CN117757331A - Special water-based paint and preparation method and application thereof - Google Patents
Special water-based paint and preparation method and application thereof Download PDFInfo
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- CN117757331A CN117757331A CN202410188309.1A CN202410188309A CN117757331A CN 117757331 A CN117757331 A CN 117757331A CN 202410188309 A CN202410188309 A CN 202410188309A CN 117757331 A CN117757331 A CN 117757331A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000003973 paint Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003822 epoxy resin Substances 0.000 claims abstract description 140
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 140
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 239000000839 emulsion Substances 0.000 claims abstract description 41
- 239000008367 deionised water Substances 0.000 claims abstract description 40
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 22
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000007797 corrosion Effects 0.000 claims abstract description 12
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 25
- 229960001124 trientine Drugs 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 229960004543 anhydrous citric acid Drugs 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- -1 polysiloxane Polymers 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000005536 corrosion prevention Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005187 foaming Methods 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of coatings, in particular to a special water-based coating and a preparation method and application thereof. The special water-based paint comprises the following components in parts by mass: 100-120 parts of carbon quantum dot modified waterborne epoxy resin emulsion, 3-5 parts of triethanolamine, 0.5-3 parts of dispersing agent, 0.5-3 parts of defoaming agent, 0.5-3 parts of leveling agent and 5-10 parts of deionized water; the carbon quantum dot modified waterborne epoxy resin emulsion is obtained by co-emulsifying epoxy resin by a carbon quantum dot modified self-emulsifying epoxy resin curing agent and a waterborne epoxy resin emulsifier. The self-made self-emulsifying epoxy resin curing agent is adopted, so that the prepared special coating has excellent corrosion resistance and can be applied to corrosion prevention in a highly corrosive environment.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a special water-based coating and a preparation method and application thereof.
Background
The special paint is mainly applied to places with severe environments and mainly comprises polyurethane paint, epoxy resin paint and vinyl chloride paint, wherein the epoxy resin paint has the widest application range and the most stable performance. The epoxy resin coating is mainly solvent-based, and although the solvent-based epoxy resin coating has excellent performance, the coating can volatilize organic solvents to pollute the environment and cause harm to constructors and surrounding masses in the construction and curing process. With the issuance and implementation of a series of environmental regulations, waterborne epoxy coatings that do not contain Volatile Organic Compounds (VOCs) or low VOCs are attracting widespread attention.
In the method for the waterborne epoxy resin, the curing agent has the curing effect in the curing agent emulsification method and the function of emulsifying the liquid epoxy resin, and the prepared waterborne epoxy emulsion has the characteristics of small particle size, high coating hardness, excellent corrosion resistance and the like, and has wide application fields. At present, the traditional polyamine curing agent is generally modified, so that the toxicity of the curing agent is reduced, the compatibility with epoxy resin is increased, and the comprehensive performance of a coating film is effectively improved.
The patent technical document CN115181260B discloses a modified epoxy resin for a water-based heavy anti-corrosion coating, which is formed by grafting a functional monomer onto the tail end of a polyfunctional epoxy molecular chain, and grafting a hydrophilic chain segment onto a main structure of the resin in chain extender and emulsion copolymerization, so that the problem that the polyfunctional epoxy resin with medium and high molecular weight is difficult to realize water-based in a self-emulsifying mode is solved, the stability of water-based emulsion is improved, and the anti-corrosion performance of a coating is improved. However, the direct chemical modification of the epoxy resin matrix has the disadvantages of high production cost, complex preparation method and poor operability.
Patent technical document CN105368241B discloses an anticorrosive coating composition containing a self-emulsifying curing agent, and the prepared epoxy resin coating has wear resistance and corrosion resistance by adopting the self-emulsifying curing agent to compound triethylene diamine and diethylene triamine as an epoxy resin curing agent. However, the self-emulsifying curing agent of the present invention contains a large amount of carboxylic acid groups, and thus cannot meet the corrosion resistance requirements in a highly corrosive environment.
Disclosure of Invention
In view of the above, the invention aims to provide a special water-based paint, a preparation method and application thereof, so as to provide a special water-based paint applicable to a strong corrosion environment, in particular to an anti-corrosion application in a high-temperature and high-humidity environment.
Based on the purposes, the invention provides a special water-based paint which comprises the following components in parts by weight: 100-120 parts of carbon quantum dot modified waterborne epoxy resin emulsion, 3-5 parts of triethanolamine, 0.5-3 parts of dispersing agent, 0.5-3 parts of defoaming agent, 0.5-3 parts of leveling agent and 5-10 parts of deionized water.
Further, the carbon quantum dot modified waterborne epoxy resin emulsion is obtained by co-emulsifying epoxy resin by a carbon quantum dot modified self-emulsifying epoxy resin curing agent and a waterborne epoxy resin emulsifier.
Further, the mass ratio of the carbon quantum dot modified self-emulsifying epoxy resin curing agent, the water-based epoxy resin emulsifier and the epoxy resin in the carbon quantum dot modified water-based epoxy resin emulsion is 15-18:4-5:100-120.
Further, the solid content of the carbon quantum dot modified waterborne epoxy resin emulsion is 57% -59%.
Further, the aqueous epoxy resin emulsifier is a polyether emulsifier.
Still further, the preparation method of the carbon quantum dot modified self-emulsifying epoxy resin curing agent comprises the following steps:
s1: adding anhydrous citric acid into a crucible, heating to 200-250 ℃, pyrolyzing for 8-10 hours, cooling, washing, centrifuging and drying to obtain carbon quantum dots;
s2: dispersing carbon quantum dots in a mixed solution of deionized water and ethanol, then adding a silane coupling agent KH-570, reacting for 5-7 hours at 60-70 ℃, washing, centrifuging, and drying to obtain epoxidized carbon quantum dots;
s3: under the protection of nitrogen, triethylene tetramine is added into propylene glycol methyl ether, the temperature is raised to 70-80 ℃, then epoxy resin E44 is added, and the reaction is carried out for 1-1.5 hours, thus obtaining triethylene tetramine modified epoxy resin solution;
s4: dispersing the epoxidized carbon quantum dots in propylene glycol methyl ether, heating to 70-80 ℃, then dropwise adding a triethylene tetramine modified epoxy resin solution, reacting for 2 hours after the dropwise adding is finished, then adding methoxy-polyethylene glycol-epoxy group, reacting for 10-20 minutes, washing, centrifuging and drying to obtain the carbon quantum dot modified self-emulsifying epoxy resin curing agent.
Further, the dispersing agent is one of BYK-P104, BYK-P105 and BYK-163.
Further, the defoamer is polysiloxane defoamer.
Further, the leveling agent is one of BYK-323 and BYK-326.
Further, the temperature rising speed in the step S1 is 3-5 ℃/min.
Further, in the step S2, the mass ratio of the carbon quantum dots, deionized water, ethanol and the silane coupling agent KH-570 is 4:30:15:1.5.
Further, in the step S3, the mass ratio of triethylene tetramine, propylene glycol methyl ether and epoxy resin is 30:80:45.
Further, in the step S4, the mass ratio of the epoxidized carbon quantum dot, the propylene glycol methyl ether, the triethylene tetramine modified epoxy resin solution and the methoxy-polyethylene glycol-epoxy group is 4:30:155:10.5.
Further, the preparation method of the carbon quantum dot modified waterborne epoxy resin emulsion comprises the following steps: adding a carbon quantum dot modified self-emulsifying epoxy resin curing agent and a water-based epoxy resin emulsifier into epoxy resin, uniformly stirring, heating to 60-80 ℃, then dropwise adding deionized water until the viscosity of the system suddenly drops, stirring for 30-60min, and continuously dropwise adding deionized water to obtain a carbon quantum dot modified water-based epoxy resin emulsion; the epoxy resin is one of epoxy resin E20, epoxy resin E44 and epoxy resin E51.
Still further, the invention also provides a preparation method of the special water-based paint, which comprises the following steps: mixing the carbon quantum dot modified aqueous epoxy resin emulsion with deionized water, adding triethanolamine, a dispersing agent, a defoaming agent and a leveling agent at the rotating speed of 800-1000rpm, and stirring for 20-30min to obtain the special aqueous coating.
Still further, the invention also provides an anti-corrosion application of the special water-based paint in a highly corrosive environment.
The invention has the beneficial effects that:
the carbon quantum dot modified waterborne epoxy resin emulsion is obtained by co-emulsifying the epoxy resin by the carbon quantum dot modified self-emulsifying epoxy resin curing agent and the waterborne epoxy resin emulsifier, wherein the carbon quantum dot modified self-emulsifying epoxy resin curing agent has the double effects of emulsification and curing by simultaneously introducing the hydrophilic flexible polyether chain, the hydrophobic epoxy resin and the carbon quantum dot on the epoxy resin E44, and has excellent miscibility with the traditional polyether emulsifier, and most importantly, the introduced carbon quantum dot has excellent interface stabilizing effect, so that the prepared carbon quantum dot modified waterborne epoxy resin emulsion has higher solid content.
The special water-based paint provided by the invention is prepared from carbon quantum dot modified water-based epoxy resin emulsion, triethanolamine, a dispersing agent, a defoaming agent, a leveling agent and deionized water through mixing and stirring, and can be coated on a substrate for curing to obtain a coating with high corrosion resistance, and still has excellent corrosion resistance in high-temperature and high-humidity environments.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
The sources and/or properties of the raw materials used in the examples and comparative examples of the present invention are as follows:
epoxy E44 is purchased from Penghui chemical products, inc. of Zhengzhou; methoxy-polyethylene glycol-epoxy group purchased from new born technology limited company of sierra, with a molecular weight of 1000; the water-based epoxy resin emulsifier is nonionic polyether, and is purchased from constant-rise new material technology Co., ltd, and the model is NP8836; the water-based curing agent is purchased from Guangdong Zhi Yuan New Material technology Co., ltd, and the model is ZW-6110.
Example 1: a preparation method of a special water-based paint comprises the following steps:
(1) Adding anhydrous citric acid into a crucible, heating to 220 ℃, pyrolyzing for 8.5 hours, cooling, then washing, centrifuging and drying to obtain carbon quantum dots;
(2) Dispersing 4g of carbon quantum dots in a mixed solution of 30g of deionized water and 15g of ethanol, then adding 1.5g of silane coupling agent KH-570, reacting for 6 hours at 65 ℃, washing, centrifuging and drying to obtain the epoxidized carbon quantum dots;
(3) Under the protection of nitrogen, adding 30g of triethylene tetramine into 80g of propylene glycol methyl ether, heating to 75 ℃, then adding 45g of epoxy resin E44, and reacting for 1.5 hours to obtain a triethylene tetramine modified epoxy resin solution;
(4) Dispersing 4g of epoxy carbon quantum dots in 30g of propylene glycol methyl ether, heating to 75 ℃, then dropwise adding 155g of triethylene tetramine modified epoxy resin solution, reacting for 2 hours after the dropwise adding is finished, then adding 10.5g of methoxy-polyethylene glycol-epoxy group, reacting for 15 minutes, washing, centrifuging and drying to obtain the carbon quantum dot modified self-emulsifying epoxy resin curing agent;
(5) Adding 15g of carbon quantum dot modified self-emulsifying epoxy resin curing agent and 2g of aqueous epoxy resin emulsifier into 100g of epoxy resin E44, uniformly stirring, heating to 70 ℃, then dropwise adding deionized water until the viscosity of the system suddenly drops, stirring for 30min, and continuously dropwise adding deionized water to obtain carbon quantum dot modified aqueous epoxy resin emulsion with the solid content of 57.4%;
(6) Mixing 100g of carbon quantum dot modified waterborne epoxy resin emulsion with 5g of deionized water, adding 3g of triethanolamine, 1g of BYK-P105,1.2g of BYK-095 and 0.7g of BYK-323 at a rotating speed of 800rpm, and stirring for 25min to obtain the special waterborne coating.
Example 2: a preparation method of a special water-based paint comprises the following steps:
(1) Adding anhydrous citric acid into a crucible, heating to 220 ℃, pyrolyzing for 8.5 hours, cooling, then washing, centrifuging and drying to obtain carbon quantum dots;
(2) Dispersing 4g of carbon quantum dots in a mixed solution of 30g of deionized water and 15g of ethanol, then adding 1.5g of silane coupling agent KH-570, reacting for 6 hours at 65 ℃, washing, centrifuging and drying to obtain the epoxidized carbon quantum dots;
(3) Under the protection of nitrogen, adding 30g of triethylene tetramine into 80g of propylene glycol methyl ether, heating to 75 ℃, then adding 45g of epoxy resin E44, and reacting for 1.5 hours to obtain a triethylene tetramine modified epoxy resin solution;
(4) Dispersing 4g of epoxy carbon quantum dots in 30g of propylene glycol methyl ether, heating to 75 ℃, then dropwise adding 155g of triethylene tetramine modified epoxy resin solution, reacting for 2 hours after the dropwise adding is finished, then adding 10.5g of methoxy-polyethylene glycol-epoxy group, reacting for 15 minutes, washing, centrifuging and drying to obtain the carbon quantum dot modified self-emulsifying epoxy resin curing agent;
(5) Adding 16g of carbon quantum dot modified self-emulsifying epoxy resin curing agent and 2.4g of aqueous epoxy resin emulsifier into 110g of epoxy resin E44, uniformly stirring, heating to 70 ℃, then dropwise adding deionized water until the viscosity of the system suddenly drops, stirring for 45min, and continuously dropwise adding deionized water to obtain carbon quantum dot modified aqueous epoxy resin emulsion with the solid content of 58.1%;
(6) 110g of carbon quantum dot modified waterborne epoxy resin emulsion and 8g of deionized water are mixed, 4g of triethanolamine, 2.5g of BYK-P105,1.5g of BYK-095 and 2g of BYK-323 are added at the rotating speed of 850rpm, and the mixture is stirred for 25min to obtain the special waterborne coating.
Example 3: a preparation method of a special water-based paint comprises the following steps:
(1) Adding anhydrous citric acid into a crucible, heating to 220 ℃, pyrolyzing for 8.5 hours, cooling, then washing, centrifuging and drying to obtain carbon quantum dots;
(2) Dispersing 4g of carbon quantum dots in a mixed solution of 30g of deionized water and 15g of ethanol, then adding 1.5g of silane coupling agent KH-570, reacting for 6 hours at 65 ℃, washing, centrifuging and drying to obtain the epoxidized carbon quantum dots;
(3) Under the protection of nitrogen, adding 30g of triethylene tetramine into 80g of propylene glycol methyl ether, heating to 75 ℃, then adding 45g of epoxy resin E44, and reacting for 1.5 hours to obtain a triethylene tetramine modified epoxy resin solution;
(4) Dispersing 4g of epoxy carbon quantum dots in 30g of propylene glycol methyl ether, heating to 75 ℃, then dropwise adding 155g of triethylene tetramine modified epoxy resin solution, reacting for 2 hours after the dropwise adding is finished, then adding 10.5g of methoxy-polyethylene glycol-epoxy group, reacting for 15 minutes, washing, centrifuging and drying to obtain the carbon quantum dot modified self-emulsifying epoxy resin curing agent;
(5) Adding 18g of carbon quantum dot modified self-emulsifying epoxy resin curing agent and 3g of water-based epoxy resin emulsifier into 120g of epoxy resin, uniformly stirring, heating to 80 ℃, then dropwise adding deionized water until the viscosity of the system suddenly drops, stirring for 50min, and continuously dropwise adding deionized water to obtain carbon quantum dot modified water-based epoxy resin emulsion with the solid content of 58.4%;
(6) 120g of carbon quantum dot modified waterborne epoxy resin emulsion and 10g of deionized water are mixed, 5g of triethanolamine, 3g of BYK-P105,3g of BYK-095 and 2.5g of BYK-323 are added at a rotating speed of 1000rpm, and the mixture is stirred for 25 minutes to obtain the special waterborne coating.
Example 4: a preparation method of a special water-based paint comprises the following steps:
(1) Adding anhydrous citric acid into a crucible, heating to 220 ℃, pyrolyzing for 8.5 hours, cooling, then washing, centrifuging and drying to obtain carbon quantum dots;
(2) Dispersing 4g of carbon quantum dots in a mixed solution of 30g of deionized water and 15g of ethanol, then adding 1.5g of silane coupling agent KH-570, reacting for 6 hours at 65 ℃, washing, centrifuging and drying to obtain the epoxidized carbon quantum dots;
(3) Under the protection of nitrogen, adding 30g of triethylene tetramine into 80g of propylene glycol methyl ether, heating to 75 ℃, then adding 45g of epoxy resin E44, and reacting for 1.5 hours to obtain a triethylene tetramine modified epoxy resin solution;
(4) Dispersing 4g of epoxy carbon quantum dots in 30g of propylene glycol methyl ether, heating to 75 ℃, then dropwise adding 155g of triethylene tetramine modified epoxy resin solution, reacting for 2 hours after the dropwise adding is finished, then adding 10.5g of methoxy-polyethylene glycol-epoxy group, reacting for 15 minutes, washing, centrifuging and drying to obtain the carbon quantum dot modified self-emulsifying epoxy resin curing agent;
(5) Adding 16g of carbon quantum dot modified self-emulsifying epoxy resin curing agent and 2.2g of aqueous epoxy resin emulsifier into 110g of epoxy resin E20, uniformly stirring, heating to 80 ℃, then dropwise adding deionized water until the viscosity of the system suddenly drops, stirring for 40min, and continuously dropwise adding deionized water to obtain carbon quantum dot modified aqueous epoxy resin emulsion with the solid content of 57.8%;
(6) 110g of carbon quantum dot modified waterborne epoxy resin emulsion and 8g of deionized water are mixed, 4g of triethanolamine, 1.5g of BYK-P105,2g of BYK-095 and 1.5g of BYK-323 are added at the rotating speed of 850rpm, and the mixture is stirred for 25 minutes to obtain the special waterborne coating.
Example 5: a preparation method of a special water-based paint comprises the following steps:
(1) Adding anhydrous citric acid into a crucible, heating to 220 ℃, pyrolyzing for 8.5 hours, cooling, then washing, centrifuging and drying to obtain carbon quantum dots;
(2) Dispersing 4g of carbon quantum dots in a mixed solution of 30g of deionized water and 15g of ethanol, then adding 1.5g of silane coupling agent KH-570, reacting for 6 hours at 65 ℃, washing, centrifuging and drying to obtain the epoxidized carbon quantum dots;
(3) Under the protection of nitrogen, adding 30g of triethylene tetramine into 80g of propylene glycol methyl ether, heating to 75 ℃, then adding 45g of epoxy resin E44, and reacting for 1.5 hours to obtain a triethylene tetramine modified epoxy resin solution;
(4) Dispersing 4g of epoxy carbon quantum dots in 30g of propylene glycol methyl ether, heating to 75 ℃, then dropwise adding 155g of triethylene tetramine modified epoxy resin solution, reacting for 2 hours after the dropwise adding is finished, then adding 10.5g of methoxy-polyethylene glycol-epoxy group, reacting for 15 minutes, washing, centrifuging and drying to obtain the carbon quantum dot modified self-emulsifying epoxy resin curing agent;
(5) Adding 18g of carbon quantum dot modified self-emulsifying epoxy resin curing agent and 2.8g of aqueous epoxy resin emulsifier into 105g of epoxy resin E51, uniformly stirring, heating to 80 ℃, then dropwise adding deionized water until the viscosity of the system suddenly drops, stirring for 40min, and continuously dropwise adding deionized water to obtain carbon quantum dot modified aqueous epoxy resin emulsion with the solid content of 58.8%;
(6) 110g of carbon quantum dot modified waterborne epoxy resin emulsion and 8g of deionized water are mixed, 3g of triethanolamine, 1g of BYK-P105,1g of BYK-095 and 2g of BYK-323 are added at the rotating speed of 850rpm, and the mixture is stirred for 25 minutes to obtain the special waterborne coating.
Comparative example 1: a preparation method of the water-based paint comprises the following steps:
(1) Adding 18.4g of aqueous epoxy resin emulsifier into 110g of epoxy resin E44, uniformly stirring, heating to 70 ℃, then dropwise adding deionized water until the viscosity of the system suddenly drops, stirring for 45min, and continuously dropwise adding deionized water to obtain aqueous epoxy resin emulsion with the solid content of 58.3%;
(2) 110g of aqueous epoxy resin emulsion and 8g of deionized water are mixed, 35g of aqueous curing agent ZW-6110,4g of triethanolamine, 2.5g of BYK-P105,1.5g of BYK-095 and 2g of BYK-323 are added at a rotating speed of 850rpm, and stirring is carried out for 25 minutes, so that the aqueous coating is obtained.
Comparative example 2: a preparation method of the water-based paint comprises the following steps:
(1) Adding anhydrous citric acid into a crucible, heating to 220 ℃, pyrolyzing for 8.5 hours, cooling, then washing, centrifuging and drying to obtain carbon quantum dots;
(2) Adding 18.4g of aqueous epoxy resin emulsifier into 110g of epoxy resin E44, uniformly stirring, heating to 70 ℃, then dropwise adding deionized water until the viscosity of the system suddenly drops, stirring for 45min, and continuously dropwise adding deionized water to obtain aqueous epoxy resin emulsion with the solid content of 58.5%;
(3) 110g of aqueous epoxy resin emulsion and 8g of deionized water are mixed, 35g of aqueous curing agent ZW-6110,4g of carbon quantum dots, 4g of triethanolamine, 2.5g of BYK-P105,1.5g of BYK-095 and 2g of BYK-323 are added at a rotating speed of 850rpm, and stirring is carried out for 25 minutes, so that the aqueous coating is obtained.
Performance test:
and (3) preparation of an adhesive film: the coatings prepared in examples 1-5 and comparative examples 1-2 were poured onto a polytetrafluoroethylene template, naturally dried for 24 hours, and then dried at 50℃for 48 hours to prepare a film having a thickness of 60.+ -. 5. Mu.m.
And (3) preparing a coating: the film was formed on a tinplate rapidly and uniformly in the longitudinal direction using a film forming machine in examples 1 to 5 and comparative examples 1 to 2, and after the film was dried, the film formation was repeated twice, and after natural drying for 24 hours, it was dried at 50℃for 48 hours to obtain a coating layer having a thickness of 60.+ -. 5. Mu.m.
Solid content: according to the national standard GB/T11175-2002, 1g of the epoxy resin emulsion prepared in examples 1-5 and comparative examples 1-2 is accurately weighed in a dry, constant weight and clean weighing bottle, placed in an oven at 105+/-2 ℃ for drying for 1 hour, taken out, cooled to room temperature and weighed. This procedure was repeated until the difference between the weights before and after the adjacent two times was less than 0.001g, the solid content was a percentage of the weight of the sample after drying and the weight of the sample before drying, and the average value was taken after three measurements for each group of samples, and the results are shown in Table 1.
Surface drying time: the coating surface dry time was measured by finger touch according to the national standard GB/T1728-89, and the test results are shown in Table 1.
Water vapor transmission rate: the adhesive film was tested according to the national standard GB/T16928-1997 by using a water vapor transmission tester, and the test results are shown in Table 1.
Chemical resistance Medium Properties: the coating is subjected to medium resistance test according to national standard GB 9274-88; the coated panels were edge sealed with a 1:1 mixture of paraffin and rosin, the edge sealing width being about 2.5mm, and the three panels were placed in a beaker containing medium (5% wt sulfuric acid solution, 5% wt sodium chloride solution, 5% wt sodium hydroxide solution), 2/3 immersed in water, heated to 50 ℃, and the panels were observed and recorded at intervals of time for changes, the results of which are shown in table 2.
TABLE 1 results of emulsion and coating base Performance test in examples 1-5 and comparative examples 1-2
| Sample of | Solids content/% | Emulsion storage stability/d | Surface dry time/h | Water vapor transmission rate/g/m 2 ·24h |
| Example 1 | 57.4 | ＞180 | 3.1 | 39 |
| Example 2 | 58.1 | ＞180 | 3.3 | 35 |
| Example 3 | 58.4 | ＞180 | 2.8 | 41 |
| Example 4 | 57.8 | ＞180 | 3.4 | 38 |
| Example 5 | 58.8 | ＞180 | 3.1 | 36 |
| Comparative example 1 | 58.3 | 95 | 3.4 | 95 |
| Comparative example 2 | 58.5 | 90 | 3.5 | 74 |
Data analysis: as can be seen from examples 1-5 in Table 1, the carbon quantum dot modified waterborne epoxy resin emulsion prepared by the invention has the characteristics of high solid content and high stability, and the prepared waterborne special coating has shorter surface drying time and extremely low water vapor transmittance. As can be seen from example 2 and comparative examples 1-2, the preparation of the carbon quantum dot modified self-emulsifying epoxy resin curing agent has a great influence on the water vapor transmission rate of the coating, the introduction of the carbon quantum dot can reduce the water vapor transmission rate, and most importantly, the grafting of the carbon quantum dot onto the curing agent as an emulsifier can greatly reduce the water vapor transmission rate of the coating, which is probably because the carbon quantum dot can improve the stability of emulsion, and form a continuous barrier in the subsequent curing process, thereby effectively improving the water blocking performance of the coating.
TABLE 2 Corrosion resistance test results of the coatings of examples 1-5 and comparative examples 1-2
| Sample of | Salt tolerance (50 ℃, 5%) | Alkali resistance (50 ℃, 5%) | Acid resistance (50 ℃, 5%) |
| Example 1 | Color change for 60 days | Foaming for 25 days | Foaming for 10 days |
| Example 2 | Color change of 63 days | Foaming for 28 days | Foaming for 11 days |
| Example 3 | Color change of 59 days | Foaming for 25 days | Foaming for 12 days |
| Example 4 | Color change for 65 days | Foaming for 26 days | Foaming for 10 days |
| Example 5 | Color change for 58 days | Foaming for 27 days | Foaming for 12 days |
| Comparative example 1 | Color change for 31 days | Foaming for 10 days | Foaming for 5 days |
| Comparative example 2 | Color change over 44 days | Foaming for 15 days | Foaming for 7 days |
Data analysis: as can be seen from examples 1-5 in Table 2, the aqueous specialty coatings prepared according to the present invention have excellent high temperature corrosion resistance. From example 2 and comparative examples 1-2, it can be seen that the carbon quantum dot modified self-emulsifying epoxy resin curing agent prepared by the invention can greatly improve the corrosion resistance of special paint, probably because the corrosion barrier formed by the carbon quantum dots effectively blocks the penetration of corrosive medium.
Claims (10)
1. The special water-based paint is characterized by comprising the following components in parts by weight: 100-120 parts of carbon quantum dot modified waterborne epoxy resin emulsion, 3-5 parts of triethanolamine, 0.5-3 parts of dispersing agent, 0.5-3 parts of defoaming agent, 0.5-3 parts of leveling agent and 5-10 parts of deionized water;
the carbon quantum dot modified waterborne epoxy resin emulsion is obtained by co-emulsifying epoxy resin by a carbon quantum dot modified self-emulsifying epoxy resin curing agent and a waterborne epoxy resin emulsifier; the mass ratio of the carbon quantum dot modified self-emulsifying epoxy resin curing agent, the water-based epoxy resin emulsifier and the epoxy resin in the carbon quantum dot modified water-based epoxy resin emulsion is 15-18:2-3:100-120; the solid content of the carbon quantum dot modified waterborne epoxy resin emulsion is 57% -59%; the aqueous epoxy resin emulsifier is a polyether emulsifier;
the preparation method of the carbon quantum dot modified self-emulsifying epoxy resin curing agent comprises the following steps:
s1: adding anhydrous citric acid into a crucible, heating to 200-250 ℃, pyrolyzing for 8-10 hours, cooling, washing, centrifuging and drying to obtain carbon quantum dots;
s2: dispersing carbon quantum dots in a mixed solution of deionized water and ethanol, then adding a silane coupling agent KH-570, reacting for 5-7 hours at 60-70 ℃, washing, centrifuging, and drying to obtain epoxidized carbon quantum dots;
s3: under the protection of nitrogen, triethylene tetramine is added into propylene glycol methyl ether, the temperature is raised to 70-80 ℃, then epoxy resin E44 is added, and the reaction is carried out for 1-1.5 hours, thus obtaining triethylene tetramine modified epoxy resin solution;
s4: dispersing the epoxidized carbon quantum dots in propylene glycol methyl ether, heating to 70-80 ℃, then dropwise adding a triethylene tetramine modified epoxy resin solution, reacting for 2 hours after the dropwise adding is finished, then adding methoxy-polyethylene glycol-epoxy group, reacting for 10-20 minutes, washing, centrifuging and drying to obtain the carbon quantum dot modified self-emulsifying epoxy resin curing agent.
2. The special water-based paint according to claim 1, wherein the dispersing agent is one of BYK-P104, BYK-P105 and BYK-163; the defoaming agent is polysiloxane defoaming agent; the leveling agent is one of BYK-323 and BYK-326.
3. The special water-based paint according to claim 1, wherein the heating rate in the step S1 is 3-5 ℃/min.
4. The special water-based paint according to claim 1, wherein the mass ratio of the carbon quantum dots, deionized water, ethanol and the silane coupling agent KH-570 in the step S2 is 4:30:15:1.5.
5. The special water-based paint according to claim 1, wherein the mass ratio of triethylene tetramine, propylene glycol methyl ether and epoxy resin in the step S3 is 30:80:45.
6. The special water-based paint according to claim 1, wherein the mass ratio of the epoxidized carbon quantum dot, the propylene glycol methyl ether, the triethylene tetramine modified epoxy resin solution and the methoxy-polyethylene glycol-epoxy group in the step S4 is 4:30:155:10.5.
7. The special water-based paint according to claim 1, wherein the preparation method of the carbon quantum dot modified water-based epoxy resin emulsion is as follows: adding the carbon quantum dot modified self-emulsifying epoxy resin curing agent and the water-based epoxy resin emulsifier into the epoxy resin, uniformly stirring, heating to 60-80 ℃, then dropwise adding deionized water until the viscosity of the system suddenly drops, then stirring for 30-60min, and then continuously dropwise adding the deionized water to obtain the carbon quantum dot modified water-based epoxy resin emulsion.
8. The special water-based paint according to claim 7, wherein the epoxy resin is one of epoxy resin E20, epoxy resin E44 and epoxy resin E51.
9. A method for preparing a special water-based paint according to any one of claims 1 to 8, characterized in that the specific preparation method is as follows: mixing the carbon quantum dot modified aqueous epoxy resin emulsion with deionized water, adding triethanolamine, a dispersing agent, a defoaming agent and a leveling agent at the rotating speed of 800-1000rpm, and stirring for 20-30min to obtain the special aqueous coating.
10. Use of a special aqueous coating according to any one of claims 1-8 for corrosion protection in highly corrosive environments.
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