CN118460028A - Water-based air-curing fluorocarbon coating and preparation method thereof - Google Patents
Water-based air-curing fluorocarbon coating and preparation method thereof Download PDFInfo
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- CN118460028A CN118460028A CN202410919236.9A CN202410919236A CN118460028A CN 118460028 A CN118460028 A CN 118460028A CN 202410919236 A CN202410919236 A CN 202410919236A CN 118460028 A CN118460028 A CN 118460028A
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- 238000000576 coating method Methods 0.000 title claims abstract description 108
- 239000011248 coating agent Substances 0.000 title claims abstract description 103
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- 238000002360 preparation method Methods 0.000 title abstract description 17
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 62
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 39
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 17
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- 238000000034 method Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000001723 curing Methods 0.000 claims description 38
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 22
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
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- 229910052731 fluorine Inorganic materials 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-OUBTZVSYSA-N aluminium-28 atom Chemical group [28Al] XAGFODPZIPBFFR-OUBTZVSYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of water-based paint, and particularly relates to a water-based air-curing fluorocarbon paint and a preparation method thereof, wherein the product formula comprises the following components in parts by weight: 20-22 parts of PVDF powder, 14-18 parts of ethylene glycol butyl ether, 18-20 parts of hydroxyethyl acrylate, 11-13 parts of styrene, 0.015-0.35 part of lithium hydroxide, 0.035-1.3 parts of nano alumina and 28-38 parts of deionized water. The aqueous single-component coating, the curing agent and the coating are mixed, the functional groups are polymerized in the presence of air to achieve the purpose of drying the coating, and the product has no VOC emission, is environment-friendly and has no environmental pollution and quick drying; the preparation method is simple and low in cost; the use is convenient, and the method is not limited by the environmental field conditions.
Description
Technical Field
The invention belongs to the technical field of water-based paint, and particularly relates to a water-based air-curing fluorocarbon paint and a preparation method thereof.
Background
The paint for the fields of metal wallboards, metal coiled materials, hardware, ceramic materials and the like mainly comprises oil paint, when the oil paint is painted, the oil paint needs to be painted with primer and then finish paint, meanwhile, the adhesion with the materials such as metal and the like is relatively poor, the labor cost is relatively high, and the corrosion resistance and the film forming performance of the product can not meet the actual requirements. More importantly, the solvent volatilizes during the production and coating processes, and the solvent-based paint contains a large amount of organic volatile matters (VOC) and is harmful to the human body due to environmental pollution.
The fluorocarbon coating is a coating taking fluororesin as a main film forming substance; also known as fluorocarbon paint, fluorine resin paint, and the like. Among various coatings, the fluororesin coating has particularly excellent properties due to the large electronegativity of the introduced fluorine element and the strong fluorocarbon bond energy. Weather resistance, heat resistance, low temperature resistance, chemical resistance, and unique non-tackiness and low friction, thereby being widely applied in various fields. The fluororesin paint with wider application mainly comprises PTFE, PVDF, FEVE types.
From the component point of view, the traditional fluorocarbon coating product is two-component and is packaged separately for use. The two-component coating has various limitations in construction, has high requirements on construction conditions and matched materials when the coating is applied to an outer wall, has no good elasticity and unstable performance, and has the technical problems of cracking and peeling phenomena, poor gloss retention, poor hardness and the like. In addition, when PVDF resin is used for preparing PVDF powder coating, because the PVDF resin is thermoplastic resin, the toughness is high, the PVDF powder coating cannot be crushed at normal temperature, the production cost is high, and the agglomeration phenomenon easily occurs in the preparation process, so that PVDF powder coating products in the market are fewer. In addition, PVDF coatings are baking coatings, which are at a much lower baking temperature than polytetrafluoroethylene, about 230 ℃, and therefore cannot be used on site, and require factory processing, which also limits further popularization of fluorocarbon coatings.
Disclosure of Invention
In order to solve the technical problems, the invention provides the aqueous air-curing fluorocarbon coating and the preparation method thereof, wherein the aqueous single-component coating, the curing agent and the coating are mixed, and the functional groups are subjected to polymerization reaction in the presence of air to achieve the purpose of drying the coating, so that the product has no VOC emission, is environment-friendly and has no environmental pollution, and the drying is fast; the preparation method is simple and low in cost; the use is convenient, and the method is not limited by the environmental field conditions.
The invention provides a water-based air-curing fluorocarbon coating for solving the technical problems, which is characterized in that: the formula comprises the following components in parts by weight:
20-22 parts of PVDF powder, 14-18 parts of ethylene glycol butyl ether, 18-20 parts of hydroxyethyl acrylate, 11-13 parts of styrene, 0.015-0.35 part of lithium hydroxide, 0.035-1.3 parts of nano alumina and 28-38 parts of deionized water.
In the optimized scheme, 21 parts of PVDF powder, 17 parts of ethylene glycol butyl ether, 19 parts of hydroxyethyl acrylate, 12 parts of styrene, 0.3 part of lithium hydroxide, 1.1 parts of nano aluminum oxide and 29.6 parts of deionized water.
In a further optimized scheme, the formula comprises the following components in parts by weight: 21 parts of PVDF powder, 15 parts of ethylene glycol butyl ether, 19 parts of hydroxyethyl acrylate, 12 parts of styrene, 0.02 part of lithium hydroxide, 0.04 part of nano aluminum oxide and 35 parts of deionized water.
The formula also comprises 0.08-0.12 part of curing agent and 0.12-0.15 part of silicon-aluminum coating auxiliary agent; in the optimization scheme, 0.1 part of curing agent and 0.13 part of silicon-aluminum coating auxiliary agent; or 0.1 part of curing agent and 0.14 part of silicon-aluminum coating auxiliary agent.
Specific: 21 parts of PVDF powder, 17 parts of ethylene glycol butyl ether, 19 parts of hydroxyethyl acrylate, 12 parts of styrene, 0.3 part of lithium hydroxide, 1.1 part of nano alumina, 29.6 parts of deionized water, 0.1 part of a curing agent and 0.13 part of a silicon-aluminum coating auxiliary agent; or 21 parts of PVDF powder, 15 parts of ethylene glycol butyl ether, 19 parts of hydroxyethyl acrylate, 12 parts of styrene, 0.02 part of lithium hydroxide, 0.04 part of nano alumina, 35 parts of deionized water, 0.1 part of a curing agent and 0.14 part of a silicon-aluminum coating auxiliary agent.
The curing agent is a prepolymer of toluene diisocyanate and coconut oil acid.
The silicon-aluminum coating auxiliary agent is dibutyl tin laurate.
The particle size of the nano alumina is less than or equal to 100nm.
The particle size of the nano alumina is 5-8 nanometers.
The product of the invention is mainly suitable for materials such as steel components, aluminum components, buildings and the like.
The PVDF powder is soluble powder in the invention. The ethylene glycol butyl ether dissolves and disperses PVDF powder, and the hydroxyethyl acrylate plays a role in dissolution, styrene film formation, lithium hydroxide catalysis and nano alumina increase the coating compactness.
The aqueous air-cured fluorocarbon coating product is prepared by mixing and packaging an aqueous single-component curing agent and a coating, and is mainly characterized in that the curing agent is subjected to coating treatment, and is polymerized with saturated air in the atmosphere to form a coating film when in use, and isocyanate functional groups in the coating react with the saturated air in the atmosphere to form a film when in reaction, namely, the curing agent and the coating are stored in the absence of reaction, and the functional groups are opened in the saturated air to react, so that the aqueous air-cured fluorocarbon coating product has very good coating performance. When in use, the coating film is formed without heating or radiation curing, and the operation is simple.
The film forming preparation process comprises the following steps: the polymer produced by the catalysis of PVD fluorocarbon powder (polyvinylidene fluoride), ethylene glycol butyl ether, hydroxyethyl acrylate, styrene and lithium hydroxide through copolymerization is treated by using nano alumina as a molecular coating, and polymerized to form a coating film under the condition of saturated air.
Specifically, the preparation method of the water-based air-curing fluorocarbon coating comprises the following steps:
(1) Pumping ethylene glycol butyl ether into a reaction kettle, starting a steam heating pipe to slowly heat to 65-75 ℃, starting stirring, slowly adding PVDF powder to heat to 115-125 ℃, and opening reflux until sampling is transparent;
(2) Cooling to 75-85 ℃, adding hydroxyethyl acrylate, slowly and sequentially adding styrene and lithium hydroxide under stirring, heating to 80-90 ℃ for continuous reaction, keeping reflux for 4-4.3h, sampling, dripping on a glass plate, drawing a film and transparency, wherein the acid value is below 4-5 mg; the cooling rate is 11 ℃/10min, and the acid value reaches the reaction end point at 4-5 mg.
(3) Cooling to 48-52deg.C, slowly adding nanometer aluminum oxide, maintaining for 0.8-1.2 hr, cooling to 22-26deg.C, filtering, packaging, and transporting or storing.
In the optimized scheme, the temperature is raised to 70 ℃ in the step (1) and then is raised to 120 ℃; the temperature rising rate is 5 ℃/10min, and the reflux time is 4-4.5h. The stepwise heating up is used for meeting the reaction condition, and 70 ℃ or 120 ℃ is the stepwise final reaction temperature.
The temperature in the step (2) is reduced to 80 ℃; the styrene and lithium hydroxide were added and the reaction was continued at 85℃for 4.1h at reflux. The reason of the stepwise cooling is to prevent the excessive reaction of the residual temperature rising, and the cooling to 80 ℃ is the optimal dilution temperature. Lithium hydroxide was added to maintain 85 ℃ for optimal catalytic performance.
And (3) cooling to 50 ℃, slowly adding nano alumina, keeping for 1h, and cooling the sampling liquid to 25 ℃ in a transparent way. The temperature required by the process is important and cannot be changed, otherwise, the performance of the product cannot be completely realized.
In a further optimized scheme, the temperature is reduced to 48-52 ℃ in the step (3), then nano alumina and a silicon-aluminum coating auxiliary agent are slowly added for maintaining for 0.8-1.2h, the temperature of the sampling liquid is reduced to 22-26 ℃ in a transparent way, a curing agent is added after the sampling liquid is filtered out of a kettle, and packaging, transportation or storage are carried out.
The product of the invention does not react when being stored, and when the product is opened, the curing agent and the coating film are treated to lead the coating layer to generate polymerization reaction with saturated air in the atmosphere to form a coating film, and isocyanate functional groups in the coating layer react with saturated air in the atmosphere to generate a film.
When the fluorocarbon coating is used, the coating spreads and contacts with saturated air to generate polymerized film, and at the moment, the nano aluminum oxide film is completely opened to endow the coating with drying performance, and compared with the traditional fluorocarbon coating, the fluorocarbon coating has water-soluble low VOC emission, and has better workability and atmospheric resistance than the traditional product.
The product has no VOC emission due to the characteristics of the invention, and the functional group can be polymerized in the air to achieve the purpose of drying the coating.
Detailed Description
The invention is further illustrated by the following description of specific embodiments:
Example 1:
The preparation process of the aqueous air-curing fluorocarbon coating comprises the following steps: the polymer produced by catalyzing and copolymerizing PVD fluorocarbon powder, ethylene glycol butyl ether, hydroxyethyl acrylate, styrene and lithium hydroxide is treated by using nano alumina as a molecular coating, and polymerized to form a coating film under the condition of saturated air. The paint formula is as follows, calculated by 100kg of finished product:
21kg of PVDF powder, 17kg of ethylene glycol butyl ether, 19kg of hydroxyethyl acrylate, 12kg of styrene, 0.3kg of lithium hydroxide, 1.1kg of nano alumina and 29.6kg of deionized water.
Pumping ethylene glycol butyl ether into a reaction kettle, starting a steam heating pipe to slowly heat to 70 ℃, starting stirring, slowly adding PVDF powder to heat to 120 ℃, opening reflux to sample transparency, cooling to 80 ℃, adding hydroxyethyl acrylate, slowly and sequentially adding styrene and lithium hydroxide under stirring, heating to keep 85 ℃ for continuous reaction to keep reflux for 4.1h, sampling, dripping the sample to a glass plate, drawing a film transparency, cooling to 50 ℃ with an acid value below 4mg, slowly adding nano alumina, keeping the temperature for 1h, transparently cooling the sampled liquid to 25 ℃, and discharging the sampled liquid from the kettle for filtration for standby.
When in use, the coating spreads out and contacts with saturated air to generate polymerized film, and the nano aluminum oxide film is completely opened to endow the coating film with drying performance. Compared with the traditional fluorocarbon coating, the coating has the advantages of water solubility, low VOC emission, better construction performance and better atmospheric resistance than the traditional product.
Example 2:
Aqueous air-cured fluorocarbon coating, based on 100kg of finished product: 21kg of PVDF powder, 15kg of ethylene glycol butyl ether, 19kg of hydroxyethyl acrylate, 12kg of styrene, 0.02kg of lithium hydroxide, 0.04kg of nano alumina and 35kg of deionized water.
Feeding materials for heating at the 11 th point of the day for 20 minutes, pumping ethylene glycol butyl ether into a reaction kettle, starting a steam heating pipe for slowly heating to 70 ℃, starting stirring, slowly adding PVDF powder for heating to 120 ℃, opening reflux to be transparent, cooling to 80 ℃, adding hydroxyethyl acrylate, slowly and sequentially adding styrene and lithium hydroxide under stirring, heating to keep 85 ℃ for continuous reaction, keeping reflux for 4.1 hours, sampling, dripping the sample on a glass plate for drawing a film for transparency, cooling to 50 ℃ below 5mg of acid value, slowly adding nano alumina for keeping for 1 hour, cooling the sample liquid for transparency to 25 ℃, and discharging the sample liquid from the kettle for filtering for standby.
And (5) measuring the acid value of the reaction end point at the point of 50 minutes at 2, wherein the acid value is 5mg/100g, and spreading a coating film on the surface of the polished tinplate for 70 minutes. The next day of dry passing is measured, the hardness H is impacted by 50kg.cm 2, no crack is observed by a 100-time magnifying glass, and the water solubility test is correct.
Example 3:
The aqueous air-curing fluorocarbon coating comprises the following components in parts by weight: 20 parts of PVDF powder, 14 parts of ethylene glycol butyl ether, 18 parts of hydroxyethyl acrylate, 11 parts of styrene, 0.015 part of lithium hydroxide, 0.035 part of nano aluminum oxide and 28 parts of deionized water.
The preparation method comprises the following steps:
(1) Pumping ethylene glycol butyl ether into a reaction kettle, starting a steam heating pipe to slowly heat to 65 ℃, starting stirring, slowly adding PVDF powder to heat to 115 ℃, and opening reflux until sampling is transparent; the temperature rising rate is 5 ℃/10mn, and the reflux time is 4 hours.
(2) Cooling to 75deg.C, adding hydroxyethyl acrylate, slowly adding styrene and lithium hydroxide under stirring, keeping the temperature of 80deg.C, keeping the reaction for 4 hr, sampling, dripping on glass plate, and making film-drawing transparent, wherein the acid value is below 4 mg; the cooling rate is 11 ℃/10min, and the acid value reaches the reaction end point at 4 mg.
(3) Cooling to 48-52 deg.C, slowly adding nano alumina, maintaining for 0.8-1.2 hr, cooling the sampled liquid to 22-26 deg.C, and filtering or storing.
Example 4:
The aqueous air-curing fluorocarbon coating comprises the following components in parts by weight: 22 parts of PVDF powder, 18 parts of ethylene glycol butyl ether, 20 parts of hydroxyethyl acrylate, 13 parts of styrene, 0.35 part of lithium hydroxide, 1.3 parts of nano aluminum oxide and 38 parts of deionized water.
The preparation method comprises the following steps:
(1) Pumping ethylene glycol butyl ether into a reaction kettle, starting a steam heating pipe to slowly heat to 75 ℃, starting stirring, slowly adding PVDF powder to heat to 125 ℃, and opening reflux until sampling is transparent; the temperature rising rate is 5 ℃/10mn, and the reflux time is 4.5h.
(2) Cooling to 85deg.C, adding hydroxyethyl acrylate, slowly adding styrene and lithium hydroxide under stirring, continuously reacting at 80-90deg.C for 4.3 hr, sampling, and dripping on glass plate to obtain transparent film with acid value below 4 mg; the cooling rate is 11 ℃/10min, and the acid value reaches the reaction end point at 4 mg.
(3) Cooling to 52 ℃, slowly adding nano alumina, keeping for 1.2 hours, cooling the sampled liquid to 26 ℃ transparently, and taking out of the kettle, filtering for standby or storage.
Example 5:
The aqueous air-curing fluorocarbon coating comprises the following components in parts by weight: 21 parts of PVDF powder, 14-18 parts of ethylene glycol butyl ether, 19 parts of hydroxyethyl acrylate, 12 parts of styrene, 0.1 part of lithium hydroxide, 0.5 part of nano aluminum oxide and 32 parts of deionized water.
The preparation method comprises the following steps:
(1) Pumping ethylene glycol butyl ether into a reaction kettle, starting a steam heating pipe to slowly heat to 68 ℃, starting stirring, slowly adding PVDF powder to heat to 118 ℃, and opening reflux until sampling is transparent; the temperature rising rate is 5 ℃/10mn, and the reflux time is 4.3h.
(2) Cooling to 78 ℃, adding hydroxyethyl acrylate, slowly and sequentially adding styrene and lithium hydroxide under stirring, keeping the temperature of 86 ℃ for continuous reaction, keeping reflux for 4.2 hours, sampling, dripping the sample on a glass plate, drawing a film and transparency, wherein the acid value is below 4 mg; the cooling rate is 11 ℃/10min, and the acid value reaches the reaction end point at 4 mg.
(3) Cooling to 49 ℃, slowly adding nano alumina, keeping for 0.9h, cooling the sampled liquid to 23 ℃ transparently, and taking out of the kettle, filtering for standby or storage.
Example 6:
The aqueous air-curing fluorocarbon coating comprises the following components in parts by weight: 21 parts of PVDF powder, 17 parts of ethylene glycol butyl ether, 19 parts of hydroxyethyl acrylate, 12 parts of styrene, 0.3 part of lithium hydroxide, 1.1 parts of nano aluminum oxide, 29.6 parts of deionized water, 0.1 part of a curing agent and 0.13 part of a silicon-aluminum coating auxiliary agent. The curing agent is a prepolymer of toluene diisocyanate and coconut oleic acid, and the silicon aluminum coating auxiliary agent is dibutyl tin laurate.
The preparation method comprises the following steps:
(1) Pumping ethylene glycol butyl ether into a reaction kettle, starting a steam heating pipe to slowly heat to 68 ℃, starting stirring, slowly adding PVDF powder to heat to 118 ℃, and opening reflux until sampling is transparent; the temperature rising rate is 5 ℃/10mn, and the reflux time is 4.3h.
(2) Cooling to 78 ℃, adding hydroxyethyl acrylate, slowly and sequentially adding styrene and lithium hydroxide under stirring, keeping the temperature of 86 ℃ for continuous reaction, keeping reflux for 4.2 hours, sampling, dripping the sample on a glass plate, drawing a film and transparency, wherein the acid value is below 4 mg; the cooling rate is 11 ℃/10min, and the acid value reaches the reaction end point at 4 mg.
(3) Cooling to 50deg.C, slowly adding nano alumina and silicon-aluminum coating assistant, maintaining for 1 hr, cooling the sample liquid to 24deg.C, filtering, adding solidifying agent, packaging, and transporting or storing.
Example 7:
the aqueous air-curing fluorocarbon coating comprises the following components in parts by weight: 21 parts of PVDF powder, 15 parts of ethylene glycol butyl ether, 19 parts of hydroxyethyl acrylate, 12 parts of styrene, 0.02 part of lithium hydroxide, 0.04 part of nano alumina, 35 parts of deionized water, 0.1 part of a curing agent and 0.14 part of a silicon-aluminum coating auxiliary agent. The curing agent is a prepolymer of toluene diisocyanate and coconut oleic acid, and the silicon aluminum coating auxiliary agent is dibutyl tin laurate.
The preparation method comprises the following steps:
(1) Pumping ethylene glycol butyl ether into a reaction kettle, starting a steam heating pipe to slowly heat to 68 ℃, starting stirring, slowly adding PVDF powder to heat to 118 ℃, and opening reflux until sampling is transparent; the temperature rising rate is 5 ℃/10mn, and the reflux time is 4.3h.
(2) Cooling to 78 ℃, adding hydroxyethyl acrylate, slowly and sequentially adding styrene and lithium hydroxide under stirring, keeping the temperature of 86 ℃ for continuous reaction, keeping reflux for 4.2 hours, sampling, dripping the sample on a glass plate, drawing a film and transparency, wherein the acid value is below 4 mg; the cooling rate is 11 ℃/10min, and the acid value reaches the reaction end point at 4 mg.
(3) Cooling to 49 ℃, slowly adding nano alumina and a silicon-aluminum coating auxiliary agent, keeping for 0.9h, transparently cooling the sampled liquid to 25 ℃, taking out of a kettle, filtering, adding a curing agent, packaging, transporting or storing.
Example 8:
the other contents are as in example 6, wherein the curing agent is 0.08 part and the silicon aluminum coating auxiliary agent is 0.12 part.
Example 9:
The other contents are as in example 6, wherein the curing agent is 0.12 part and the silicon aluminum coating auxiliary agent is 0.15 part.
Test one
The raw materials are sequentially put into a dispersing kettle according to the prescription and process, stirring and dispersing are started to 60um, the mixture is transferred into a sanding top for grinding to 20um, a sample is sprayed on a plate, and after the mixture is dried, the coating is detected, and the indexes are shown in the following table 1:
TABLE 1
| Index (I) | Detection Performance (value) | Detection instrument |
| Appearance of the coating | Leveling without visible chromatic aberration | Color difference meter |
| Surface dry | ≤4H | Coating drier |
| Drying | Normal temperature of 24H or less | Coating drier |
| Artificial weathering | ≥500H | Xenon lamp aging box |
| Adhesion force | Grade less than or equal to 0 | Circle drawing adhesive force instrument |
| VOC/L | Less than or equal to 50g of VOL content which accords with the environment-friendly coating standard and is extremely low | Gas chromatograph |
As can be seen from Table 1, the coating of the invention has the advantages of quick drying, good impact resistance and aging resistance, and prolonged service life.
The reaction principle of the invention is that FEVE resin is emulsified to become hydrophilic resin, hydrophilic prepolymer with isocyanate functional group (NCO) is slowly added according to the amount of 11% under the working condition of below 30 ℃ and is stirred at low speed for standby.
In the invention, isocyanate functional groups are subjected to sealing treatment in a silicon-aluminum coating mode, and ring opening reaction is required under saturated air condition. The silicon-aluminum coating mode is wet coating, and the specific operation steps are that when the temperature is reduced to 50 ℃, silicon-aluminum coating auxiliary agent is slowly added, the auxiliary agent is dibutyl tin laurate, functional groups are locked, and when the air reaches the saturation degree, the functional groups automatically open loops, so that the effect of coating reaction is achieved.
In the following formula, carbon bonds and hydrogen bonds in the FEVE of the coating film forming and curing principle are double bond structures, and the reaction is completely in a single double bond structure:
，
It can be seen that the structure following the mid-symbol of the formula indicates that the NCO functional group is not present to participate in the film-forming polymerization, i.e., that the NCO functional group is present, but in excess air, a polymerized film is produced.
The formula shows that the coating realizes single-component coating and has the effects of no need of dilution and no need of baking.
Test II
Three-neck flask standing cold reflux belt stirring:
21g of PVDF powder, 15g of ethylene glycol butyl ether, 13g of hydroxyethyl acrylate, 17g of styrene, 0.01g of lithium hydroxide, 0.03g of nano alumina and 35g of deionized water.
Feeding and heating reaction at 2 points 21 on the day of 7 months and 4 days, wherein the reaction temperature is 70 ℃, 120 ℃, 80 ℃ and 50 ℃ respectively. The acid value at the end of the reaction was 5mg at point 37 minutes. The coating film was spread on the surface of the polished tinplate for 57min. The 17-point test is carried out on the next day, the coating passes through a real dry test, the hardness is greater than H, the coating is cracked through an impact test, and the coating is analyzed to have great defects due to overlarge polymerization degree.
The consumption of the styrene is too large, the time and the temperature of the catalyst are added to be adjusted, the water solubility test is correct, the reflux time is too long, the polymerization degree is too long, and the hydroxy functional group is too small to cause the air reaction to be too fast.
From the above, the raw materials are used in proper amounts, and the invention has very good effects.
Test three
Comparative example 1, comparative example 2 and comparative example 3 were set as follows:
In comparative example 1, the other contents were as in example 1, wherein the formulation was free of lithium hydroxide and nano alumina.
In comparative example 2, the oxidized particle size was 200nm as in example 1.
In comparative example 3, the other contents were as in example 1, and the nano alumina particle size was 10 nm.
Analysis of results:
comparative example 1 the paint was self-polymerized during the preparation process, and a good paint could not be formed.
The coating prepared in comparative example 2 did not meet the coating requirements set forth in Table 1 above at all.
The coating prepared in comparative example 3 had a significant decrease in coating hardness during use.
The above examples/experiments are only examples for clarity of illustration and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. An aqueous air-cured fluorocarbon coating, characterized in that: the formula comprises the following components in parts by weight:
20-22 parts of PVDF powder, 14-18 parts of ethylene glycol butyl ether, 18-20 parts of hydroxyethyl acrylate, 11-13 parts of styrene, 0.015-0.35 part of lithium hydroxide, 0.035-1.3 parts of nano alumina and 28-38 parts of deionized water.
2. An aqueous air-curable fluorocarbon coating according to claim 1, wherein: the formula comprises the following components in parts by weight: 21 parts of PVDF powder, 17 parts of ethylene glycol butyl ether, 19 parts of hydroxyethyl acrylate, 12 parts of styrene, 0.3 part of lithium hydroxide, 1.1 parts of nano aluminum oxide and 29.6 parts of deionized water.
3. An aqueous air-curable fluorocarbon coating according to claim 1, wherein: the formula comprises the following components in parts by weight: 21 parts of PVDF powder, 15 parts of ethylene glycol butyl ether, 19 parts of hydroxyethyl acrylate, 12 parts of styrene, 0.02 part of lithium hydroxide, 0.04 part of nano aluminum oxide and 35 parts of deionized water.
4. An aqueous air-curable fluorocarbon coating according to any one of claims 1-3, characterized in that: the particle size of the nano alumina is less than or equal to 100nm.
5. An aqueous air-curable fluorocarbon coating according to claim 4, wherein: the particle size of the nano alumina is 5-8 nanometers.
6. An aqueous air-curable fluorocarbon coating according to any one of claims 1-3, characterized in that: the formula also comprises 0.08-0.12 part of curing agent and 0.12-0.15 part of silicon-aluminum coating auxiliary agent, wherein the curing agent is a prepolymer of toluene diisocyanate and coconut oleic acid, and the silicon-aluminum coating auxiliary agent is dibutyl tin laurate.
7. An aqueous air-curable fluorocarbon coating according to claim 6, wherein: 0.1 part of the curing agent and 0.13 part of the silicon-aluminum coating auxiliary agent; or 0.1 part of curing agent and 0.14 part of silicon-aluminum coating auxiliary agent.
8. The method for preparing the aqueous air-curing fluorocarbon coating as claimed in claim 1, wherein: the method comprises the following steps:
(1) Pumping ethylene glycol butyl ether into a reaction kettle, heating to 65-75 ℃, adding PVDF powder in stirring, and heating to 115-125 ℃;
(2) Cooling to 75-85 ℃, adding hydroxyethyl acrylate, sequentially adding styrene and lithium hydroxide under stirring, keeping the temperature at 80-90 ℃ for continuous reaction, and keeping reflux for 4-4.3h;
(3) Cooling to 48-52deg.C, adding nano alumina, maintaining for 0.8-1.2 hr, cooling to 22-26deg.C when the sample liquid is transparent, and filtering or storing.
9. The method for preparing the aqueous air-curing fluorocarbon coating as claimed in claim 8, wherein: in the step (1), the temperature is raised to 70 ℃ and then to 120 ℃; and/or the temperature is reduced to 80 ℃ in the step (2); the lithium hydroxide is added and the reaction is kept at 85 ℃ for 4.1 hours under reflux.
10. The method for preparing the aqueous air-curing fluorocarbon coating as claimed in claim 8, wherein: and (3) cooling to 50 ℃, slowly adding nano alumina, keeping for 1h, and cooling the sampling liquid to 25 ℃ in a transparent way.
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| CN116285425A (en) * | 2022-12-15 | 2023-06-23 | 宜宾天原海丰和泰有限公司 | Titanium dioxide silicon-aluminum coating method |
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