CN112940558A - Electrophoretic paint curing agent with good water solubility and application thereof - Google Patents
Electrophoretic paint curing agent with good water solubility and application thereof Download PDFInfo
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- CN112940558A CN112940558A CN202110043069.2A CN202110043069A CN112940558A CN 112940558 A CN112940558 A CN 112940558A CN 202110043069 A CN202110043069 A CN 202110043069A CN 112940558 A CN112940558 A CN 112940558A
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 112
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000003973 paint Substances 0.000 title claims description 18
- 238000001962 electrophoresis Methods 0.000 claims abstract description 79
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003822 epoxy resin Substances 0.000 claims abstract description 45
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 45
- 239000000839 emulsion Substances 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000006184 cosolvent Substances 0.000 claims abstract description 17
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 72
- 238000003756 stirring Methods 0.000 claims description 70
- 238000002156 mixing Methods 0.000 claims description 56
- 238000010438 heat treatment Methods 0.000 claims description 52
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- QHBZHVUGQROELI-SOFGYWHQSA-N (E)-10-hydroxydec-2-enoic acid Chemical compound OCCCCCCC\C=C\C(O)=O QHBZHVUGQROELI-SOFGYWHQSA-N 0.000 claims description 39
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 38
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 37
- 229910000831 Steel Inorganic materials 0.000 claims description 35
- 239000010959 steel Substances 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 30
- 125000002091 cationic group Chemical group 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 27
- GJOWSEBTWQNKPC-UHFFFAOYSA-N 3-methyloxiran-2-ol Chemical compound CC1OC1O GJOWSEBTWQNKPC-UHFFFAOYSA-N 0.000 claims description 25
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 25
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001704 evaporation Methods 0.000 claims description 24
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 18
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 17
- 239000012948 isocyanate Substances 0.000 claims description 17
- 150000002513 isocyanates Chemical class 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 14
- 238000010907 mechanical stirring Methods 0.000 claims description 14
- 230000003472 neutralizing effect Effects 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 13
- 125000003700 epoxy group Chemical group 0.000 claims description 13
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003337 fertilizer Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 40
- 239000011248 coating agent Substances 0.000 abstract description 39
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 19
- 239000010410 layer Substances 0.000 abstract description 14
- 238000004132 cross linking Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 239000011247 coating layer Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 205
- 238000001723 curing Methods 0.000 description 110
- 230000000052 comparative effect Effects 0.000 description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 14
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 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 7
- 235000019253 formic acid Nutrition 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010511 deprotection reaction Methods 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- QHBZHVUGQROELI-UHFFFAOYSA-N Royal Jelly acid Natural products OCCCCCCCC=CC(O)=O QHBZHVUGQROELI-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- LBUSGXDHOHEPQQ-UHFFFAOYSA-N propane-1,1,1-triol Chemical class CCC(O)(O)O LBUSGXDHOHEPQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004383 yellowing 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
- C09D5/4453—Polyepoxides characterised by the nature of the curing agent
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of electrophoretic coating, and discloses an electrophoretic coating curing agent with good water solubility and application thereof, aiming at the problem of poor crosslinking capability of the existing electrophoretic coating curing agent. The additive comprises the following components in parts by mass based on 100 parts by mass: 25-35% of epoxy resin matrix, 10-15% of curing agent, 8-10% of cosolvent, 1-3% of toner, 3-5% of oxalic acid and the balance of water. According to the invention, the curing agent with multiple active sites and fluidity is prepared by improving the synthesis process of the curing agent, multiple benzene rings and multiple long-chain branches are introduced on the curing agent, the multiple benzene rings can improve the thermal stability and the wear resistance of a coating layer, and the long-chain branches can ensure the compatibility and the fluidity of the multiple benzene rings and a resin emulsion, so that the wear resistance, the thermal stability, the weather resistance and the comprehensive mechanical properties of an electrophoresis film layer are finally improved.
Description
Technical Field
The invention relates to the technical field of electrophoretic coating, in particular to an electrophoretic coating curing agent with good water solubility and application thereof.
Background
The electrophoretic coating is one of water-based coatings with wide application, and in recent years, along with the progress and development of cathode electrophoretic coating technology, the functionality, the decoration, the economy and the application range of the electrophoretic coating are greatly improved, and the electrophoretic coating is mainly reflected in the aspects of corrosion resistance, the decoration, the environmental protection performance, the weather resistance, the energy saving performance and the like of the electrophoretic coating. The electrophoretic coating has the advantages of no tin, no lead, low harm, flat coating appearance, high throwing power, high corrosion resistance, high stone impact resistance, low-temperature curing to save energy cost, wider curing temperature to ensure excellent curing performance and yellowing resistance of the coating, and is the development direction of the cathode electrophoretic coating. The electrophoretic paint contains the curing agent with the largest content except the resin matrix, and the performance of the curing agent directly influences the comprehensive mechanical property of the final electrophoretic paint. However, the existing curing agent has the defects of poor water solubility, small fluidity and the like.
The invention discloses a preparation method of a special blocked polyisocyanate curing agent for 120 ℃ low-temperature curing electrophoretic paint, which is disclosed by the patent number CN201410796679.X, and relates to a preparation method of a special blocked polyisocyanate curing agent for 120 ℃ low-temperature curing electrophoretic paint. The cathode electrophoretic paint prepared by using the curing agent has good decorative coating characteristics, and can realize the complete curing of a coating film at a lower curing temperature (120 ℃ and 0.5h), thereby expanding the decorative coating of the electrophoretic paint on the surface of a substrate workpiece such as copper, aluminum and the like. Specifically, the curing agent is prepared by using dicyanate monomers with polar structures, dicyanate tripolymers and dicyanate and trihydroxypropane adducts as main raw materials, adopting compounds capable of providing active hydrogen for end capping, and reacting at a lower temperature.
The defects are that the curing agent has few reactive active sites and poor crosslinking capability.
Disclosure of Invention
The invention provides an electrophoretic paint curing agent with good water solubility and application thereof, aiming at overcoming the problem of poor crosslinking capability of the existing electrophoretic paint curing agent. According to the invention, the curing agent with multiple active sites and fluidity is prepared by improving the synthesis process of the curing agent, multiple benzene rings and multiple long-chain branches are introduced on the curing agent, the multiple benzene rings can improve the thermal stability and the wear resistance of a coating layer, and the long-chain branches can ensure the compatibility and the fluidity of the multiple benzene rings and a resin emulsion, so that the wear resistance, the thermal stability, the weather resistance and the comprehensive mechanical properties of an electrophoresis film layer are finally improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the molecular structure of the curing agent is a multi-benzene-ring long branched chain structure with good fluidity.
Preferably, the preparation steps are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.06-0.08 percent of the weight of the isocyanate and butanone accounting for 3-5 percent of the weight of the isocyanate, reacting at a constant temperature of 95-100 ℃, and stopping the reaction when the molar content of-NCO is reduced to 48-50 percent of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 0.75-1% of the total weight of the product I and the queen bee acid, heating to 84-86 ℃, and reacting for 2-2.5h to obtain a product II;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 118-122 ℃, dropwise adding dodecyl trimethyl ammonium bromide, continuously preserving the temperature for 3.2-3.5h after the dropwise adding is finished, and evaporating to remove the solvent after the reaction is finished to obtain a product III;
(4) and (3) mixing the product III in a mass ratio of 1: 1-1.2, dissolving in ethanol, heating to 62-66 ℃, continuously dripping tetraethylenepentamine, and continuously reacting for 4.2-4.5 hours under the condition of heat preservation to obtain a product IV;
(5) dropwise adding epoxy propanol accounting for 0.5-0.8% of the mass fraction of the product IV into the product IV, heating to 65-70 ℃ for reaction for 3.2-3.8h, and evaporating ethanol after the reaction is finished to obtain a capped amino product;
(6) and dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 50-60%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 60-65 ℃ for 1-1.5h to obtain an end-capped hydroxyl product.
The invention obtains the polyphenyl ring long branched chain structure with good fluidity through the six steps, and in the step (1), the tripolymer containing a plurality of benzene rings is obtained through the self-polymerization of the diphenylmethane diisocyanate; adding the queen bee acid to carry out chain extension to obtain an active intermediate with the queen bee acid, and introducing an active reaction group carboxyl; adding 1, 4-butanediol diglycidyl ether to enable an epoxy group at one end to react with carboxyl, further amplifying the length of a linear branched chain, and generating hydroxyl with high reaction activity; adding tetraethylenepentamine in the step (4) to amplify the length of the linear branched chain again and continuously introducing hydroxyl with high reaction activity; and (5) introducing epoxy propanol, so that an epoxy group can react with an amino group at the end of the branched chain to generate two hydroxyl groups, and finally each branched chain contains a plurality of hydroxyl groups, thereby greatly improving the reaction activity of the curing agent. Considering that the electrophoretic paint needs to be mixed and cured for a long time in advance to enable the components to permeate into each other as much as possible, in order to avoid cross-linking in the mixing process and the electrophoresis process, a plurality of hydroxyl groups on the branched chain of the curing agent need to be protected, and the trimethylsilyl group in the step (6) is introduced to temporarily protect the hydroxyl groups.
The curing agent prepared by the invention has the characteristic of linear long branched chain structure around a middle multiple benzene ring, and has the following characteristics: (1) because the benzene ring has stronger rigidity and thermal stability, the introduction of a plurality of benzene rings can greatly improve the thermal stability and the wear resistance of the electrophoresis film; (2) because the mobility of the multi-benzene ring in the resin emulsion is poor, and the number of active reaction groups of the prepolymer is small, the linear branched chain structure with long length and multiple active groups is introduced around the multi-benzene ring prepolymer, the mobility of the macromolecular polymer and the compatibility of the macromolecular polymer with other components can be improved by the linear structure, and the protected hydroxyl still has strong polarity, so that the water solubility of the curing agent is greatly enhanced, the linear long branched chain structure is easier to permeate into other components in the mixing process, and the finally obtained electrophoretic emulsion has better uniformity.
Preferably, in the step (2), the mass ratio of the product I to the queen bee acid is 1: 4.5-6.
Preferably, in step (3), n (carboxyl) to 1, 4-butanediol diglycidyl ether n (epoxy) in product II is 1: 2; and/or dodecyl trimethyl ammonium bromide accounts for 2-5% of the weight of the 1, 4-butanediol diglycidyl ether.
Preferably, in step (4), n (epoxy) to n (tetraethylenepentamine) in product III is 1: 2.
Preferably, in the step (5), the mass ratio of the product IV to the epoxypropanol is 1: 0.005-0.008.
Preferably, in the step (6), the mass ratio of the blocked amino product to the trimethylsilyl group is 1: 0.12-0.15.
The curing agent is applied to the electrophoretic coating, and the preparation process of the electrophoretic coating comprises the following steps: mixing an epoxy resin matrix, a cosolvent and the curing agent at 50-60 ℃, stirring for 30-40min, adding oxalic acid under stirring, and neutralizing for 0.5-0.8h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding toner and deionized water under the stirring state, stirring for 20-30min to obtain uniformly dispersed cathode electrophoresis emulsion, and curing for 22-24 h; taking a steel plate as a cathode, and performing electrophoresis for 2.5-3min under the electrophoresis voltage of 150V; after electrophoresis, taking out the steel plate, cleaning the steel plate by using deionized water, firstly preserving the heat at 80-100 ℃ for 40-50min, and then baking the steel plate at 150-160 ℃ for 30-35min to obtain the electrophoresis film.
Preferably, sulfosalicylic acid accounting for 0.8-1.5% of the weight of the curing agent is added into the aged cathode electrophoresis emulsion before electrophoresis, and the stirring is continued for 5-10 min.
In the process of preparing the electrophoretic coating, the added components are uniformly mixed, and then the uniformly mixed components are cured, so that the components are further mixed. Sulfosalicylic acid is added to the aged cathodic electrophoretic emulsion to deprotect the protected hydroxyl groups, and the deprotection reaction occurs when heated to a temperature above the thermal reaction temperature. Sulfosalicylic acid is uniformly distributed in the electrophoretic emulsion at normal temperature and electrophoresed on a steel plate, when the temperature is raised by heating, hydroxyl begins to be exposed and can participate in reaction, when the temperature reaches 80-100 ℃, sulfosalicylic acid begins to be decomposed into sulfonic acid and salicylic acid, the content of carboxyl is increased, the deprotection reaction of the hydroxyl is further increased, after the heat preservation is finished, the temperature is continuously raised, on one hand, the crosslinking reaction of a curing agent and the resin emulsion can be promoted, on the other hand, small molecular components are rapidly volatilized, and the finally prepared electrophoretic film has high crosslinking degree, high density, high weather resistance, high wear resistance, high thermal stability and high permeability.
In addition, the invention adopts the processes of heat preservation and baking for gradual temperature rise, so that hydroxyl can be fully deprotected, and meanwhile, the crosslinking reaction process of the curing agent provides reaction conditions for gradual reaction to guide final high-temperature heating so as to fully volatilize small molecules and residual solvents, so that the crosslinking reaction is more sufficient, and the prepared electrophoretic membrane has high flatness and good compactness.
Preferably, the additive components and the ratio thereof are calculated according to 100 mass portions as follows: 25-35% of epoxy resin matrix, 10-15% of curing agent, 8-10% of cosolvent, 1-3% of toner, 3-5% of oxalic acid and the balance of water.
Therefore, the invention has the following beneficial effects:
(1) according to the invention, the curing agent with multiple active sites and fluidity is prepared by improving the synthesis process of the curing agent, multiple benzene rings and multiple long-chain branches are introduced on the curing agent, the multiple benzene rings can improve the thermal stability and the wear resistance of a coating layer, and the long-chain branches can ensure the compatibility and the fluidity of the multiple benzene rings and a resin emulsion, so that the wear resistance, the thermal stability, the weather resistance and the comprehensive mechanical property of an electrophoresis film layer are finally improved;
(2) due to the fact that the benzene rings have high rigidity and thermal stability, the introduction of the multiple benzene rings can greatly improve the thermal stability and the wear resistance of the finally prepared electrophoresis film;
(3) by introducing the linear branched chain structure with long length and multiple active groups around the polyphenyl ring prepolymer, the linear structure can increase the fluidity of the macromolecular polymer and the compatibility of the macromolecular polymer with other components, and the linear long branched chain structure can be more easily infiltrated into other components in the mixing process, so that the finally obtained electrophoretic emulsion has better uniformity.
Detailed Description
General examples
The preparation method of the electrophoretic coating containing the multi-benzene ring long branched chain structure curing agent comprises the following steps: mixing 25-35% of epoxy resin matrix, 8-10% of cosolvent and 10-15% of curing agent at 50-60 ℃, stirring for 30-40min, adding 3-5% of oxalic acid under stirring, and neutralizing for 0.5-0.8h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 1-3% of toner and deionized water under the stirring state, stirring for 20-30min to obtain uniformly dispersed cathode electrophoresis emulsion, and curing for 22-24 h; adding sulfosalicylic acid 0.8-1.5 wt% of the curing agent, and stirring for 5-10 min; taking a steel plate as a cathode, and performing electrophoresis for 2.5-3min under the electrophoresis voltage of 150V; after electrophoresis, taking out the steel plate, cleaning the steel plate by using deionized water, firstly preserving the heat at 80-100 ℃ for 40-50min, and then baking the steel plate at 150-160 ℃ for 30-35min to obtain the electrophoresis film.
The preparation steps of the curing agent are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.06-0.08 percent of the weight of the isocyanate and butanone accounting for 3-5 percent of the weight of the isocyanate, reacting at a constant temperature of 95-100 ℃, and stopping the reaction when the molar content of-NCO is reduced to 48-50 percent of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 0.75-1% of the total weight of the product I and the queen bee acid, heating to 84-86 ℃, and reacting for 2-2.5h to obtain a product II; the mass ratio of the product I to the queen bee acid is 1: 4.5-6;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 118-122 ℃, dropwise adding dodecyl trimethyl ammonium bromide accounting for 2-5% of the weight of the 1, 4-butanediol diglycidyl ether, continuing to keep the temperature for 3.2-3.5h after the dropwise adding is finished, and evaporating the solvent after the reaction is finished to obtain a product III; in the product II, n (carboxyl) and n (epoxy) in 1, 4-butanediol diglycidyl ether are 1: 2;
(4) and (3) mixing the product III in a mass ratio of 1: 1-1.2, dissolving in ethanol, heating to 62-66 ℃, continuously dripping tetraethylenepentamine, and continuously reacting for 4.2-4.5 hours under the condition of heat preservation to obtain a product IV; in the product III, n (epoxy group) to n (tetraethylenepentamine) is 1: 2;
(5) dropwise adding epoxy propanol accounting for 0.5-0.8% of the mass fraction of the product IV into the product IV, heating to 65-70 ℃ for reaction for 3.2-3.8h, and evaporating ethanol after the reaction is finished to obtain a capped amino product; the mass ratio of the product IV to the epoxypropanol is 1: 0.005-0.008;
(6) dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 50-60%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 60-65 ℃ for 1-1.5h to obtain an end-capped hydroxyl product; the mass ratio of the end-capped amino product to the trimethylsilyl group is 1: 0.12-0.15.
Example 1
The preparation method of the electrophoretic coating containing the multi-benzene ring long branched chain structure curing agent comprises the following steps: mixing 30% of epoxy resin matrix, 9% of cosolvent and 13% of curing agent at 55 ℃, stirring for 35min, adding 4% of oxalic acid under stirring, and neutralizing for 0.65h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 2% of toner and deionized water under the stirring state, stirring for 25min to obtain a uniformly dispersed cathode electrophoresis emulsion, and curing for 23 h; adding sulfosalicylic acid 1.2% of the curing agent, and continuously stirring for 8 min; taking a steel plate as a cathode, and carrying out electrophoresis for 2.8min under the electrophoresis voltage of 150V; after electrophoresis is finished, the steel plate is taken out, washed by deionized water, firstly kept at 90 ℃ for 45min, and then baked at 155 ℃ for 32min, so that an electrophoresis film layer is obtained.
The preparation steps of the curing agent are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.07 percent of the weight of the isocyanate and 4 percent of butanone, reacting at constant temperature of 98 ℃, and stopping the reaction when the molar content of-NCO is reduced to 49 percent of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 0.85 percent of the total weight of the product I and the queen bee acid, heating to 85 ℃ and reacting for 2.2 hours to obtain a product II; the mass ratio of the product I to the queen bee acid is 1: 5.2;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 120 ℃, dropwise adding dodecyl trimethyl ammonium bromide accounting for 3.5 percent of the weight of the 1, 4-butanediol diglycidyl ether, continuously preserving the temperature for 3.4 hours after the dropwise adding is finished, and evaporating the solvent after the reaction is finished to obtain a product III; in the product II, n (carboxyl) and n (epoxy) in 1, 4-butanediol diglycidyl ether are 1: 2;
(4) and (3) mixing the product III in a mass ratio of 1: 1.1 dissolving into ethanol, heating to 64 ℃, continuously dropwise adding tetraethylenepentamine, and continuously reacting for 4.4 hours under the condition of heat preservation to obtain a product IV; in the product III, n (epoxy group) to n (tetraethylenepentamine) is 1: 2;
(5) dropwise adding epoxy propanol accounting for 0.65% of the mass fraction of the product IV into the product IV, heating to 68 ℃ for reaction for 3.5 hours, and evaporating ethanol after the reaction is finished to obtain a capped amino product; the mass ratio of the product IV to the epoxypropanol is 1: 0.0065;
(6) dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 55%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 62 ℃ for 1.2h to obtain an end-capped hydroxyl product; the mass ratio of the end-capped amino product to the trimethylsilyl group is 1: 0.13.
example 2
The preparation method of the electrophoretic coating containing the multi-benzene ring long branched chain structure curing agent comprises the following steps: mixing 21% of epoxy resin matrix, 8.5% of cosolvent and 11% of curing agent at 52 ℃, stirring for 32min, adding 3.5% of oxalic acid under stirring, and neutralizing for 0.6h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 1.5% of toner and deionized water under the stirring state, stirring for 22min to obtain uniformly dispersed cathode electrophoresis emulsion, and curing for 22.5 h; adding sulfosalicylic acid 0.9 wt% of the curing agent, and stirring for 6 min; taking a steel plate as a cathode, and carrying out electrophoresis for 2.7min under the electrophoresis voltage of 150V; after electrophoresis is finished, the steel plate is taken out, washed by deionized water, firstly kept at 85 ℃ for 42min, and then baked at 152 ℃ for 31min, so that an electrophoresis film layer is obtained.
The preparation steps of the curing agent are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.065 percent of the weight of the isocyanate and butanone accounting for 3.5 percent of the weight of the isocyanate, reacting at constant temperature of 96 ℃, and stopping the reaction when the molar content of-NCO is reduced to 48.5 percent of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 0.8 percent of the total weight of the product I and the queen bee acid, heating to 84.5 ℃, and reacting for 2.1 hours to obtain a product II; the mass ratio of the product I to the queen bee acid is 1: 4.6;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 119 ℃, dropwise adding dodecyl trimethyl ammonium bromide accounting for 2.5 percent of the weight of the 1, 4-butanediol diglycidyl ether, continuously preserving the temperature for 3.3 hours after the dropwise adding is finished, and evaporating the solvent after the reaction is finished to obtain a product III; in the product II, n (carboxyl) and n (epoxy) in 1, 4-butanediol diglycidyl ether are 1: 2;
(4) and (3) mixing the product III in a mass ratio of 1: 1.05 dissolving into ethanol, heating to 63 ℃, continuously dripping tetraethylenepentamine, and continuously reacting for 4.3 hours under the condition of heat preservation to obtain a product IV; in the product III, n (epoxy group) to n (tetraethylenepentamine) is 1: 2;
(5) dropwise adding epoxy propanol accounting for 0.6% of the mass fraction of the product IV into the product IV, heating to 66 ℃ for reaction for 3.4 hours, and evaporating ethanol after the reaction is finished to obtain a capped amino product; the mass ratio of the product IV to the epoxypropanol is 1: 0.006;
(6) dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 50-60%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 63 ℃ for 1.1h to obtain an end-capped hydroxyl product; the mass ratio of the end-capped amino product to the trimethylsilyl group is 1: 0.13.
example 3
The preparation method of the electrophoretic coating containing the multi-benzene ring long branched chain structure curing agent comprises the following steps: mixing 32% of epoxy resin matrix, 9.5% of cosolvent and 14% of curing agent at 58 ℃, stirring for 38min, adding 4.5% of oxalic acid under the stirring state, and neutralizing for 0.7h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 2.5% of toner and deionized water under the stirring state, stirring for 28min to obtain uniformly dispersed cathode electrophoresis emulsion, and curing for 23.5 h; adding sulfosalicylic acid 1.4% of the curing agent, and continuously stirring for 9.5 min; taking a steel plate as a cathode, and carrying out electrophoresis for 2.9min under the electrophoresis voltage of 150V; after electrophoresis is finished, the steel plate is taken out, washed by deionized water, firstly kept at 95 ℃ for 48min, and then baked at 158 ℃ for 34min to obtain an electrophoresis film layer.
The preparation steps of the curing agent are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.075 percent of the weight of the isocyanate and butanone accounting for 4.5 percent of the weight of the isocyanate, reacting at a constant temperature of 99 ℃, and stopping the reaction when the molar content of-NCO is reduced to 48.5 percent of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 0.9 percent of the total weight of the product I and the queen bee acid, heating to 85.5 ℃, and reacting for 2.4 hours to obtain a product II; the mass ratio of the product I to the queen bee acid is 1: 5.5;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 121 ℃, dropwise adding dodecyl trimethyl ammonium bromide accounting for 4% of the weight of the 1, 4-butanediol diglycidyl ether, continuously preserving the temperature for 3.4 hours after dropwise adding is finished, and evaporating the solvent after the reaction is finished to obtain a product III; in the product II, n (carboxyl) and n (epoxy) in 1, 4-butanediol diglycidyl ether are 1: 2;
(4) and (3) mixing the product III in a mass ratio of 1: 1.15 dissolving into ethanol, heating to 65 ℃, continuously dropwise adding tetraethylenepentamine, and continuously reacting for 4.4 hours under the condition of heat preservation to obtain a product IV; in the product III, n (epoxy group) to n (tetraethylenepentamine) is 1: 2;
(5) dropwise adding epoxy propanol accounting for 0.7% of the mass fraction of the product IV into the product IV, heating to 68 ℃ for reaction for 3.6 hours, and evaporating ethanol after the reaction is finished to obtain a capped amino product; the mass ratio of the product IV to the epoxypropanol is 1: 0.007;
(6) dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 58%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 64 ℃ for 1.1h to obtain an end-capped hydroxyl product; the mass ratio of the end-capped amino product to the trimethylsilyl group is 1: 0.13.
example 4
The preparation method of the electrophoretic coating containing the multi-benzene ring long branched chain structure curing agent comprises the following steps: mixing and stirring 35% of epoxy resin matrix, 8% of cosolvent and 15% of curing agent for 30min at 50 ℃, adding 5% of oxalic acid under stirring, and neutralizing for 0.5h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 1% of toner and deionized water under the stirring state, stirring for 30min to obtain a uniformly dispersed cathode electrophoresis emulsion, and curing for 22 h; adding sulfosalicylic acid 0.8% of the curing agent, and continuously stirring for 10 min; taking a steel plate as a cathode, and carrying out electrophoresis for 2.5min under the electrophoresis voltage of 150V; after electrophoresis is finished, the steel plate is taken out, washed by deionized water, firstly kept at 100 ℃ for 40min, and then baked at 160 ℃ for 30min to obtain an electrophoresis film layer.
The preparation steps of the curing agent are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.06% of the weight of the isocyanate and butanone accounting for 5%, reacting at a constant temperature of 95 ℃, and stopping the reaction when the molar content of-NCO is reduced to 50% of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 0.75 percent of the total weight of the product I and the queen bee acid, heating to 86 ℃ and reacting for 2 hours to obtain a product II; the mass ratio of the product I to the queen bee acid is 1: 4.5;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 118 ℃, dropwise adding dodecyl trimethyl ammonium bromide accounting for 5% of the weight of the 1, 4-butanediol diglycidyl ether, continuously preserving the temperature for 3.2 hours after the dropwise adding is finished, and evaporating the solvent after the reaction is finished to obtain a product III; in the product II, n (carboxyl) and n (epoxy) in 1, 4-butanediol diglycidyl ether are 1: 2;
(4) and (3) mixing the product III in a mass ratio of 1: 1, dissolving the product into ethanol, heating to 66 ℃, continuously dropwise adding tetraethylenepentamine, and continuously reacting for 4.2 hours under the condition of heat preservation to obtain a product IV; in the product III, n (epoxy group) to n (tetraethylenepentamine) is 1: 2;
(5) dropwise adding epoxy propanol accounting for 0.5% of the mass fraction of the product IV into the product IV, heating to 70 ℃ for reaction for 3.2 hours, and evaporating ethanol after the reaction is finished to obtain a capped amino product; the mass ratio of the product IV to the epoxypropanol is 1: 0.005;
(6) dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 50%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 65 ℃ for 1h to obtain an end-capped hydroxyl product; the mass ratio of the end-capped amino product to the trimethylsilyl group is 1: 0.12.
example 5
The preparation method of the electrophoretic coating containing the multi-benzene ring long branched chain structure curing agent comprises the following steps: at 60 ℃, mixing and stirring 25% of epoxy resin matrix, 10% of cosolvent and 10% of curing agent for 40min, adding 5% of oxalic acid under the stirring state, and neutralizing for 0.5h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 3% of toner and deionized water under the stirring state, stirring for 20min to obtain a uniformly dispersed cathode electrophoresis emulsion, and curing for 24 h; adding sulfosalicylic acid 0.8% of the curing agent, and continuously stirring for 10 min; taking a steel plate as a cathode, and carrying out electrophoresis for 3min under the electrophoresis voltage of 150V; after electrophoresis is finished, the steel plate is taken out, washed by deionized water, firstly kept at 80 ℃ for 50min, and then baked at 150 ℃ for 35min to obtain an electrophoresis film layer.
The preparation steps of the curing agent are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.08 percent of the weight of the isocyanate and 3 percent of butanone, reacting at constant temperature of 100 ℃, and stopping the reaction when the molar content of-NCO is reduced to 50 percent of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 1% of the total weight of the product I and the queen bee acid, heating to 84 ℃ and reacting for 2.5 hours to obtain a product II; the mass ratio of the product I to the queen bee acid is 1: 6;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 122 ℃, dropwise adding dodecyl trimethyl ammonium bromide accounting for 2% of the weight of the 1, 4-butanediol diglycidyl ether, continuously preserving the temperature for 3.5 hours after dropwise adding is finished, and evaporating to remove the solvent after the reaction is finished to obtain a product III; in the product II, n (carboxyl) and n (epoxy) in 1, 4-butanediol diglycidyl ether are 1: 2;
(4) and (3) mixing the product III in a mass ratio of 1: 1.2 dissolving into ethanol, heating to 62 ℃, continuously dropwise adding tetraethylenepentamine, and continuously reacting for 4.5 hours under the condition of heat preservation to obtain a product IV; in the product III, n (epoxy group) to n (tetraethylenepentamine) is 1: 2;
(5) dropwise adding epoxy propanol accounting for 0.8% of the mass fraction of the product IV into the product IV, heating to 65 ℃ for reaction for 3.8h, and evaporating ethanol after the reaction is finished to obtain a capped amino product; the mass ratio of the product IV to the epoxypropanol is 1: 0.005;
(6) dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 60%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 60 ℃ for 1.5h to obtain an end-capped hydroxyl product; the mass ratio of the end-capped amino product to the trimethylsilyl group is 1: 0.15.
comparative example 1 (different from example 1 in that the curing agent was replaced with a blocked polyisocyanate curing agent.)
The preparation method of the electrophoretic coating containing the multi-benzene ring long branched chain structure curing agent comprises the following steps: mixing 30% of epoxy resin matrix, 9% of cosolvent and 13% of blocked polyisocyanate curing agent at 55 ℃, stirring for 35min, adding 4% of oxalic acid under stirring, and neutralizing for 0.65h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 2% of toner and deionized water under the stirring state, stirring for 25min to obtain a uniformly dispersed cathode electrophoresis emulsion, and curing for 23 h; adding sulfosalicylic acid 1.2% of the curing agent, and continuously stirring for 8 min; taking a steel plate as a cathode, and carrying out electrophoresis for 2.8min under the electrophoresis voltage of 150V; after electrophoresis is finished, the steel plate is taken out, washed by deionized water, firstly kept at 90 ℃ for 45min, and then baked at 155 ℃ for 32min, so that an electrophoresis film layer is obtained.
Comparative example 2 (differing from example 1 in that no prepolymerization of diphenylmethane diisocyanate was carried out, i.e.step (1) was omitted.)
The preparation method of the electrophoretic coating containing the multi-benzene ring long branched chain structure curing agent comprises the following steps: mixing 30% of epoxy resin matrix, 9% of cosolvent and 13% of curing agent at 55 ℃, stirring for 35min, adding 4% of oxalic acid under stirring, and neutralizing for 0.65h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 2% of toner and deionized water under the stirring state, stirring for 25min to obtain a uniformly dispersed cathode electrophoresis emulsion, and curing for 23 h; adding sulfosalicylic acid 1.2% of the curing agent, and continuously stirring for 8 min; taking a steel plate as a cathode, and carrying out electrophoresis for 2.8min under the electrophoresis voltage of 150V; after electrophoresis is finished, the steel plate is taken out, washed by deionized water, firstly kept at 90 ℃ for 45min, and then baked at 155 ℃ for 32min, so that an electrophoresis film layer is obtained.
The preparation steps of the curing agent are as follows:
(2) adding the royal jelly acid into the diphenylmethane diisocyanate, uniformly mixing, adding stannous octoate accounting for 0.85 percent of the total weight of the product I and the royal jelly acid, heating to 85 ℃, and reacting for 2.2 hours to obtain a product II; the mass ratio of the product I to the queen bee acid is 1: 5.2;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 120 ℃, dropwise adding dodecyl trimethyl ammonium bromide accounting for 3.5 percent of the weight of the 1, 4-butanediol diglycidyl ether, continuously preserving the temperature for 3.4 hours after the dropwise adding is finished, and evaporating the solvent after the reaction is finished to obtain a product III; in the product II, n (carboxyl) and n (epoxy) in 1, 4-butanediol diglycidyl ether are 1: 2;
(4) and (3) mixing the product III in a mass ratio of 1: 1.1 dissolving into ethanol, heating to 64 ℃, continuously dropwise adding tetraethylenepentamine, and continuously reacting for 4.4 hours under the condition of heat preservation to obtain a product IV; in the product III, n (epoxy group) to n (tetraethylenepentamine) is 1: 2;
(5) dropwise adding epoxy propanol accounting for 0.65% of the mass fraction of the product IV into the product IV, heating to 68 ℃ for reaction for 3.5 hours, and evaporating ethanol after the reaction is finished to obtain a capped amino product; the mass ratio of the product IV to the epoxypropanol is 1: 0.0065;
(6) dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 55%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 62 ℃ for 1.2h to obtain an end-capped hydroxyl product; the mass ratio of the end-capped amino product to the trimethylsilyl group is 1: 0.13.
comparative example 3 (different from example 1 in that the royal acid of step (2) was replaced with 5-hydroxym-benzoic acid.) preparation of an electrodeposition coating film containing a multi-benzene ring long branched chain structure curing agent: mixing 30% of epoxy resin matrix, 9% of cosolvent and 13% of curing agent at 55 ℃, stirring for 35min, adding 4% of oxalic acid under stirring, and neutralizing for 0.65h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 2% of toner and deionized water under the stirring state, stirring for 25min to obtain a uniformly dispersed cathode electrophoresis emulsion, and curing for 23 h; adding sulfosalicylic acid 1.2% of the curing agent, and continuously stirring for 8 min; taking a steel plate as a cathode, and carrying out electrophoresis for 2.8min under the electrophoresis voltage of 150V; after electrophoresis is finished, the steel plate is taken out, washed by deionized water, firstly kept at 90 ℃ for 45min, and then baked at 155 ℃ for 32min, so that an electrophoresis film layer is obtained.
The preparation steps of the curing agent are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.07 percent of the weight of the isocyanate and 4 percent of butanone, reacting at constant temperature of 98 ℃, and stopping the reaction when the molar content of-NCO is reduced to 49 percent of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 0.85 percent of the total weight of the product I and the 5-hydroxy m-benzoic acid, heating to 85 ℃ and reacting for 2.2 hours to obtain a product II; the mass ratio of the product I to the 5-hydroxy-m-benzoic acid is 1: 5.2;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 120 ℃, dropwise adding dodecyl trimethyl ammonium bromide accounting for 3.5 percent of the weight of the 1, 4-butanediol diglycidyl ether, continuously preserving the temperature for 3.4 hours after the dropwise adding is finished, and evaporating the solvent after the reaction is finished to obtain a product III; in the product II, n (carboxyl) and n (epoxy) in 1, 4-butanediol diglycidyl ether are 1: 2;
(4) and (3) mixing the product III in a mass ratio of 1: 1.1 dissolving into ethanol, heating to 64 ℃, continuously dropwise adding tetraethylenepentamine, and continuously reacting for 4.4 hours under the condition of heat preservation to obtain a product IV; in the product III, n (epoxy group) to n (tetraethylenepentamine) is 1: 2;
(5) dropwise adding epoxy propanol accounting for 0.65% of the mass fraction of the product IV into the product IV, heating to 68 ℃ for reaction for 3.5 hours, and evaporating ethanol after the reaction is finished to obtain a capped amino product; the mass ratio of the product IV to the epoxypropanol is 1: 0.0065;
(6) dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 55%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 62 ℃ for 1.2h to obtain an end-capped hydroxyl product; the mass ratio of the end-capped amino product to the trimethylsilyl group is 1: 0.13.
comparative example 4 (differing from example 1 in that the curing agent was not further chain extended, i.e., step (3) and step (4))
The preparation method of the electrophoretic coating containing the multi-benzene ring long branched chain structure curing agent comprises the following steps: mixing 30% of epoxy resin matrix, 9% of cosolvent and 13% of curing agent at 55 ℃, stirring for 35min, adding 4% of oxalic acid under stirring, and neutralizing for 0.65h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 2% of toner and deionized water under the stirring state, stirring for 25min to obtain a uniformly dispersed cathode electrophoresis emulsion, and curing for 23 h; adding sulfosalicylic acid 1.2% of the curing agent, and continuously stirring for 8 min; taking a steel plate as a cathode, and carrying out electrophoresis for 2.8min under the electrophoresis voltage of 150V; after electrophoresis is finished, the steel plate is taken out, washed by deionized water, firstly kept at 90 ℃ for 45min, and then baked at 155 ℃ for 32min, so that an electrophoresis film layer is obtained.
The preparation steps of the curing agent are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.07 percent of the weight of the isocyanate and 4 percent of butanone, reacting at constant temperature of 98 ℃, and stopping the reaction when the molar content of-NCO is reduced to 49 percent of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 0.85 percent of the total weight of the product I and the queen bee acid, heating to 85 ℃ and reacting for 2.2 hours to obtain a product II; the mass ratio of the product I to the queen bee acid is 1: 5.2;
(5) dropwise adding epoxy propanol accounting for 0.65% of the mass fraction of the product IV into the product IV, heating to 68 ℃ for reaction for 3.5 hours, and evaporating ethanol after the reaction is finished to obtain a capped amino product; the mass ratio of the product IV to the epoxypropanol is 1: 0.0065;
(6) dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 55%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 62 ℃ for 1.2h to obtain an end-capped hydroxyl product; the mass ratio of the end-capped amino product to the trimethylsilyl group is 1: 0.13.
comparative example 5 (different from example 1 in that the amino group was not blocked, i.e., step (5) was omitted.)
The preparation method of the electrophoretic coating containing the multi-benzene ring long branched chain structure curing agent comprises the following steps: mixing 30% of epoxy resin matrix, 9% of cosolvent and 13% of curing agent at 55 ℃, stirring for 35min, adding 4% of oxalic acid under stirring, and neutralizing for 0.65h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 2% of toner and deionized water under the stirring state, stirring for 25min to obtain a uniformly dispersed cathode electrophoresis emulsion, and curing for 23 h; adding sulfosalicylic acid 1.2% of the curing agent, and continuously stirring for 8 min; taking a steel plate as a cathode, and carrying out electrophoresis for 2.8min under the electrophoresis voltage of 150V; after electrophoresis is finished, the steel plate is taken out, washed by deionized water, firstly kept at 90 ℃ for 45min, and then baked at 155 ℃ for 32min, so that an electrophoresis film layer is obtained.
The preparation steps of the curing agent are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.07 percent of the weight of the isocyanate and 4 percent of butanone, reacting at constant temperature of 98 ℃, and stopping the reaction when the molar content of-NCO is reduced to 49 percent of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 0.85 percent of the total weight of the product I and the queen bee acid, heating to 85 ℃ and reacting for 2.2 hours to obtain a product II; the mass ratio of the product I to the queen bee acid is 1: 5.2;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 120 ℃, dropwise adding dodecyl trimethyl ammonium bromide accounting for 3.5 percent of the weight of the 1, 4-butanediol diglycidyl ether, continuously preserving the temperature for 3.4 hours after the dropwise adding is finished, and evaporating the solvent after the reaction is finished to obtain a product III; in the product II, n (carboxyl) and n (epoxy) in 1, 4-butanediol diglycidyl ether are 1: 2;
(4) and (3) mixing the product III in a mass ratio of 1: 1.1 dissolving into ethanol, heating to 64 ℃, continuously dropwise adding tetraethylenepentamine, and continuously reacting for 4.4 hours under the condition of heat preservation to obtain a product IV; in the product III, n (epoxy group) to n (tetraethylenepentamine) is 1: 2;
(6) dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 55%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 62 ℃ for 1.2h to obtain an end-capped hydroxyl product; the mass ratio of the end-capped amino product to the trimethylsilyl group is 1: 0.13.
comparative example 6 (different from example 1 in that sulfosalicylic acid was replaced with formic acid.)
The preparation method of the electrophoretic coating containing the multi-benzene ring long branched chain structure curing agent comprises the following steps: mixing 30% of epoxy resin matrix, 9% of cosolvent and 13% of curing agent at 55 ℃, stirring for 35min, adding 4% of oxalic acid under stirring, and neutralizing for 0.65h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding 2% of toner and deionized water under the stirring state, stirring for 25min to obtain a uniformly dispersed cathode electrophoresis emulsion, and curing for 23 h; adding formic acid accounting for 1.2 percent of the weight of the curing agent, and continuing stirring for 8 min; taking a steel plate as a cathode, and carrying out electrophoresis for 2.8min under the electrophoresis voltage of 150V; after electrophoresis is finished, the steel plate is taken out, washed by deionized water, firstly kept at 90 ℃ for 45min, and then baked at 155 ℃ for 32min, so that an electrophoresis film layer is obtained.
The preparation steps of the curing agent are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.07 percent of the weight of the isocyanate and 4 percent of butanone, reacting at constant temperature of 98 ℃, and stopping the reaction when the molar content of-NCO is reduced to 49 percent of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 0.85 percent of the total weight of the product I and the queen bee acid, heating to 85 ℃ and reacting for 2.2 hours to obtain a product II; the mass ratio of the product I to the queen bee acid is 1: 5.2;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 120 ℃, dropwise adding dodecyl trimethyl ammonium bromide accounting for 3.5 percent of the weight of the 1, 4-butanediol diglycidyl ether, continuously preserving the temperature for 3.4 hours after the dropwise adding is finished, and evaporating the solvent after the reaction is finished to obtain a product III; in the product II, n (carboxyl) and n (epoxy) in 1, 4-butanediol diglycidyl ether are 1: 2;
(4) and (3) mixing the product III in a mass ratio of 1: 1.1 dissolving into ethanol, heating to 64 ℃, continuously dropwise adding tetraethylenepentamine, and continuously reacting for 4.4 hours under the condition of heat preservation to obtain a product IV; in the product III, n (epoxy group) to n (tetraethylenepentamine) is 1: 2;
(5) dropwise adding epoxy propanol accounting for 0.65% of the mass fraction of the product IV into the product IV, heating to 68 ℃ for reaction for 3.5 hours, and evaporating ethanol after the reaction is finished to obtain a capped amino product; the mass ratio of the product IV to the epoxypropanol is 1: 0.0065;
(6) dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 55%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 62 ℃ for 1.2h to obtain an end-capped hydroxyl product; the mass ratio of the end-capped amino product to the trimethylsilyl group is 1: 0.13.
performance test:
examples 1 to 5 and comparative examples 1 to 6, respectively, were subjected to performance tests in accordance with the relevant standards, and the test results obtained are shown in Table 1.
Table 1 shows the physical properties of the items and the prepared electrophoretic coating film
And (4) conclusion: the data of the embodiment and the comparative example show that the performance of each parameter of the electrophoretic coating obtained within the ranges of the filler addition component, the addition content and the preparation sequence protected by the invention is superior to that of the electrophoretic coating not strictly prepared according to the parameter ranges defined by the protection ranges of the invention, the embodiment 1-5 shows that the curing agent with multiple active sites and fluidity is prepared by improving the synthesis process of the curing agent, a plurality of benzene rings and a plurality of long chain branches are introduced on the curing agent, the long chain branches can ensure the compatibility and fluidity of the benzene rings and the resin emulsion while the thermal stability and the wear resistance of the coating layer are improved, and finally the wear resistance, the thermal stability, the weather resistance and the comprehensive mechanical property of the electrophoretic coating layer are improved.
Comparative example 1 differs from example 1 in that the curing agent is replaced with a blocked polyisocyanate curing agent; the blocked polyisocyanate curing agent has the advantages that only isocyanate groups are used as reactive bonds in a macromolecular chain structure of the blocked polyisocyanate curing agent, the number of reactive groups is small, the crosslinking capability is poor, in addition, a linear long branched chain structure is not provided, and the blocked polyisocyanate curing agent is difficult to permeate into other components, so that the integrity and the comprehensive mechanical property of the final electrophoretic coating film are reduced.
Comparative example 2 differs from example 1 in that the diphenylmethane diisocyanate was not prepolymerized, i.e. step (1) was omitted; the catalyst is not prepolymerized, the number of the core benzene rings of each catalyst structure is obviously reduced by only two, and the catalyst only contains two long branched chain structures, so that the overall rigidity and the thermal stability of macromolecules are obviously reduced, the wear resistance of the macromolecule is also obviously reduced, and the related weather resistance is further influenced.
The difference between the comparative example 3 and the example 1 is that the 5-hydroxy-m-benzoic acid is replaced by the queen bee acid in the step (2), and a benzene ring and a nonlinear branched chain are introduced to the chain extending branched chain, so that the steric hindrance of a macromolecular chain is enlarged, the overall fluidity of the curing agent and the permeability of the linear long branched chain in other substances are reduced, and the overall uniformity, compactness and overall mechanical property of the electrophoretic coating are further reduced.
Comparative example 4 differs from example 1 in that the curing agent was not further chain extended, i.e., step (3) and step (4) were omitted; the extension of chain extension of the diphenylmethane diisocyanate prepolymer is not carried out, polar hydrophilic groups on a linear molecular chain are reduced, the fluidity and water solubility of the molecular structure of the curing agent are firstly reduced, and the mixing uniformity of the curing agent and other components is ensured.
Comparative example 5 differs from example 1 in that the amino group is not blocked, i.e. step (5) is omitted; the absence of a blocked amino group results in a slight crosslinking of the amino group during the mixing of the ingredients, reducing the flowability of the curing agent and reducing the hydroxyl-reactive groups on the linear branches, thus reducing the overall mechanical properties.
Comparative example 6 differs from example 1 in that sulfosalicylic acid is replaced with formic acid; firstly, the acidity of formic acid is weak, the concentration of catalytic ions of the formic acid is low, and secondly, the formic acid does not have stronger catalytic activity with the increase of the heating temperature, so that the hydroxyl group deprotection effect by adopting the formic acid is poor, the crosslinking capability of a curing agent is poor, and finally, the whole electrophoretic coating film is reduced compared with that of the electrophoretic coating film in example 1.
From the data of examples 1 to 5 and comparative examples 1 to 6, it is clear that the above requirements can be satisfied in all aspects only by the embodiments within the scope of the claims of the present invention, and a preparation scheme of an electrophoretic film having excellent overall properties can be obtained. The change of the mixture ratio, the replacement/addition/subtraction of raw materials or the change of the feeding sequence can bring corresponding negative effects.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The electrophoretic paint curing agent with good water solubility is characterized in that the molecular structure of the curing agent is a multi-benzene-ring long branched chain structure with good fluidity.
2. The curing agent for electrophoretic paint with good water solubility according to claim 1, wherein the preparation steps are as follows:
(1) putting diphenylmethane diisocyanate into a reaction vessel, adding a catalyst accounting for 0.06-0.08 percent of the weight of the isocyanate and butanone accounting for 3-5 percent of the weight of the isocyanate, reacting at a constant temperature of 95-100 ℃, and stopping the reaction when the molar content of-NCO is reduced to 48-50 percent of the initial content to obtain a product I;
(2) adding the queen bee acid into the product I, uniformly mixing, adding stannous octoate accounting for 0.75-1% of the total weight of the product I and the queen bee acid, heating to 84-86 ℃, and reacting for 2-2.5h to obtain a product II;
(3) adding 1, 4-butanediol diglycidyl ether into the product II, uniformly mixing, heating to 118-122 ℃, dropwise adding dodecyl trimethyl ammonium bromide, continuously preserving the temperature for 3.2-3.5h after the dropwise adding is finished, and evaporating to remove the solvent after the reaction is finished to obtain a product III;
(4) and (3) mixing the product III in a mass ratio of 1: 1-1.2, dissolving in ethanol, heating to 62-66 ℃, continuously dripping tetraethylenepentamine, and continuously reacting for 4.2-4.5 hours under the condition of heat preservation to obtain a product IV;
(5) dropwise adding epoxy propanol accounting for 0.5-0.8% of the mass fraction of the product IV into the product IV, heating to 65-70 ℃ for reaction for 3.2-3.8h, and evaporating ethanol after the reaction is finished to obtain a capped amino product;
(6) and dissolving the end-capped amino product in distilled water to obtain an end-capped hydroxyl solution with the mass concentration of 50-60%, continuously adding trimethylsilyl into the end-capped hydroxyl solution, and reacting at 60-65 ℃ for 1-1.5h to obtain an end-capped hydroxyl product.
3. The curing agent for electrophoretic paint with good water solubility as claimed in claim 2, wherein in the step (2), the mass ratio of the product I and the queen acid is 1: 4.5-6.
4. The curing agent for the electrophoretic paint with good water solubility according to claim 2, wherein in the step (3), n (carboxyl) in the product II and n (epoxy) in 1, 4-butanediol diglycidyl ether are respectively 1: 2; and/or
Dodecyl trimethyl ammonium bromide accounts for 2-5% of 1, 4-butanediol diglycidyl ether.
5. The curing agent for the electrophoretic paint with good water solubility as claimed in claim 2, wherein in the step (4), n (epoxy group) = n (tetraethylenepentamine) = 1: 2 in the product III.
6. The curing agent for the electrophoretic paint with good water solubility according to claim 2, wherein in the step (5), the mass ratio of the product IV to the epoxypropanol is 1: 0.005-0.008.
7. The curing agent for the electrophoretic paint with good water solubility according to claim 2, wherein in the step (6), the mass ratio of the blocked amino product to the trimethylsilyl group is 1: 0.12-0.15.
8. Use of the curing agent according to any one of claims 1 to 7 in an electrocoat film, wherein the electrocoat film is prepared by: mixing an epoxy resin matrix, a cosolvent and the curing agent at 50-60 ℃, stirring for 30-40min, adding oxalic acid under stirring, and neutralizing for 0.5-0.8h to obtain cationic epoxy resin; transferring the cationic epoxy resin into a dispersion container, controlling the mechanical stirring speed to be 3000rmp, adding toner and deionized water under the stirring state, stirring for 20-30min to obtain uniformly dispersed cathode electrophoresis emulsion, and curing for 22-24 h; taking a steel plate as a cathode, and performing electrophoresis for 2.5-3min under the electrophoresis voltage of 150V; after electrophoresis, taking out the steel plate, cleaning the steel plate by using deionized water, firstly preserving the heat at 80-100 ℃ for 40-50min, and then baking the steel plate at 150-160 ℃ for 30-35min to obtain the electrophoresis film.
9. The use of claim 8, wherein sulfosalicylic acid in an amount of 0.8-1.5% by weight of the curing agent is added to the aged cathodic electrophoretic emulsion before electrophoresis, and stirring is continued for 5-10 min.
10. The application of the compound fertilizer as claimed in claim 8, wherein the additive components and the ratio thereof are as follows by 100 mass percent: 25-35% of epoxy resin matrix, 10-15% of curing agent, 8-10% of cosolvent, 1-3% of toner, 3-5% of oxalic acid and the balance of water.
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| CN104829787A (en) * | 2015-05-04 | 2015-08-12 | 天津科技大学 | Preparation method and application of functional material for adsorption of 10-hydroxy-2-decenoic acid |
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| CN108395819A (en) * | 2018-04-10 | 2018-08-14 | 安徽陵阳新材料有限公司 | A kind of preparation method for the cathode electrophoresis dope that nonshrink pore performance is excellent |
| CN108929427A (en) * | 2018-06-12 | 2018-12-04 | 湖南大学 | Improve the preparation method of the blocked isocyanate of cathode electrophoresis dope filming performance |
| CN110218475A (en) * | 2019-06-13 | 2019-09-10 | 深圳市志邦科技有限公司 | A kind of dedicated blocked polyisocyanates curing agent of electrophoretic paint and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105778047A (en) * | 2014-12-22 | 2016-07-20 | 深圳市志邦科技有限公司 | Preparation method of terminated polyisocyanate curing agent specially used for 120DEG C low temperature-curable electrophoresis paint |
| CN104829787A (en) * | 2015-05-04 | 2015-08-12 | 天津科技大学 | Preparation method and application of functional material for adsorption of 10-hydroxy-2-decenoic acid |
| CN108395819A (en) * | 2018-04-10 | 2018-08-14 | 安徽陵阳新材料有限公司 | A kind of preparation method for the cathode electrophoresis dope that nonshrink pore performance is excellent |
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