolamine and diethylenetriamine ketimine are added when the temperature is below 105 ℃, the early reaction is slow, the temperature can be naturally raised to 110 ℃, and the control of the subsequent reaction temperature is facilitated.
The flexible emulsion uses diethylenetriamine ketimine and methyl monoethanolamine, so that the emulsion has better conductivity, and meanwhile, the viscosity of the neutralized resin is reduced, thereby being beneficial to reducing the content of solvent in the emulsion and improving the throwing power of the electrophoretic paint and the storage stability of the emulsion.
The air pressure in the emulsifying kettle is less than 0.1MPa, the negative pressure has the effect of increasing the flow of the neutralizing resin, the flow control during the emulsification is very critical, the smaller the flow is, the poorer the emulsification effect is, the larger the particle size of the emulsion is, and the adverse effect is caused on the subsequent storage stability.
In the preparation of the cross-linking agent 1, trimethylolpropane and toluene diisocyanate have violent exothermic reaction, and must be slowly dripped, and the temperature is controlled to be between 55 and 60 ℃ to prevent the occurrence of the cross-linking reaction. Trimethylolpropane is used in the formula of the cross-linking agent, so that heating decrement of the electrophoretic paint is reduced, and the cross-linking density of a paint film is improved.
In the preparation of the cross-linking agent 2, the triurea HI100 is used as a reactant, and the synthesized cross-linked resin can reduce the hardness of the resin, increase the toughness of the resin and improve the cross-linking density of a paint film.
The preparation method of the flexible emulsion can prepare the emulsion with high flexibility, and the prepared emulsion has the characteristics of low solvent content, high electrophoretic permeability, good flexibility and the like, and is suitable for an electrophoretic post-processing process.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Firstly, preparing raw materials of the ketimine modified epoxy flexible emulsion, wherein the preparation method of the cross-linking agent 1 comprises the following steps:
the method comprises the following steps: putting 7.6 parts of methyl ethyl ketone and 9.5 parts of trimethylolpropane into a dropwise adding tank, opening and stirring, heating the dropwise adding tank to 65 ℃ (not exceeding 75 ℃) to enable the trimethylolpropane to be dissolved uniformly, and preserving heat at the temperature of not lower than 50 ℃ for later use;
step two: adding 39 parts of toluene diisocyanate, 3.5 parts of methyl ethyl ketone and 0.02 part of dibutyltin dilaurate into a reaction kettle, stirring in a nitrogen atmosphere, and heating to 45 ℃; slowly dripping the mixed solution obtained in the step one at a constant speed, controlling the temperature of the reaction kettle to be 55-60 ℃, fully stirring, and preserving the temperature for 1 hour after the mixed solution is dripped;
step three: continuously dropwise adding 31.2 parts of butyl cellosolve, controlling the temperature of the reaction kettle to be 65-70 ℃, after the dropwise adding is finished, keeping the temperature at 75 ℃ for 2 hours, and sampling to measure the NCO value;
in the embodiment, the catalyst is dibutyltin dilaurate, wherein the reaction principle of the first step and the second step is as follows: toluene diisocyanate OCN-R1-NCO reacts with trimethylolpropane or ethylene glycol monobutyl ether OH-R2 to generate a substance A, R2-O-C (O) -NH-R1-NH-C (O) -O-R2, and methyl ethyl ketone is used as a solvent at the position to dissolve and dilute without participating in the reaction.
Step four: and (3) after the NCO value is qualified, adding 9.18 parts of ethylene glycol monobutyl ether into the solution obtained in the third step, cooling to 60 ℃, and keeping the temperature for later use.
The preparation method of the cross-linking agent 2 comprises the following steps:
the method comprises the following steps: adding 48.1 parts of triurea HI100 and 17 parts of methyl isobutyl ketone into a reaction kettle, stirring under a nitrogen atmosphere, and heating to 50 ℃; and slowly dripping 31 parts of di-n-butylamine at a constant speed, controlling the temperature of the reaction kettle to be 50-60 ℃ when dripping is finished, preserving the temperature at 65-70 ℃ for 1.5-2.5 hours after dripping is finished, and sampling to measure the NCO value.
Step two: and after the NCO value is qualified, adding 3.9 parts of n-butyl alcohol, cooling to 58-62 ℃, and preserving heat for later use.
The reaction principle in the first step in this example is: reacting the-NCO molecule of the triurea HI100 with-NH of di-n-butylamine to generate R1-NH-C (O) -O-R2, wherein the methyl isobutyl ketone is used as a solvent to dissolve and dilute and does not participate in the reaction.
After the raw material of the ketimine modified epoxy flexible emulsion is obtained, the emulsion is prepared, and the preparation of the emulsion comprises the following steps:
the method comprises the following steps: adding 11.1 parts of epoxy resin, 2.8 parts of bisphenol A, 4 parts of bisphenol A polyoxyethylene ether and 1.5 parts of xylene formaldehyde resin into a reaction kettle, and adding 0.02 part of dimethylbenzylamine for the first time when the temperature is raised to 146 ℃ in a nitrogen atmosphere and is stable; and continuously heating to 180 ℃ and preserving heat for 30 minutes, then quickly cooling to 150 ℃ and when the temperature is stable, adding 0.03 part of dimethylbenzylamine for the second time, preserving heat at 150 ℃ for 4 hours, and detecting the epoxy value.
When dimethylbenzylamine is added for the first time, epoxy resin O (CH2CH) -R1- (CHCH2) O reacts with bisphenol A OH-R2-OH to generate B substance O (CH2CH) -R1-CH (OH) CH2-O-R2-OH, and epoxy resin O (CH2CH) -R1- (CHCH2) O reacts with bisphenol A polyoxyethylene ether OH-R3 to generate C substance O (CH2CH) -R1-CH (OH) CH 2-O-R3.
When dimethylbenzylamine is added for the second time, substance C O (CH2CH) -R1-CH (OH) CH2-O-R3 reacts with substance B O (CH2CH) -R1-CH (OH) CH2-O-R2-OH to generate substance D O (CH2CH) -R1-CH (OH) CH2-O-R2-CH (OH) CH2-R1-CH (OH) CH 2-O-R3.
Step two: after the epoxy value reaches a specified value, adding 0.27 part of ethylene glycol butyl ether and 1.3 parts of propylene glycol phenyl ether into a reaction kettle, quickly adding 10.9 parts of cross-linking agent 1 and 2.9 parts of cross-linking agent 2 when the temperature is reduced to 120 ℃, and stirring for 30 minutes; continuously cooling to below 105 ℃, quickly adding 1 part of methyl monoethanolamine and 1.4 parts of diethylenetriamine ketimine, heating to 120 ℃, keeping the temperature for 2 hours, and sampling to detect the total amine value;
the methyl monoethanolamine and the diethylenetriamineketimine R-NH in the step can respectively react with the substance C O (CH2CH) -R1-CH (OH) CH2-O-R3 and the substance D O (CH2CH) -R1-CH (OH) CH2-O-R2-CH (OH) CH2-R1-CH (OH) CH2-O-R3 in the solution in the step one, the reaction product comprises substance E, R-N-CH2CH (OH) -R1-CH (OH) CH2-O-R3 and substance F, R-N-CH2CH (OH) -R1-CH (OH) CH2-O-R2-CH (OH) CH2-R1-CH (OH) CH 2-O-R3-O (CH2CH) -R1-CH (OH) CH 2-O-R3.
The third step is a neutralization process: after the total amine value is qualified, cooling to 80 ℃, adding 0.15 part of polypropylene glycol ether, 0.8 part of plasticizer and 0.12 part of surface wetting agent, then continuously cooling to 75 ℃, adding 0.5 part of formic acid for neutralization, and stirring for 60 minutes at the controlled temperature of 75-80 ℃;
the fourth step is an emulsification process: and adding the neutralized materials into an emulsifying kettle within 60 +/-5 minutes, and stirring and emulsifying the neutralized materials, 0.4 part of acetic acid and 61 parts of pure water which are uniformly stirred in the emulsifying kettle in advance and have the temperature of more than 20 ℃ for 1 hour to finish the preparation of the flexible emulsion.
The reaction principle in the third step and the fourth step is as follows: formic acid and lactic acid R4-COOH are subjected to neutralization reaction with amine resin to generate G substance R-N+H(-CH2CH(OH)-R1-CH(OH)CH2-O-R3) -O--C (O) -R4, H species R-N+H(CH2CH(OH)-R1-CH(OH)CH2-O-R2- CH(OH)CH2-R1-CH(OH)CH2-O-R3-O(CH2CH)-R1-CH(OH)CH2-O-R3)-O-
-C(O)-R4。
After the flexible emulsion is obtained, the parameters of the ketimine modified epoxy flexible emulsion and the Hunan Weibang 842 emulsion are compared, and through respective detection, the comparison data is shown as follows:
the comparison of two emulsion parameters shows that the flexible emulsion has smaller particle size and is beneficial to the storage stability of the emulsion.
The flexible emulsion can be used in paint, the paint is used as a decorative material and needs to be endowed with color, the conventional cathode electrophoretic paint adopts two components, namely a resin component and a color paste component, the emulsion prepared in the embodiment is the resin component, the resin component endows the paint film with physical properties, and the color paste component endows the paint film with color.
In order to further verify the influence of the flexible emulsion on the performance of the coating, 842 emulsion and flexible emulsion are used, the same black color paste is added, and the ratio is black color paste: emulsion: water 1: 7: 15, mixing for 48 hours, performing electrophoresis by using a standard phosphatizing plate, washing and drying to obtain a complete paint film, and then performing physical property inspection, wherein the film coating performance parameters are compared as follows:
under the condition of the same parameters, a 0.8mm sample plate is used for carrying out an impact resistance test, the result shows that the paint film of the flexible emulsion has no cracks and peeling phenomena under the experimental conditions that the impact height is 50cm and the impact quality is 1000g, while the impact height of the 842 emulsion can only reach 20cm, cracks appear on the paint film surface of the 842 emulsion, and the paint film peeling situation appears in severe cases, and the experimental data shows that the flexible emulsion has good flexibility.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. The ketimine modified epoxy flexible emulsion is characterized by comprising the following raw materials: 9-12 parts of epoxy resin, 2-4 parts of bisphenol A, 3-5 parts of bisphenol A polyoxyethylene ether, 1-2 parts of xylene formaldehyde resin, 0.03-0.07 part of dimethylbenzylamine, 9-12 parts of a cross-linking agent 1, 2-4 parts of a cross-linking agent 2, 10.3-0.5 part of ethylene glycol butyl ether, 1.0-1.5 parts of propylene glycol phenyl ether, 0.3-0.5 part of a cross-linking agent, 0.8-1.2 parts of methyl monoethanolamine, 1.1-1.5 parts of diethylenetriamine ketimine, 0.1-1.3 parts of polypropylene glycol ether, 0.6-1.2 parts of a plasticizer, 0.08-0.12 part of a wetting agent, 0.3-0.5 part of formic acid, 0.3-0.5 part of acetic acid and 55-65 parts of pure water.
2. The ketimine-modified epoxy flexible emulsion according to claim 1, characterized in that the preparation method of the crosslinking agent 1 comprises the following steps:
the method comprises the following steps: mixing and stirring 6-9 parts of methyl ethyl ketone and 8-11 parts of trimethylolpropane uniformly, raising the temperature to 60-70 ℃ at the same time, dissolving the solid material uniformly, and preserving the temperature of the prepared mixed solution at more than 50 ℃ for later use;
step two: adding 38-42 parts of toluene diisocyanate, 3-5 parts of methyl ethyl ketone and 0.01-0.03 part of dibutyltin dilaurate into a reaction kettle, stirring in a nitrogen atmosphere, and heating to 40-50 ℃; then slowly dripping the mixed solution of the methyl ethyl ketone and the trimethylolpropane in the step I at a constant speed, fully stirring, controlling the temperature of the reaction kettle to be 55-60 ℃ during dripping, and preserving heat for 50-70 minutes at the temperature after dripping;
step three: continuously dropwise adding 28-35 parts of ethylene glycol butyl ether, controlling the temperature of the reaction kettle at 65-70 ℃, then keeping the temperature at 73-77 ℃ for 1.5-2.5 hours, and sampling to measure the NCO value;
step four: and after the NCO value is qualified, adding 8-11 parts of ethylene glycol butyl ether, cooling to 58-62 ℃, and preserving heat for later use.
3. The ketimine-modified epoxy flexible emulsion according to claim 2, characterized in that the preparation method of the crosslinking agent 2 comprises the following steps:
the method comprises the following steps: adding 45-52 parts of triurea HI100 and 15-20 parts of methyl isobutyl ketone into a reaction kettle, stirring in a nitrogen atmosphere, and heating to 40-50 ℃; then slowly dripping 28-35 parts of di-n-butylamine at a constant speed, fully stirring, controlling the temperature of the reaction kettle to be 50-60 ℃ during dripping, preserving the temperature at 65-70 ℃ for 1.5-2.5 hours after dripping, and sampling to measure the NCO value;
step two: and after the NCO value is qualified, adding 2-5 parts of n-butyl alcohol, cooling to 58-62 ℃, and preserving heat for later use.
4. The method for preparing the ketimine-modified epoxy flexible emulsion as recited in claim 3, characterized by comprising the steps of:
adding epoxy resin, bisphenol A polyoxyethylene ether and xylene formaldehyde resin into a reaction kettle, and adding dimethylbenzylamine for the first time when the temperature is raised to 140-150 ℃ in a nitrogen atmosphere and is stable; continuously heating to 175-185 ℃ and preserving heat for 20-40 minutes, then quickly cooling to 140-150 ℃ and when the temperature is stable, adding dimethylbenzylamine for the second time, preserving heat for 3-5 hours at 140-150 ℃, and detecting the epoxy value;
step two, after the epoxy value reaches a specified value, adding ethylene glycol butyl ether and propylene glycol phenyl ether into a reaction kettle, cooling to 115-125 ℃, quickly adding a crosslinking agent 1 and a crosslinking agent 2, and stirring for 20-40 minutes; continuously cooling to below 105 ℃, quickly adding methyl monoethanolamine and diethylenetriamine ketimine, heating to 115-125 ℃, keeping the temperature for 1-3 hours, and sampling to detect the total amine value;
step three: after the total amine value is qualified, cooling to 70-75 ℃, adding polypropylene glycol ether, a plasticizer and a wetting agent, then continuously cooling to 60-65 ℃, adding formic acid for neutralization, and stirring for 50-70 minutes at the temperature of 65-70 ℃;
step four: and adding the neutralized materials into an emulsifying kettle, controlling the adding flow to be 50-100 Kg/min, and stirring and emulsifying the neutralized materials with acetic acid and pure water in the emulsifying kettle for 0.5-1.5 hours to finish the preparation of the ketimine modified epoxy flexible emulsion.
5. The method for preparing the ketimine-modified epoxy flexible emulsion as recited in claim 4, wherein the acetic acid and the pure water are stirred uniformly in advance in the emulsifying kettle, and the temperature is controlled between 20-30 ℃.
6. The method for preparing the ketimine-modified epoxy flexible emulsion as recited in claim 4, wherein an air pressure in the emulsification vessel is less than 0.1 MPa.
7. A coating comprising as its starting material a ketimine modified epoxy flexible emulsion prepared according to the process of claim 4.
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