CN113004482B - Waterborne polyurethane acrylate and preparation method and application thereof - Google Patents
Waterborne polyurethane acrylate and preparation method and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention discloses a waterborne polyurethane acrylate and a preparation method and application thereof, wherein the waterborne polyurethane acrylate comprises the following raw materials: fluorine-silicon modified dihydric alcohol and an auxiliary agent I; the preparation method comprises the following steps: s1, mixing the fluorine-silicon modified dihydric alcohol and the hydrophilic monomer, heating for reaction, and cooling to obtain a precursor; s2, heating and reacting the precursor, the catalyst and the isocyanate to obtain an intermediate; and S3, mixing the intermediate, the cross-linking agent and the polymerization inhibitor for reaction, and adding a neutralizing agent to obtain the waterborne polyurethane acrylate. The waterborne polyurethane acrylate of the invention adopts the introduction of the organic silicon chain segment on the molecular chain segment to provide smooth feeling, hand feeling and stain resistance, and simultaneously introduces the organic fluorine chain segment on the molecular side chain to further improve the stain resistance and low surface tension.
Description
Technical Field
The invention relates to the field of coatings, and particularly relates to a waterborne polyurethane acrylate and a preparation method and application thereof.
Background
With the development of science and technology and the improvement of living standard, mobile consumer goods such as mobile phones, computers and the like become an indispensable part of daily life of people. However, these mobile consumer products are easily stained with other contaminants such as oil stains and hand sweats during the use process, which affects the beauty. The contamination of mobile consumer products is often ameliorated by spraying a coating on the plastic surface of the mobile consumer product.
The stain resistance of the water-based UV coating system is achieved by adding the stain resistance auxiliary agent, but the molecular structure providing the stain resistance is obtained in such a way that the molecular structure is not crosslinked with other components in the coating system, and only a thin stain resistance layer is formed on the surface of a paint film, so that the stain resistance of the paint film is poor, and the paint film has poor durability and is not wear-resistant.
The waterborne PU system provides lasting stain resistance by crosslinking the silicon-fluorine continuous segments in a paint film with other components in the system through heat curing, but the performance of the PU system is difficult to meet the performance requirements in the 3C field.
In view of the above, there is a need for development of an aqueous urethane acrylate that can produce an aqueous coating having good stain resistance and low surface tension.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows: the water-based polyurethane acrylate is provided, and the water-based paint prepared from the water-based polyurethane acrylate has good stain resistance and low surface tension.
The second technical problem to be solved by the invention is as follows: provides a preparation method of the waterborne polyurethane acrylate.
The third technical problem to be solved by the invention is as follows: provides the application of the waterborne polyurethane acrylate.
In order to solve the first technical problem, the technical scheme provided by the invention is as follows: the water-based polyurethane acrylate comprises the following raw materials: fluorine-silicon modified dihydric alcohol and an auxiliary agent I;
wherein the structure of the waterborne polyurethane acrylate is shown as the following formula:
the structure of the fluorine-silicon modified dihydric alcohol is shown as the following formula:
wherein the value range of m is 2-20;
the value range of n is 8-50.
According to some embodiments of the invention, m ranges from 5 to 12.
According to some embodiments of the invention, n ranges from 10 to 20.
The value of n is in the range of 8 to 50, preferably 10 to 20, because when the molecular weight is too low, the silicone segment distributed in the main chain cannot provide a smooth feeling and a thick feeling, and when the molecular weight is too high, the smooth feeling and the thick feeling can be provided, but the hardness, the water resistance and other properties of the paint film are affected.
m is from 2 to 20, preferably from 5 to 12, since too short a fluorine segment does not provide stain resistance and low surface tension, and too long a fluorine segment affects the crosslinking density of the urethane acrylate, thereby reducing the resistance of the paint film.
According to some embodiments of the invention, the auxiliary agent i comprises a hydrophilic monomer, a catalyst, a polymerization inhibitor, an isocyanate, a neutralizing agent and a crosslinking agent.
According to some embodiments of the invention, the aqueous urethane acrylate comprises the following raw materials in parts by weight: 100 to 120 portions of fluorine-silicon modified dihydric alcohol, 10 to 12 portions of hydrophilic monomer, 1 to 1.2 portions of catalyst, 0.4 to 0.5 portion of polymerization inhibitor, 40 to 43 portions of isocyanate, 7 to 9 portions of neutralizer and 100 to 280 portions of cross-linking agent.
According to some embodiments of the present invention, the fluorosilicone modified glycol is prepared from the following raw materials: a double-ended epoxy silicone, a perfluoropolyether carboxylic acid, and a phosphine catalyst.
According to some embodiments of the invention, the double-ended epoxy silicone has the structure shown below:
wherein the value range of x is 8-50; preferably, the value range of x is 10-20.
According to some embodiments of the invention, the perfluoropolyether carboxylic acid has the structure:
wherein the value range of y is 2-20; preferably, the value range of y is 5-12.
According to some embodiments of the invention, the mass ratio of the double-end epoxy organosilicon, the perfluoropolyether carboxylic acid and the phosphine catalyst is 70-80: 140-160: 1-3.
According to some embodiments of the invention, the double-ended epoxy silicone has a relative molecular mass of 1000 to 7000.
According to some embodiments of the invention, the relative molecular mass of the perfluoropolyether carboxylic acid is 600 to 4000.
According to some embodiments of the invention, the phosphine catalyst is triphenylphosphine.
According to some embodiments of the invention, the hydrophilic monomer comprises 2, 2-dimethylolpropionic acid (DMPA), 2-dimethylolbutyric acid.
According to some embodiments of the invention, the catalyst comprises an organotin drier and an organobismuth catalyst; preferably, the organotin drier comprises dibutyltin dilaurate (T-12).
According to some embodiments of the invention, the polymerization inhibitor comprises hydroquinone monomethyl ether (MQ).
According to some embodiments of the invention, the isocyanate comprises at least one of isophorone diisocyanate (IPDI), toluene diisocyanate, and diphenylmethane diisocyanate.
According to some embodiments of the invention, the isocyanate comprises isophorone diisocyanate.
According to some embodiments of the invention, the neutralizing agent comprises an organic amine.
According to some embodiments of the invention, the organic amine comprises at least one of triethylamine and triethanolamine.
According to some embodiments of the invention, the cross-linking agent comprises high hydroxyl value pentaerythritol triacrylate.
According to some embodiments of the present invention, the high hydroxyl pentaerythritol triacrylate has a hydroxyl value of 35 to 70mg KOH/g.
The waterborne polyurethane acrylate according to the embodiment of the invention has at least the following beneficial effects: the waterborne polyurethane acrylate of the invention adopts the introduction of the organic silicon chain segment on the molecular chain segment to provide smooth feeling, thick feeling and stain resistance, and simultaneously introduces the organic fluorine chain segment on the molecular side chain to further improve the stain resistance and low surface tension.
To solve the second technical problem, the present invention provides the following technical solutions: the preparation method of the waterborne polyurethane acrylate comprises the following steps:
s1, mixing the fluorine-silicon modified dihydric alcohol and the hydrophilic monomer, heating for reaction, and cooling to obtain a precursor;
s2, heating and reacting the precursor, the catalyst and isocyanate to obtain an intermediate;
and S3, mixing the intermediate, the cross-linking agent and the polymerization inhibitor for reaction, and adding a neutralizing agent to obtain the waterborne polyurethane acrylate.
According to some embodiments of the present invention, the method for preparing the aqueous urethane acrylate further comprises the steps of: and mixing and reacting the double-end-group epoxy organic silicon, the perfluoropolyether carboxylic acid and the phosphine catalyst until the acid value is 5mg KOH/g, and cooling to obtain the fluorine-silicon modified dihydric alcohol.
According to some embodiments of the invention, the temperature of the heating in the step S1 is 100 ℃ to 110 ℃.
According to some embodiments of the invention, the temperature of the temperature reduction in the step S1 is 50 ℃ to 55 ℃.
According to some embodiments of the invention, the temperature of heating in the step S2 is 75 ℃ to 85 ℃.
According to some embodiments of the invention, the temperature of the mixing reaction in the step S3 is 75 ℃ to 85 ℃.
According to some embodiments of the invention, the time of neutralization is 10 min.
According to some embodiments of the invention, the temperature of the neutralization is between 50 ℃ and 55 ℃.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects: the technical route of the invention realizes that the organic silicon molecular chain segment is connected on the main chain of the polyurethane acrylate, thereby providing a certain stain resistance, excellent smoothness and thickness for the paint film, and the fluorine-containing chain segment connected on the molecular side chain can swing freely, thereby being capable of transferring to the surface of the paint film in the process of baking a wet film, so that the paint film has better wear resistance, extremely low surface tension and extremely high water contact angle. The end-capped hydroxyl monomer can be selected as desired to achieve adjustment of different functionalities.
In order to solve the third technical problem, the technical scheme provided by the invention is as follows: the application of the waterborne polyurethane acrylate in preparing waterborne coatings.
According to some embodiments of the invention, the aqueous stain resistant resin comprises the following raw materials: the waterborne polyurethane acrylate and an auxiliary agent II.
According to some embodiments of the invention, the auxiliary agent ii comprises matte powder, a wetting agent, a leveling agent, a thickener, a defoamer, an initiator, a cosolvent and water.
According to the application of the embodiment of the invention, at least the following beneficial effects are achieved: according to the invention, the waterborne polyurethane acrylate synthesized by organic fluorine modified organosilicon is applied to a waterborne photocureable coating system, and the whole paint film is crosslinked together; during crosslinking, the fluorine-containing segment on the acrylic branch of the aqueous polyurethane migrates to the surface of the paint film, thereby providing stain resistance and low surface tension, and such properties are durable for a long period of time. Meanwhile, the organosilicon chain segment of the main chain of the waterborne polyurethane acrylic acid is also crosslinked in the paint film, thereby providing lasting smooth and thick feeling. Under the dual synergistic effect of the organic fluorine chain segment and the organic silicon chain segment, the paint film has lasting smooth feeling, thick feeling, low surface tension and stain resistance. The requirements in the 3C field are completely met by extremely low surface tension, extremely high water contact angle, excellent wear resistance and good RCA test; when the glossiness is lower than 4 degrees, the wear-resisting property, the stain resistance and the higher water contact angle are still good.
Drawings
FIG. 1 is a scheme showing the synthesis scheme of intermediate 1 in examples one and three of the present invention;
FIG. 2 is a synthesis scheme of the aqueous urethane acrylate dispersion in the first and third examples of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The first embodiment of the invention is as follows: a preparation method of waterborne polyurethane acrylate comprises the following steps: the method comprises the following steps:
s1, synthesis of fluorine modified organic silicon dihydric alcohol:
adding 300g of double-end epoxy organosilicon with molecular weight of 1570, 600g of perfluoropolyether carboxylic acid with molecular weight of 1096 and 4.5g of catalyst triphenylphosphine into a 1000mL four-neck flask with a stirring device, starting stirring, heating to 110 ℃, preserving heat for 4 hours, reducing the temperature after the acid value is reduced to 5mgKOH/g, discharging for later use to obtain fluorine modified organosilicon diol (intermediate 1), carrying out a hydroxyl value test on the intermediate, wherein the hydroxyl value is 37mgKOH/g, and a synthetic scheme is shown in figure 1;
the structure of the obtained intermediate 1 is shown as the following formula:
s2, synthesis of aqueous polyurethane acrylate dispersion:
100g of fluorine-modified organosilicon diol (intermediate 1) and 10g of hydrophilic monomer DMPA are put into a 1000mL reaction kettle with a stirring and vacuumizing device, the temperature is raised to 100 ℃, water is pumped for 2h, and the temperature is reduced to 50 ℃.
40g of IPDI and 1g of catalyst T-12 are added into a reaction kettle, nitrogen is introduced for protection, the temperature is raised to 80 ℃, and the temperature is kept for 4h until the NCO percent is not changed.
Adding 280G of high hydroxyl value dipentaerythritol pentaacrylate (national chemical, GM66G0A) and 0.5G of polymerization inhibitor MQ into a reaction kettle, preserving the temperature at 80 ℃ until the NCO percent is less than or equal to 0.1 percent, cooling to 50 ℃, adding 7.5G of neutralizing agent triethylamine, and neutralizing for 10min to obtain the waterborne polyurethane acrylic acid; then 430g of deionized water is added for dispersion to obtain the aqueous polyurethane acrylate dispersion, and the synthetic route is shown in figure 2.
The structure of the obtained waterborne polyurethane acrylate is shown as the following formula:
the second embodiment of the invention is as follows: the water-based paint comprises the following raw materials in parts by weight: example one aqueous urethane acrylate dispersion 100 parts, matte powder (dongtao 1011)5 parts, wetting agent (digao 270)0.5 part, leveling agent (BYK381)0.5 part, thickener (digao 3030)0.5 part, defoaming agent (digao 902W)0.1 part, initiator (basf 500)3 parts, cosolvent (DPM)4 parts, and water 20 parts.
The third embodiment of the invention is as follows: a preparation method of waterborne polyurethane acrylate comprises the following steps: the method comprises the following steps:
s1, synthesis of fluorine modified organic silicon dihydric alcohol:
adding 300g of 1174-molecular-weight double-end epoxy organosilicon, 600g of 646-molecular-weight perfluoropolyether carboxylic acid and 4.5g of catalyst triphenylphosphine into a 1000mL four-neck flask with a stirring device, starting stirring, heating to 110 ℃, keeping the temperature for 4 hours, reducing the acid value to 5mgKOH/g, cooling and discharging for later use to obtain fluorine-modified organosilicon diol (intermediate 1), carrying out a hydroxyl value test on the intermediate, wherein the hydroxyl value is 37mgKOH/g, and a synthesis scheme is shown in figure 1;
the structure of the obtained intermediate 1 is shown as the following formula:
s2, synthesis of the aqueous polyurethane acrylate dispersion:
adding 120g of fluorine-modified organic silicon dihydric alcohol (intermediate 1) and 12g of hydrophilic monomer DMPA into 1000mL of a reaction kettle with a stirring and vacuumizing device, heating to 100 ℃, pumping water for 2h, and cooling to 50 ℃.
43g of IPDI and 1g of catalyst T-12 are added into a reaction kettle, nitrogen is introduced for protection, the temperature is raised to 80 ℃, and the temperature is kept for 4h until NCO% is not changed.
Adding 100G of high hydroxyl value pentaerythritol triacrylate (GM 66G00) and 0.4G of polymerization inhibitor MQ into a reaction kettle, keeping the temperature at 80 ℃ until the NCO% is less than or equal to 0.1%, cooling to 50 ℃, adding a neutralizing agent triethylamine, and neutralizing for 10min to obtain waterborne polyurethane acrylic acid; 275g of deionized water is added for dispersion to obtain the aqueous polyurethane acrylate dispersion, the solid content is 50%, and the synthetic route is shown in figure 2.
The structure of the obtained waterborne polyurethane acrylate is shown as the following formula:
the fourth embodiment of the invention is as follows: the water-based paint comprises the following raw materials in parts by weight: 100 parts of the aqueous polyurethane acrylate dispersion prepared in example three, 5 parts of matte powder (Tosoh 1011), 0.5 part of wetting agent (digao 270), 0.5 part of leveling agent (BYK381), 0.5 part of thickener (digao 3030), 0.1 part of defoamer (digao 902W), 3 parts of initiator (basf 500), 4 parts of cosolvent (DPM) and 20 parts of water.
The fifth embodiment of the invention is as follows: a preparation method of waterborne polyurethane acrylate comprises the following steps: the method comprises the following steps:
s1, synthesis of fluorine modified organic silicon dihydric alcohol:
adding 300g of double-end epoxy organosilicon with the molecular weight of 6718, 600g of perfluoropolyether carboxylic acid with the molecular weight of 3346 and 4.5g of catalyst triphenylphosphine into a 1000mL four-neck flask with a stirring device, starting stirring, heating to 110 ℃, keeping the temperature for 4 hours, reducing the acid value to 5mgKOH/g, cooling and discharging for later use to obtain fluorine modified organosilicon diol (intermediate 1), carrying out a hydroxyl value test on the intermediate, wherein the hydroxyl value is 37mgKOH/g, and a synthetic scheme is shown in figure 1;
the structure of the obtained intermediate 1 is shown as the following formula:
s2, synthesis of aqueous polyurethane acrylate dispersion:
adding 120g of fluorine-modified organic silicon dihydric alcohol (intermediate 1) and 12g of hydrophilic monomer DMPA into 1000mL of a reaction kettle with a stirring and vacuumizing device, heating to 100 ℃, pumping water for 2h, and cooling to 50 ℃.
43g of IPDI and 1g of catalyst T-12 are added into a reaction kettle, nitrogen is introduced for protection, the temperature is raised to 80 ℃, and the temperature is kept for 4h until NCO% is not changed.
Adding 100G of high hydroxyl value pentaerythritol triacrylate (GM 66G00) and 0.4G of polymerization inhibitor MQ into a reaction kettle, preserving the temperature at 80 ℃ until the NCO percent is less than or equal to 0.1 percent, cooling to 50 ℃, adding a neutralizing agent triethylamine, and neutralizing for 10min to obtain aqueous polyurethane acrylic acid; and 275g of deionized water is added for dispersion to obtain the aqueous polyurethane acrylate dispersion, wherein the solid content is 50%.
The structure of the obtained waterborne polyurethane acrylate is shown as the following formula:
the sixth embodiment of the invention is as follows: the water-based paint comprises the following raw materials in parts by weight: 100 parts of the aqueous polyurethane acrylate dispersion prepared in example three, 5 parts of matte powder (Tosoh 1011), 0.5 part of wetting agent (digao 270), 0.5 part of leveling agent (BYK381), 0.5 part of thickener (digao 3030), 0.1 part of defoamer (digao 902W), 3 parts of initiator (basf 500), 4 parts of cosolvent (DPM) and 20 parts of water.
The seventh embodiment of the invention is: a preparation method of waterborne polyurethane acrylate comprises the following steps: the method comprises the following steps:
s1, synthesis of fluorine modified organic silicon dihydric alcohol:
adding 300g of double-end-group epoxy organosilicon with molecular weight of 2758, 600g of perfluoropolyether carboxylic acid with molecular weight of 2146 and 4.5g of catalyst triphenylphosphine into a 1000mL four-neck flask with a stirring device, starting stirring, heating to 110 ℃, keeping the temperature for 4 hours, reducing the temperature after the acid value is reduced to 5mgKOH/g, discharging for later use to obtain fluorine-modified organosilicon diol (intermediate 1), carrying out a hydroxyl value test on the intermediate, wherein the hydroxyl value is 37mgKOH/g, and a synthetic scheme is shown in a figure 1;
the structure of the obtained intermediate 1 is shown as the following formula:
s2, synthesis of aqueous polyurethane acrylate dispersion:
adding 120g of fluorine-modified organic silicon dihydric alcohol (intermediate 1) and 12g of hydrophilic monomer DMPA into 1000mL of a reaction kettle with a stirring and vacuumizing device, heating to 100 ℃, pumping water for 2h, and cooling to 50 ℃.
43g of IPDI and 1g of catalyst T-12 are added into a reaction kettle, nitrogen is introduced for protection, the temperature is raised to 80 ℃, and the temperature is kept for 4h until NCO% is not changed.
Adding 100G of high hydroxyl value pentaerythritol triacrylate (GM 66G00) and 0.4G of polymerization inhibitor MQ into a reaction kettle, preserving the temperature at 80 ℃ until the NCO percent is less than or equal to 0.1 percent, cooling to 50 ℃, adding a neutralizing agent triethylamine, and neutralizing for 10min to obtain aqueous polyurethane acrylic acid; and 275g of deionized water is added for dispersion to obtain the aqueous polyurethane acrylate dispersion, wherein the solid content is 50%.
The structure of the obtained waterborne polyurethane acrylate is shown as the following formula:
the eighth embodiment of the present invention is: the water-based paint comprises the following raw materials in parts by weight: 100 parts of the aqueous polyurethane acrylate dispersion prepared in example three, 5 parts of matte powder (Tosoh 1011), 0.5 part of wetting agent (digao 270), 0.5 part of leveling agent (BYK381), 0.5 part of thickener (digao 3030), 0.1 part of defoamer (digao 902W), 3 parts of initiator (basf 500), 4 parts of cosolvent (DPM) and 20 parts of water.
The first comparative example of the present invention is: a preparation method of waterborne polyurethane acrylate comprises the following steps: the method comprises the following steps:
s1, putting 100g of polyester diol (molecular weight is 3000) and 10g of hydrophilic monomer DMPA into 1000mL of reaction kettle with a stirring and vacuumizing device, heating to 100 ℃, pumping water for 2h, and cooling to 50 ℃.
S2, adding 40g of IPDI and 1g of catalyst T-12 into the reaction kettle, introducing nitrogen for protection, heating to 80 ℃, and keeping the temperature for 4h until the NCO% is not changed.
S3, adding 280G of high hydroxyl pentaerythritol triacrylate (Guojinghua, GM66G00) and 0.5G of polymerization inhibitor MQ into a reaction kettle, preserving the temperature at 80 ℃ until the NCO percent is less than or equal to 0.1 percent, cooling to 50 ℃, adding triethylamine serving as a neutralizing agent, neutralizing for 10min, and adding 430G of deionized water for dispersion to obtain the aqueous photocuring polyurethane acrylate dispersion with the solid content of 50 percent.
The second comparative example of the present invention is: the water-based paint comprises the following raw materials in parts by weight: example one aqueous urethane acrylate dispersion 100 parts, matte powder (dongtao 1011)5 parts, wetting agent (digao 270)0.5 part, leveling agent (BYK381)0.5 part, thickener (digao 3030)0.5 part, defoaming agent (digao 902W)0.1 part, initiator (basf 500)3 parts, cosolvent (DPM)4 parts, and water 20 parts.
The performance test method of the coating comprises the following steps: the glossiness test adopts a 60-degree glossiness instrument;
and (3) testing the water boiling performance: and (4) performing a boiling test at 85 ℃, taking out after boiling for a period of time, cooling to room temperature at normal temperature, and performing an adhesion test after checking the appearance (the adhesion test is qualified if being superior to 4B).
RCA value test standard reference: ASTM F2357-04, test load 175 g;
the water contact angle test uses a contact angle meter.
The results of the performance tests on the water-based paint prepared in the second, fourth and second inventive examples are shown in Table 1.
TABLE 1 results of performance tests on aqueous coating materials prepared in example two, example four and comparative example two of the present invention
As is apparent from table 1, examples two and four of the present invention provide a smooth feel and a fleshy feel by introducing silicone on the molecular main chain, while introducing organic fluorine on the side chain, thereby allowing the resin to have excellent stain resistance and extremely low surface tension and extremely high water contact angle. Organic fluorine is introduced into a molecular side chain, so that fluorine atoms have good freedom and can freely swing, and the resin has excellent performance. Through the structural design, the resin not only utilizes the smoothness and hand feeling of the organic silicon, but also utilizes the low surface tension and extremely high water contact angle of the organic fluorine. The modified organic fluorine is adopted, so that fluorine atoms are distributed on side chains, and the modified organic fluorine has better degree of freedom and can provide good performances of wear resistance, stain resistance, low surface tension and the like.
In conclusion, the waterborne coating provided by the invention has the advantages that the performance of the waterborne coating is improved by crosslinking the waterborne polyurethane acrylate synthesized by organic fluorine-modified organosilicon with the whole paint film; during crosslinking, the fluorine-containing segment on the acrylic branch of the aqueous polyurethane migrates to the surface of the paint film, thereby providing stain resistance and low surface tension, and such properties are durable for a long period of time. Meanwhile, the organic silicon chain segment of the main chain of the waterborne polyurethane acrylic acid is also crosslinked in the paint film, thereby providing lasting smooth and thick feeling. Under the dual synergistic effect of the organic fluorine chain segment and the organic silicon chain segment, the paint film has lasting smooth feeling, thick feeling, low surface tension and stain resistance. The requirements of the 3C field are completely met by extremely low surface tension, extremely high water contact angle, excellent wear resistance and good RCA test; when the glossiness is lower than 4 degrees, the wear-resisting property, the stain resistance and the higher water contact angle are still good.
While the embodiments of the present invention have been described in detail with reference to the drawings and the description, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict. The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (24)
1. An aqueous urethane acrylate characterized by: the method comprises the following raw materials: the structure of the aqueous polyurethane acrylate is shown as the following formula:
the structure of the fluorine-silicon modified dihydric alcohol is shown as the following formula:
wherein the value range of m is 2-20;
the value range of n is 8-50.
2. The aqueous urethane acrylate according to claim 1, wherein: the auxiliary agent I comprises a hydrophilic monomer, a catalyst, a polymerization inhibitor, isocyanate, a neutralizer and a crosslinking agent.
3. The aqueous urethane acrylate according to claim 2, wherein: the composite material comprises the following raw materials in parts by weight: 100 to 120 portions of fluorine-silicon modified dihydric alcohol, 10 to 12 portions of hydrophilic monomer, 1 to 1.2 portions of catalyst, 0.4 to 0.5 portion of polymerization inhibitor, 40 to 43 portions of isocyanate, 7 to 9 portions of neutralizer and 100 to 280 portions of cross-linking agent.
4. The aqueous urethane acrylate according to any one of claims 1 to 3, wherein: the fluorine-silicon modified dihydric alcohol is prepared from the following raw materials: a double-ended epoxy silicone, a perfluoropolyether carboxylic acid, and a phosphine catalyst.
5. The aqueous urethane acrylate according to claim 4, wherein: the mass ratio of the double-end-group epoxy organosilicon to the perfluoropolyether carboxylic acid to the phosphine catalyst is 70-80: 140-160: 1-3.
6. The aqueous urethane acrylate according to claim 4, wherein: the relative molecular mass of the double-end epoxy organosilicon is 1000-7000.
7. The aqueous urethane acrylate according to claim 4, wherein: the relative molecular mass of the perfluoropolyether carboxylic acid is 600-4000.
8. The aqueous urethane acrylate according to claim 4, wherein: the phosphine catalyst is triphenylphosphine.
9. The aqueous urethane acrylate according to claim 2 or 3, wherein: the hydrophilic monomer is 2, 2-dimethylolpropionic acid.
10. The aqueous urethane acrylate according to claim 2 or 3, wherein: the catalyst is an organic tin drier.
11. The aqueous urethane acrylate according to claim 10, wherein: the organotin drier is T-12.
12. The aqueous urethane acrylate according to claim 2 or 3, wherein: the polymerization inhibitor is hydroquinone monomethyl ether.
13. The aqueous urethane acrylate according to claim 2 or 3, wherein: the isocyanate is at least one of isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate.
14. The aqueous urethane acrylate according to claim 13, wherein: the isocyanate is isophorone diisocyanate.
15. The aqueous urethane acrylate according to claim 2 or 3, wherein: the neutralizing agent is organic amine.
16. The aqueous urethane acrylate according to claim 15, wherein: the organic amine is at least one of triethylamine and triethanolamine.
17. The aqueous urethane acrylate according to claim 2 or 3, wherein: the cross-linking agent is pentaerythritol triacrylate with high hydroxyl value.
18. The aqueous urethane acrylate according to claim 17, wherein: the hydroxyl value of the high hydroxyl value pentaerythritol triacrylate is 35mg KOH/g to 70mg KOH/g.
19. A method for preparing the aqueous urethane acrylate according to any one of claims 1 to 18, characterized in that: the method comprises the following steps:
s1, mixing the fluorine-silicon modified dihydric alcohol and the hydrophilic monomer, heating for reaction, and cooling to obtain a precursor;
s2, heating and reacting the precursor, the catalyst and isocyanate to obtain an intermediate;
and S3, mixing the intermediate, the cross-linking agent and the polymerization inhibitor for reaction, and adding a neutralizing agent to obtain the waterborne polyurethane acrylate.
20. The method of claim 19, wherein: further comprising the steps of: and mixing and reacting the double-end-group epoxy organic silicon, the perfluoropolyether carboxylic acid and the phosphine catalyst until the acid value is 5mg KOH/g, and cooling to obtain the fluorine-silicon modified dihydric alcohol.
21. The method of claim 19, wherein: the heating temperature in the step S1 is 100-110 ℃; the temperature of the temperature reduction in the step S1 is 50-55 ℃.
22. The method of claim 19, wherein: the heating temperature in the step S2 is 75-85 ℃.
23. The method of claim 19, wherein: the temperature of the mixing reaction in the step S3 is 75-85 ℃; the neutralization time is 10 min; the temperature of neutralization is 50-55 ℃.
24. Use of the aqueous polyurethane acrylate according to any one of claims 1 to 18 for the preparation of an aqueous coating.
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