CN114181599A - Preparation method of epoxy modified solvent-free polyurea coating - Google Patents
Preparation method of epoxy modified solvent-free polyurea coating Download PDFInfo
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- CN114181599A CN114181599A CN202111491240.2A CN202111491240A CN114181599A CN 114181599 A CN114181599 A CN 114181599A CN 202111491240 A CN202111491240 A CN 202111491240A CN 114181599 A CN114181599 A CN 114181599A
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- epoxy modified
- preparing
- epoxy
- resin
- paint
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 41
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 40
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 66
- 239000011347 resin Substances 0.000 claims abstract description 66
- 239000003973 paint Substances 0.000 claims abstract description 41
- -1 aromatic primary amino compound Chemical class 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 11
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 238000006845 Michael addition reaction Methods 0.000 claims abstract description 4
- 238000007259 addition reaction Methods 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 11
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 11
- 239000002518 antifoaming agent Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000000080 wetting agent Substances 0.000 claims description 8
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 8
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 claims description 6
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000013638 trimer Substances 0.000 claims description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 7
- 230000006750 UV protection Effects 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003595 mist Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- ZTFZSHLWORMEHO-UHFFFAOYSA-A pentaaluminum;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ZTFZSHLWORMEHO-UHFFFAOYSA-A 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 230000026045 iodination Effects 0.000 description 3
- 238000006192 iodination reaction Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229920006334 epoxy coating Polymers 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
- C08G18/584—Epoxy resins having nitrogen
-
- 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
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C08G2150/00—Compositions for coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
Abstract
The invention relates to the technical field of solvent-free coatings, in particular to a preparation method of an epoxy modified solvent-free polyurea coating, which comprises the following steps: s1 resin synthesis 1) carrying out Michael addition reaction on a bifunctional non-aromatic primary amino compound and an unsaturated ester compound to obtain a mixture of unilateral primary amino and unilateral secondary amino; 2) performing addition reaction on the mixture of the unilateral primary amino group and the unilateral secondary amino group obtained in the step 1) and a bifunctional epoxy compound to obtain epoxy modified polyurea resin; s2 preparing coating, 1) grinding into thick liquid; 2) preparing paint; the invention uses a brand-new epoxy modified polyurea resin, and the prepared coating has the properties of high reaction activity, high adhesive force, high toughness, ultraviolet resistance, salt mist resistance, zero voc and the like which can be randomly adjusted in a certain range. And the bottom surfaces can be integrated, one paint film easily reaches more than 200 micrometers, the paint film does not need to be baked and quickly cured, and the construction process is greatly simplified.
Description
Technical Field
The invention relates to the technical field of solvent-free coatings, in particular to a preparation method of an epoxy modified solvent-free polyurea coating.
Background
Nowadays, the environmental protection pressure is increasingly increased, solvent-based coatings can not be used on a large scale, water-based coatings have great limitation in the aspect of heavy corrosion resistance due to performance problems, and solvent-free coatings are increasingly regarded as high-performance environment-friendly coatings with zero voc and high film-forming efficiency.
The conventional solvent-free polyurea coating has excellent ultraviolet resistance, a paint film is tough and wear-resistant, and the curing speed is extremely high, however, the extremely high curing speed causes that the wetting time of the coating to a substrate is insufficient, and the urea-diester structure formed after curing is not stable enough, and a cyclization reaction can occur to form cyclic ureide, so that a huge cohesive shrinkage tendency is brought, and therefore, the conventional polyurea coating has poor adhesion to the substrate, and even a phenomenon that a whole paint film falls off can occur. Therefore, the epoxy primer must be used to obtain the desired properties, and the primer cannot be used for primer-topcoat.
The most common solvent-free coating also belongs to a solvent-free two-component epoxy coating, the epoxy coating has strong adhesion to a base material and corrosion resistance, but a large number of benzene rings in the main chain of the epoxy resin determine the weak wear resistance and ultraviolet resistance, so that the epoxy resin can only be used as a primer or used in an environment without strong ultraviolet radiation, such as an underground pipeline. And because of the low reactivity, the curing is slow at the temperature of less than 10 ℃, even is not cured at the temperature of less than 5 ℃, at least half of China is in the environment of less than 10 ℃ for a long time in winter, and the construction in the environment can be greatly difficult.
Disclosure of Invention
The purpose of the invention is: the coating prepared by the preparation method has the properties of high reaction activity, high adhesive force, high toughness, ultraviolet resistance, salt spray resistance, zero voc and the like which can be randomly adjusted within a certain range. And the bottom surfaces can be integrated, one paint film easily reaches more than 200 micrometers, the paint film does not need to be baked and quickly cured, and the construction process is greatly simplified.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of an epoxy modified solvent-free polyurea coating comprises the following steps:
s1 resin Synthesis
1) Performing Michael addition reaction on a bifunctional non-aromatic primary amino compound and an unsaturated ester compound to obtain a mixture of unilateral primary amino and unilateral secondary amino;
2) performing addition reaction on the mixture of the unilateral primary amino group and the unilateral secondary amino group obtained in the step 1) and a bifunctional epoxy compound to obtain epoxy modified polyurea resin;
s2 paint formulation
2) Grinding: adding a dispersing agent and powder into the epoxy modified polyurea resin prepared in the step S1, and after primary dispersion, feeding the mixture into grinding equipment to grind the particle size of the powder to be less than 20 microns to obtain pigment slurry;
2) preparing paint: adding pigment slurry, epoxy modified polyurea resin and paint auxiliary agent, dispersing uniformly to obtain resin component, adding curing agent non-aromatic polyisocyanate to obtain the required paint.
Further, the difunctional non-aromatic primary amino compound in step 1) of step S1 includes, but is not limited to, ethylenediamine, 1, 2-propylenediamine, 1, 4-butylenediamine, 1, 6-hexamethylenediamine, 4, 4-diaminodicyclohexylmethane, 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane, isophoronediamine or a mixture thereof, polyoxypropylene, polyoxyethylene, or an amino-terminated compound of an oxyethylene oxypropylene copolymer;
unsaturated esters include, but are not limited to, diethyl maleate, dimethyl maleate, methyl acrylate, methyl methacrylate, ethyl acrylate and mixtures thereof.
Further, the molar ratio of the difunctional non-aromatic primary amino compound to the unsaturated ester in step 1) in step S1 is 1: 0.75-1.25 at 50-70 deg.c; the reaction time is 8-15 hours.
Further, the difunctional epoxy compounds in step 2) of step S1 include, but are not limited to, glycidyl ester, glycidyl amine, glycidyl ether, bisglycidyl ether, triglycidyl ether and derivatives thereof such as E51, van Epon828, DOW DER331, hensemy GY-250, Ciba GY-250 low viscosity bisphenol a resin, Ciba GY-281, DOW DER354 low viscosity bisphenol F resin.
Further, the molar ratio of the mixture of the single-sided primary amino group and the single-sided secondary amino group in the step 2) in the step S1 to the bifunctional epoxy compound is 1: 0.75-1.25, 40-70 deg.C, and 8-15 hr reaction time.
Further, BYK110 is selected as the dispersing agent in the grinding step in the step S2, and the powder material comprises titanium dioxide, zinc phosphate, aluminum tripolyphosphate and an antifoaming agent BYK 066N.
Further, the non-aromatic polyisocyanate in the step of preparing the paint in step S2 includes, but is not limited to, hexamethylene diisocyanate, isophorone diisocyanate, 4, 4-diisocyanate-dicyclohexylmethane and biuret or trimer thereof.
Further, the coating auxiliary agents in the step of preparing the paint in the step S2 include, but are not limited to, Tego270, Tego4100 wetting agent, BYK333, BYK331, Tego280 leveling agent, and other functional auxiliary agents.
The technical scheme adopted by the invention has the beneficial effects that:
the invention uses a brand-new epoxy modified polyurea resin, integrates the advantages of epoxy and polyurea resin, and avoids the respective disadvantages. The prepared coating has the properties of high reaction activity, high adhesive force, high toughness, ultraviolet resistance, salt mist resistance, zero voc and the like which can be randomly adjusted within a certain range. And the bottom surfaces can be integrated, one paint film easily reaches more than 200 micrometers, the paint film does not need to be baked and quickly cured, and the construction process is greatly simplified.
Detailed Description
The preparation method of the epoxy-modified solvent-free polyurea coating according to the present invention is further described below with reference to the following embodiments.
A preparation method of an epoxy modified solvent-free polyurea coating comprises the following steps:
s1 resin Synthesis
1) Performing Michael addition reaction on a bifunctional non-aromatic primary amino compound and an unsaturated ester compound to obtain a mixture of unilateral primary amino and unilateral secondary amino; in the reaction formula, the molar ratio of the amino compound to the unsaturated ester is 1: 0.75-1.25 at 50-70 deg.c; the reaction time is 8-15 hours;
difunctional non-aromatic primary amino compounds including, but not limited to, ethylenediamine, 1, 2-propylenediamine, 1, 4-butanediamine, 1, 6-hexanediamine, 4, 4-diaminodicyclohexylmethane, 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane, isophoronediamine or mixtures thereof, polyoxypropylene, polyoxyethylene, or the terminal amino compounds of oxyethylene oxypropylene copolymers;
unsaturated esters include, but are not limited to, diethyl maleate, dimethyl maleate, methyl acrylate, methyl methacrylate, ethyl acrylate and mixtures thereof;
2) performing addition reaction on the mixture of the unilateral primary amino group and the unilateral secondary amino group obtained in the step 1) and a bifunctional epoxy compound to obtain epoxy modified polyurea resin; the molar ratio in the reaction formula is 1: 0.75-1.25, the temperature is 40-70 ℃, and the reaction time is 8-15 hours;
difunctional epoxy compounds include, but are not limited to, glycidyl esters, glycidyl amines, glycidyl ethers, bisglycidyl ethers, triglycidyl ethers and derivatives thereof such as E51, Vast Epon828, DOW DER331, Hensmai GY-250, Ciba GY-250 low viscosity bisphenol A resins, Ciba GY-281, DOW DER354 low viscosity bisphenol F resins.
The invention uses a brand-new epoxy modified polyurea resin, integrates the advantages of epoxy and polyurea resin, and avoids the respective disadvantages. The prepared coating has the properties of high reaction activity, high adhesive force, high toughness, ultraviolet resistance, salt mist resistance, zero voc and the like which can be randomly adjusted within a certain range. And the bottom surfaces can be integrated, one paint film easily reaches more than 200 micrometers, the paint film does not need to be baked and quickly cured, and the construction process is greatly simplified.
Most importantly, the epoxy is modified on the side chain of the polymer, so that the benzene ring is also present on the side chain, and the amino compound and the isocyanate compound which form the main chain are both non-aromatic. Even if aromatic ether bonds in surface layer molecules of the paint film are completely broken due to strong ultraviolet irradiation, the main chain can still be kept intact, and the high toughness of the polyurea can be kept continuously without pulverization. Further, because the surface layer is relatively complete, the surface paint film still has the capability of resisting ultraviolet rays for the middle and lower paint films, the aromatic ether bonds at the bottom layer of the paint film can be kept complete, and the long-term adhesive force of the whole paint film is ensured.
S2 paint formulation
1) Grinding: adding a dispersing agent and powder into the epoxy modified polyurea resin prepared in the step S1, and after primary dispersion, feeding the mixture into grinding equipment to grind the particle size of the powder to be less than 20 microns to obtain pigment slurry;
the dispersant is BYK110, and the powder comprises titanium dioxide, zinc phosphate, aluminum tripolyphosphate and a defoaming agent BYK 066N;
2) preparing paint: adding pigment slurry, epoxy modified polyurea resin and coating auxiliary agent, dispersing uniformly to obtain a resin component, and adding a curing agent non-aromatic polyisocyanate to obtain the required coating;
non-aromatic polyisocyanates include, but are not limited to, hexamethylene diisocyanate, isophorone diisocyanate, 4, 4-diisocyanate-dicyclohexylmethane and biurets or trimers of the foregoing.
Coating aids include, but are not limited to, Tego270, Tego4100 wetting agents and BYK333, BYK331, Tego280 leveling agents and other functional aids.
Example 1
S1 resin Synthesis
1) Adding 0.5mol (105.2g) of 4, 4' -diamino-dicyclohexylmethane into a 500ml four-neck flask respectively provided with an electric stirring device, a thermometer, a dropping funnel and a nitrogen conduit pipe, starting stirring, introducing nitrogen, slowly heating to 40-45 ℃, starting dropwise adding 0.5mol (86.09g) of diethyl maleate, controlling the temperature not to exceed 60 ℃, keeping the temperature within 30-40 minutes, finishing dropwise adding, then reacting for 15 hours at the temperature of 50-55 ℃, cooling to 40 ℃, and discharging to obtain the first-step product. The product was a pale yellow transparent liquid, at which point the conversion was 90% by "iodination" and 94% after 48 hours.
2) Adding 0.5mol (170.2g) of diglycidyl ether into a 500ml four-neck flask respectively provided with an electric stirring device, a thermometer, a dropping funnel and a nitrogen conduit, starting stirring, introducing nitrogen, slowly heating to 40-45 ℃, starting dropwise adding 0.5mol (191.29g) of a first-step product, controlling the temperature to be not more than 60 ℃, keeping the temperature within 20-30 minutes, finishing dropwise adding, then reacting for 15 hours at the temperature of 40-45 ℃, cooling to 40 ℃ and discharging to obtain a final resin product. The product is a light yellow transparent liquid.
3) Grinding:
epoxy-modified polyurea resin | 40g |
BYK110 dispersant | 1.3g |
Carbon black powder | 4g |
Zinc phosphate | 15g |
Aluminium triphosphate | 14g |
BYK066N defoaming agent | 0.5g |
The materials are put into a dispersion cylinder in sequence for uniform dispersion, and then are put into a ball mill for grinding until the particle size is less than 20 microns.
4) Preparing paint: resin component (c):
epoxy-modified polyurea resin | 24.8g |
Pigment paste | 74.8g |
Tego270 wetting agent | 0.2g |
BYK333 leveling agent | 0.2g |
Curing agent component:
scientific wound Desmodur N3300 | 38g |
5) Coating construction: and respectively putting the resin component and the curing agent component into a two-component airless high-pressure spraying device, increasing the temperature of the two storage tanks, and maintaining the temperature of the resin component and the curing agent component at 60 ℃. The ratio of the flow rate of the resin component raw material pump to the flow rate of the curing agent component raw material pump is 100: 38, starting the equipment to spray the two components after the two components are impacted and mixed by the gun head, and controlling the film thickness of the paint film on the sample plate to be between 200 and 300 micrometers.
And (3) performance detection:
example 2
S1 resin Synthesis
1) Adding 0.25mol (59.5g) of 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane and 0.25mol (100g) of D400 polyetheramine into a 500ml four-neck flask respectively provided with an electric stirring device, a thermometer, a dropping funnel and a nitrogen conduit, starting stirring, introducing nitrogen, slowly heating to 40-45 ℃, starting dropwise adding 0.625mol (107.6g) of diethyl maleate, controlling the temperature not to exceed 60 ℃, keeping the temperature within 30-40 minutes, finishing dropwise adding, reacting for 12 hours at 60-65 ℃, cooling to 40 ℃, and discharging to obtain the first-step product. The product was a pale yellow transparent liquid, at which time the conversion was 89% as determined by the "iodination method" and 92% after 48 hours.
2) Adding 0.375mol (70.3g) of E51 epoxy resin into a 1000ml four-neck flask respectively provided with an electric stirring device, a thermometer, a dropping funnel and a nitrogen conduit, starting stirring, introducing nitrogen, slowly heating to 40-45 ℃, starting dropwise adding 0.5mol (266.8g) of the first-step product, controlling the temperature not to exceed 60 ℃, keeping the temperature within 20-30 minutes, finishing dropwise adding, then reacting for 12 hours at 55-60 ℃, cooling to 40 ℃ and discharging to obtain the final resin product. The product is a light yellow transparent liquid.
3) Grinding:
epoxy-modified polyurea resin | 45g |
BYK110 dispersant | 1.3g |
Carbon black powder | 4g |
Zinc phosphate | 15g |
Aluminium triphosphate | 14g |
BYK066N defoaming agent | 0.5g |
The materials are put into a dispersion cylinder in sequence for uniform dispersion, and then are put into a ball mill for grinding until the particle size is less than 20 microns.
4) Preparing paint: resin component (c):
epoxy-modified polyurea resin | 19.8g |
Pigment paste | 79.8g |
Tego4100 wetting agent | 0.2g |
tego280 leveling agent | 0.2g |
Curing agent component:
scientific wound Desmodur N3300 | 40.7g |
6) Coating construction: and respectively putting the resin component and the curing agent component into a two-component airless high-pressure spraying device, increasing the temperature of the two storage tanks, and maintaining the temperature of the resin component and the curing agent component at 65 ℃. The ratio of the flow rate of the resin component raw material pump to the flow rate of the curing agent component raw material pump is 100: 40.7, then starting the equipment to enable the two components to be sprayed out after the gun head is impacted and mixed, and controlling the film thickness of a paint film on the sample plate to be 200-300 microns.
And (3) performance detection:
example 3
S1 resin Synthesis
1) Adding 0.25mol (29.05g) of hexamethylene diamine and 0.25mol (500g) of D2000 polyether amine into a 500ml four-neck flask respectively provided with an electric stirring device, a thermometer, a dropping funnel and a nitrogen guide pipe, starting stirring, introducing nitrogen, slowly heating to 40-45 ℃, starting dropwise adding 0.375mol (64.6g) of diethyl maleate, controlling the temperature not to exceed 60 ℃, keeping the temperature within 30-40 minutes, finishing dropwise adding, then reacting for 8 hours at 70-75 ℃, cooling to 40 ℃, and discharging to obtain a first-step product. The product was a pale yellow transparent liquid, at which time the conversion was 89% as determined by the "iodination method" and 92% after 48 hours.
2) Adding 0.625mol (212.75g) of diglycidyl ether into a 1000ml four-neck flask respectively provided with an electric stirring device, a thermometer, a dropping funnel and a nitrogen conduit, starting stirring, introducing nitrogen, slowly heating to 40-45 ℃, starting dropwise adding 0.5mol (593.65g) of the first-step product, controlling the temperature not to exceed 60 ℃, keeping the temperature within 20-30 minutes, finishing dropwise adding, then reacting for 8 hours at 70-75 ℃, cooling to 40 ℃ and discharging to obtain the final resin product. The product is a light yellow transparent liquid.
3) Grinding:
epoxy-modified polyurea resin | 50g |
BYK110 dispersant | 1.3g |
Carbon black powder | 4g |
Zinc phosphate | 15g |
Aluminium triphosphate | 14g |
BYK066N defoaming agent | 0.5g |
The materials are put into a dispersion cylinder in sequence for uniform dispersion, and then are put into a ball mill for grinding until the particle size is less than 20 microns.
4) Preparing paint: resin component (c):
epoxy-modified polyurea resin | 14.8g |
Pigment paste | 84.8g |
Tego4100 wetting agent | 0.2g |
tego280 leveling agent | 0.2g |
Curing agent component:
scientific wound Desmodur N3300 | 34g |
7) Coating construction: and respectively putting the resin component and the curing agent component into a two-component airless high-pressure spraying device, increasing the temperature of the two storage tanks, and maintaining the temperature of the resin component and the curing agent component at 65 ℃. The ratio of the flow rate of the resin component raw material pump to the flow rate of the curing agent component raw material pump is 100: 34, starting the equipment to spray the two components after the two components are impacted and mixed by the gun head, and controlling the film thickness of the paint film on the sample plate to be between 200 and 300 micrometers.
And (3) performance detection:
comparative example 1
The resin synthesized in S1 was replaced with E51 commercial resin, and the curing agent was replaced with hexamethylenediamine.
Grinding:
e51 epoxy resin | 50g |
BYK110 dispersant | 1.3g |
Carbon black powder | 4g |
Zinc phosphate | 15g |
Aluminium triphosphate | 14g |
BYK066N defoaming agent | 0.5g |
The materials are put into a dispersion cylinder in sequence for uniform dispersion, and then are put into a ball mill for grinding until the particle size is less than 20 microns.
Preparing paint: resin component (c):
e51 epoxy resin | 14.8g |
Pigment paste | 84.8g |
Tego4100 wetting agent | 0.2g |
tego280 leveling agent | 0.2g |
Curing agent component:
hexamethylene diamine | 20g |
5) Coating construction: the resin component and the curing agent component are respectively put into a two-component airless high-pressure spraying device, the temperature of the two storage tanks is increased, and the resin component is maintained at 65 ℃ and the curing agent component is maintained at 45 ℃. The ratio of the flow rate of the resin component raw material pump to the flow rate of the curing agent component raw material pump is 100: and 20, starting the equipment to enable the two components to be sprayed out after the two components are impacted and mixed by the gun head, and controlling the film thickness of a paint film on the sample plate to be between 200 and 300 micrometers.
And (3) self-drying the sample plate in an environment of 10 ℃, and detecting surface drying time, actual drying time, aging resistance, adhesive force, acid resistance, alkali resistance and salt resistance.
From the data in comparative example 1, the addition of the pure epoxy component is resistant to violet heterodyne and slow to cure.
Comparative example 2
The resin synthesized in S1 was replaced with a commercial resin, and the curing agent was replaced with N3300.
Grinding:
NH1220 resin | 50g |
BYK110 dispersant | 1.3g |
Carbon black powder | 4g |
Zinc phosphate | 15g |
Aluminium triphosphate | 14g |
BYK066N defoaming agent | 0.5g |
The materials are put into a dispersion cylinder in sequence for uniform dispersion, and then are put into a ball mill for grinding until the particle size is less than 20 microns.
Preparing paint: resin component (c):
epoxy-modified polyurea resin | 14.8g |
Pigment paste | 84.8g |
Tego4100 wetting agent | 0.2g |
tego280 leveling agent | 0.2g |
Curing agent component:
N3300 | 60g |
6) coating construction: and respectively putting the resin component and the curing agent component into a two-component airless high-pressure spraying device, increasing the temperature of the two storage tanks, and maintaining the temperature of the resin component and the temperature of the curing agent component at 65 ℃. The ratio of the flow rate of the resin component raw material pump to the flow rate of the curing agent component raw material pump is 100: and 60, starting the equipment to enable the two components to be sprayed out after the two components are impacted and mixed by the gun head, and controlling the film thickness of a paint film on the sample plate to be between 200 and 300 micrometers.
And (3) self-drying the sample plate in an environment of 10 ℃, and detecting surface drying time, actual drying time, aging resistance, adhesive force, acid resistance, alkali resistance and salt resistance.
As can be seen from comparative example 2, the adhesion of the paint film is poor with the addition of the pure polyurea component.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment contains only one independent claim, and such description is for clarity only, and those skilled in the art will be able to make the description as a whole, and the embodiments may be appropriately combined to form other embodiments understood by those skilled in the art.
Claims (8)
1. A preparation method of an epoxy modified solvent-free polyurea coating is characterized by comprising the following steps: the preparation method comprises the following steps:
s1 resin Synthesis
1) Performing Michael addition reaction on a bifunctional non-aromatic primary amino compound and an unsaturated ester compound to obtain a mixture of unilateral primary amino and unilateral secondary amino;
2) performing addition reaction on the mixture of the unilateral primary amino group and the unilateral secondary amino group obtained in the step 1) and a bifunctional epoxy compound to obtain epoxy modified polyurea resin;
s2 paint formulation
1) Grinding: adding a dispersing agent and powder into the epoxy modified polyurea resin prepared in the step S1, and after primary dispersion, feeding the mixture into grinding equipment to grind the particle size of the powder to be less than 20 microns to obtain pigment slurry;
2) preparing paint: adding pigment slurry, epoxy modified polyurea resin and paint auxiliary agent, dispersing uniformly to obtain resin component, adding curing agent non-aromatic polyisocyanate to obtain the required paint.
2. The method for preparing the epoxy modified solvent-free polyurea coating according to claim 1, wherein the method comprises the following steps: a difunctional non-aromatic primary amino compound of step 1) of said step S1, including but not limited to ethylenediamine, 1, 2-propylenediamine, 1, 4-butylenediamine, 1, 6-hexamethylenediamine, 4, 4-diaminodicyclohexylmethane, 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane, isophoronediamine or mixtures thereof, polyoxypropylene, polyoxyethylene, or an oxyethylene oxypropylene copolymer;
unsaturated esters include, but are not limited to, diethyl maleate, dimethyl maleate, methyl acrylate, methyl methacrylate, ethyl acrylate and mixtures thereof.
3. The method for preparing the epoxy modified solvent-free polyurea coating according to claim 1, wherein the method comprises the following steps: the molar ratio of the difunctional non-aromatic primary amino compound to the unsaturated ester in step 1) in step S1 is 1: 0.75-1.25 at 50-70 deg.c; the reaction time is 8-15 hours.
4. The method for preparing the epoxy modified solvent-free polyurea coating according to claim 1, wherein the method comprises the following steps: the difunctional epoxy compound in step 2) of step S1 includes, but is not limited to, glycidyl ester, glycidyl amine, glycidyl ether, diglycidyl ether, triglycidyl ether and E51 derived therefrom, Vast Epon828, DOW DER331, Hunsmey GY-250, GY-250 low viscosity bisphenol A resins from Ciba, GY-281 from Ciba, and DER354 low viscosity bisphenol F resins from DOW.
5. The method for preparing the epoxy modified solvent-free polyurea coating according to claim 1, wherein the method comprises the following steps: the molar ratio of the mixture of single-sided primary amino groups and single-sided secondary amino groups in the step 2) in the step S1 to the bifunctional epoxy compound is 1: 0.75-1.25, 40-70 deg.C, and 8-15 hr reaction time.
6. The method for preparing the epoxy modified solvent-free polyurea coating according to claim 1, wherein the method comprises the following steps: in the step S2, BYK110 is selected as the dispersing agent in the step of grinding, and the powder material comprises titanium dioxide, zinc phosphate, aluminum tripolyphosphate and an antifoaming agent BYK 066N.
7. The method for preparing the epoxy modified solvent-free polyurea coating according to claim 1, wherein the method comprises the following steps: the non-aromatic polyisocyanate in the step of preparing the paint in step S2 includes, but is not limited to, hexamethylene diisocyanate, isophorone diisocyanate, 4, 4-diisocyanate-dicyclohexylmethane and biuret or trimer of the above.
8. The method for preparing the epoxy modified solvent-free polyurea coating according to claim 1, wherein the method comprises the following steps: the coating auxiliary agents in the paint preparing step in the step S2 include but are not limited to Tego270, Tego4100 wetting agent, BYK333, BYK331, Tego280 leveling agent and other functional auxiliary agents.
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