CN106905504B - Water-based ultraviolet-curing polyurethane resin and preparation method and application thereof - Google Patents
Water-based ultraviolet-curing polyurethane resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a water-based ultraviolet curing polyurethane resin and a preparation method and application thereof. The water-based ultraviolet curing polyurethane resin comprises the following raw material components in parts by weight: 25-40 parts of diisocyanate, 1-5 parts of castor oil, 20-30 parts of polyol, 5-10 parts of epoxy acrylate, 5-10 parts of 2, 2-dimethylolpropionic acid, 10-15 parts of pentaerythritol triacrylate, 1-5 parts of 1, 4-butanediol, 0.0057-0.006 part of catalyst, 0.002-0.005 part of polymerization inhibitor and 0.004-0.005 part of blocking agent. The water-based ultraviolet curing polyurethane resin disclosed by the invention has the advantages of high photocuring speed, high production efficiency, high gloss and hardness after film curing, good adhesive force and flexibility and the like, and is excellent in comprehensive performance by adopting the specific monomer as a raw material component.
Description
Technical Field
The invention relates to a high polymer material, in particular to a water-based ultraviolet curing polyurethane resin and a preparation method and application thereof.
Background
In recent years, with global attention on environmental protection and development of green chemical engineering technology, each country starts to limit the content of VOC, and the aqueous ultraviolet-curable polyurethane resin (aqueous UV polyurethane resin) uses water instead of an organic solvent as a dispersion medium, has an obvious environmental protection value, and has the advantages of high curing speed, capability of operating at room temperature, low energy consumption, excellent coating performance and the like by adopting an ultraviolet curing technology. The water-based UV polyurethane resin can be applied to the aspects of coatings, adhesives, water-based leather finishing agents, fabric finishing agents and the like, and is increasingly paid more attention by people.
However, the existing aqueous ultraviolet light curing polyurethane resin is difficult to combine excellent mechanical properties and good water resistance and solvent resistance, and has the defects of low crosslinking density, slow light curing rate and the like. In addition, if the aqueous ultraviolet curing polyurethane resin is simply applied, the defects of poor weather resistance and heat resistance, low bonding strength and the like exist, so that the popularization and application of the aqueous ultraviolet curing polyurethane resin are limited.
Disclosure of Invention
Based on the above, there is a need for an aqueous ultraviolet-curable polyurethane resin which has high solid content, high photocuring rate, and excellent overall properties such as gloss, hardness, adhesion, flexibility, water resistance, solvent resistance and the like after a coating film is cured.
The water-based ultraviolet curing polyurethane resin comprises the following raw material components in parts by weight:
according to the water-based ultraviolet-curing polyurethane resin, the specific monomer is adopted as the raw material component, so that the prepared resin has the advantages of high solid content, high photocuring speed, high production efficiency, high gloss and hardness after film coating, good adhesive force, good flexibility and the like. The principle is as follows:
firstly, the invention comprehensively adopts epoxy acrylate and castor oil to modify the waterborne polyurethane resin. The epoxy acrylate has the advantages of high epoxy resin modulus, high strength, good chemical resistance, good thermal stability and the like, and has the characteristics of good water resistance, physical properties, weather resistance and low cost. Castor oil is a renewable vegetable oil and has rich sources. The castor oil mainly comprises triglyceride of higher fatty acid, wherein 80-90% of fatty acid is ricinoleic acid (9-alkenyl-12-hydroxyoctadecanoic acid), the hydroxyl value of the castor oil is 163mgKOH/g, the hydroxyl content is 4.94%, and the mole number of the hydroxyl is 345. Calculated according to the hydroxyl value, the castor oil contains 70% of trifunctional and 30% of difunctional, the average functionality of hydroxyl is 2.7, and the specific structure of the castor oil can be used as a soft segment in the synthesis of polyurethane resin, so that the flexibility is increased, the castor oil can also play a role of a cross-linking agent, the cross-linking degree of the polyurethane resin is improved, and the water resistance, the solvent resistance, the mechanical property and the like of a paint film are improved. In addition, the branched chain of the castor oil also contains a large amount of unsaturated carbon-carbon double bonds, which can provide active points for further grafting modification of the castor oil and further improve the performance of the coating.
Secondly, introducing 2, 2-dimethylolpropionic acid on the basis of the polyurethane resin to prepare a carboxyl-containing polyurethane prepolymer, and then introducing pentaerythritol triacrylate into a terminal group to prepare the multiple double-bond terminated waterborne polyurethane acrylate, thereby greatly improving the double-bond content in the system and ensuring the photocuring speed and the production efficiency of the resin. Meanwhile, the resin has higher solid content, the time of complex processes such as hot drying or infrared drying after resin coating can be reduced, and the production efficiency is improved.
In one embodiment, the aqueous ultraviolet curing polyurethane resin comprises the following raw material components in parts by weight:
in one embodiment, the molecular weight of the polyol is 500-1500 g/mol.
In one embodiment, the polyol is one or more of polyether diol, polytetrahydrofuran ether diol, polycaprolactone diol, and polycarbonate diol.
In one embodiment, the diisocyanate is one or more of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, and 1, 6-hexamethylene diisocyanate.
In one embodiment, the epoxy acrylate has a molecular weight of 450-460 g/mol and a solid content of 100%.
In one embodiment, the polymerization inhibitor is one or more of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl, 2,6, 6-tetramethylpiperidine-1-oxyl and hydroquinone; the end-capping reagent is a monohydric alcohol. Methanol and/or absolute ethanol are preferred.
In one embodiment, the paint also comprises 4-5 parts by weight of tertiary amine, preferably triethylamine or triethanolamine, and 6-8 parts by weight of water. And tertiary amine and water are further added into the resin, so that salt-forming emulsification can be performed, and the storage stability of the resin can be improved.
The invention also provides a preparation method of the water-based ultraviolet curing polyurethane resin, which comprises the following steps:
(1) preparation of carboxyl-containing polyurethane prepolymer:
adding castor oil and a part of catalyst into the diisocyanate, and reacting for 1.5-2 h at 45-55 ℃;
then adding the polyol dissolved with the rest of the catalyst into the reaction solution, heating to 75-80 ℃ and reacting for 2-2.5 h;
then cooling to 40-50 ℃, adding the 1, 4-butanediol and the epoxy acrylate into the reaction solution, and then heating to 70-75 ℃ for reaction for 1-1.5;
then cooling to 40-50 ℃, adding the 2-dimethylolpropionic acid into the reaction liquid, and then heating to 70-75 ℃ to react for 2-2.5 h to obtain the carboxyl-containing polyurethane prepolymer;
(2) preparation of aqueous ultraviolet light curing polyurethane resin:
cooling the carboxyl-containing polyurethane prepolymer to 40-50 ℃, adding pentaerythritol triacrylate dissolved with the polymerization inhibitor into the reaction liquid, heating to 60-70 ℃, and reacting for 2-3 hours;
and then adding the end-capping reagent, and terminating the reaction when the NCO content is less than 0.2 wt%, thereby obtaining the aqueous ultraviolet curing polyurethane resin.
In one embodiment, in the step (2), after the NCO content is less than 0.2 wt%, the temperature of the reaction mass is reduced to be below 40 ℃, and the tertiary amine and water are added for salt-forming emulsification.
In one embodiment, the salt-forming emulsification method is as follows: stirring for 0.5-1 h at the speed of 1100-1300 r/min, and controlling the pH value to be 6-8.
The invention also provides a waterborne polyurethane coating which comprises the following components in percentage by weight:
compared with the prior art, the invention has the following beneficial effects:
1. the water-based ultraviolet curing polyurethane resin disclosed by the invention has the advantages of high photocuring speed, high production efficiency, high gloss and hardness after film curing, good adhesive force and flexibility and the like, and is excellent in comprehensive performance by adopting the specific monomer as a raw material component.
2. The aqueous ultraviolet curing polyurethane resin has higher solid content, can reduce the time of complex processes such as heat drying or infrared drying and the like after resin coating, and improves the production efficiency.
3. The preparation method of the water-based ultraviolet curing polyurethane resin has simple process and easy operation, does not need to add a large amount of organic solvent in the process, and has good significance for environmental protection.
Detailed Description
The following describes the aqueous uv curable polyurethane resin of the present invention, its preparation method and application in further detail with reference to specific examples.
Example 1
The embodiment of the invention relates to a water-based ultraviolet curing polyurethane resin, which comprises the following raw materials in part by weight:
1) under the protection of nitrogen, 28 parts of toluene diisocyanate is placed in a four-neck flask provided with a mechanical stirrer, a dropping funnel and a reflux condenser tube, the temperature is increased to 30-40 ℃,2 parts of castor oil and 0.0004 part of dibutyltin dilaurate are dripped, and the reaction is carried out for 1.5-2 h at the temperature of 50 +/-2 ℃ after the dripping is finished.
2) Dripping 28 parts of polycarbonate dihydric alcohol (with the molecular weight of 1000g/mol) dissolved with 0.0056 part of dibutyltin dilaurate at the temperature of 50-55 ℃, finishing dripping within 1h, heating to 75-80 ℃ after finishing dripping, and reacting for 2-2.5 h;
3) and (3) cooling to 40-50 ℃, dropwise adding 3 parts of 1, 4-butanediol and 6 parts of epoxy acrylate dissolved with a small amount of acetone, and finishing dropwise adding within 1 hour. Raising the temperature to 70-75 ℃ and reacting for 1-1.5 h.
4) Cooling to 40-50 ℃, dissolving 7 parts of 2, 2-dimethylolpropionic acid (DMPA) in a small amount of N-methylpyrrolidone, directly adding the mixture into a reaction kettle at one time, raising the temperature to 70-75 ℃ for reaction for 2-2.5 hours, and adding a small amount of acetone in the reaction process to control the viscosity of a reaction system to obtain the carboxyl-containing polyurethane prepolymer.
5) Cooling to 40-50 ℃, dropwise adding 14 parts of pentaerythritol triacrylate (PETA) dissolved with a polymerization inhibitor (4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical, 0.004 parts) into the prepolymer in the step 4) while stirring, and dropwise adding within 1 hour; after the dripping is finished, heating to 60-70 ℃, reacting for 2-3 h, adding 0.0045 parts of micromolecule monohydric alcohol (methanol) for end capping reaction for 0.5-1 h, then measuring the content of isocyanic acid radical (by a di-n-butylamine method), and stopping the reaction when the-NCO content is less than 0.2 wt.% to obtain the castor oil capped with unsaturated acrylate and the prepolymer of epoxy polyurethane modified polyurethane acrylate.
6) Cooling to below 40 ℃, adding 5 parts of triethylamine and 7 parts of deionized water into the prepolymer in the step 5) for salt forming emulsification, reacting for 1h at the speed of 1200r/min to obtain the castor oil and epoxy polyurethane modified waterborne UV resin, wherein the pH value is controlled to be about 7.0, and the solid content is 83%.
In the above steps, all the components need to be strictly dewatered.
Example 2
The embodiment of the invention relates to a water-based ultraviolet curing polyurethane resin, which comprises the following raw materials in part by weight:
1) under the protection of nitrogen, 36 parts of dicyclohexylmethane diisocyanate are placed in a four-neck flask provided with a mechanical stirrer, a dropping funnel and a reflux condenser tube, the temperature is increased to 30-40 ℃, 1 part of castor oil and 0.0002 part of dibutyltin dilaurate are dripped, and the reaction is carried out for 1.5-2 hours at the temperature of 50 +/-2 ℃ after the dripping is finished.
2) At the temperature of 50-55 ℃, dripping 23 parts of polyether glycol (with the molecular weight of 1000g/mol) dissolved with 0.0057 part of dibutyltin dilaurate into the solution, finishing dripping within 1 hour, heating to 75-80 ℃ after finishing dripping, and reacting for 2-2.5 hours.
3) And (3) cooling to 40-50 ℃, dropwise adding 3 parts of 1, 4-butanediol and 5 parts of epoxy acrylate dissolved with a small amount of acetone, and finishing dropwise adding within 1 hour. Raising the temperature to 70-75 ℃ and reacting for 1-1.5 h.
4) Cooling to 40-50 ℃, dissolving 6 parts of 2, 2-dimethylolpropionic acid (DMPA) in a small amount of N-methylpyrrolidone, directly adding the mixture into a reaction kettle at one time, raising the temperature to 70-75 ℃ for reaction for 2-2.5 hours, and adding a small amount of acetone in the reaction process to control the viscosity of a reaction system to obtain the carboxyl-containing polyurethane prepolymer.
5) Cooling to 40-50 ℃, dropwise adding 12 parts of pentaerythritol triacrylate (PETA) dissolved with a polymerization inhibitor (2,2,6, 6-tetramethylpiperidine-1-oxygen radical, 0.003 part) into the prepolymer while stirring, and dropwise adding within 1 hour; after the dripping is finished, heating to 60-70 ℃, reacting for 2-3 h, adding 0.0045 parts of micromolecule monohydric alcohol (absolute ethyl alcohol) for end capping reaction for 0.5-1 h, then measuring the content of isocyanate (by a di-n-butylamine method), and stopping the reaction when the-NCO content is less than 0.2 wt.% to obtain the castor oil capped with unsaturated acrylate and the epoxy polyurethane modified polyurethane acrylate prepolymer.
6) And (2) cooling to below 40 ℃, adding 4 parts of triethylamine and 9 parts of deionized water into the prepolymer for salt forming emulsification, stirring and reacting at the speed of 1100r/min for 1h to obtain the castor oil and epoxy polyurethane modified waterborne UV resin, wherein the pH value is controlled to be about 7.0, and the solid content is 84%.
In the above steps, all the components need to be strictly dewatered.
Example 3
The embodiment of the invention relates to a water-based ultraviolet curing polyurethane resin, which comprises the following raw materials in part by weight:
1) under the protection of nitrogen, 28 parts of toluene diisocyanate is placed in a four-neck flask provided with a mechanical stirrer, a dropping funnel and a reflux condenser tube, the temperature is increased to 30-40 ℃,2 parts of castor oil and 0.0004 part of dibutyltin dilaurate are dripped, and the reaction is carried out for 1.5-2 h at the temperature of 50 +/-2 ℃ after the dripping is finished.
2) Dripping 28 parts of polytetrahydrofuran dihydric alcohol (with the molecular weight of 1000g/mol) dissolved with 0.0054 part of dibutyltin dilaurate at the temperature of 50-55 ℃, finishing dripping within 1h, heating to 75-80 ℃ after finishing dripping, and reacting for 2-2.5 h;
3) and (3) cooling to 40-50 ℃, dropwise adding 3 parts of 1, 4-butanediol and 6 parts of epoxy acrylate dissolved with a small amount of acetone, and finishing dropwise adding within 1 hour. Raising the temperature to 70-75 ℃ and reacting for 1-1.5 h.
4) Cooling to 40-50 ℃, dissolving 7 parts of 2, 2-dimethylolpropionic acid (DMPA) in a small amount of N-methylpyrrolidone, directly adding the mixture into a reaction kettle at one time, raising the temperature to 70-75 ℃ for reaction for 2-2.5 hours, and adding a small amount of acetone in the reaction process to control the viscosity of a reaction system to obtain the carboxyl-containing polyurethane prepolymer.
5) Cooling to 40-50 ℃, dropwise adding 14 parts of pentaerythritol triacrylate (PETA) dissolved with a polymerization inhibitor (4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical, 0.005 part) into the prepolymer while stirring, and dropwise adding within 1 hour; after the dripping is finished, heating to 60-70 ℃, reacting for 2-3 h, adding 0.004 parts of micromolecule monohydric alcohol (methanol) to carry out end capping reaction for 0.5-1 h, then measuring the content of the isocyanic acid radical (by using a di-n-butylamine method), and stopping the reaction when the-NCO content is less than 0.2 wt.% to obtain the castor oil and the epoxy polyurethane modified polyurethane acrylate prepolymer of the unsaturated acrylate end capping.
6) And (2) cooling to below 40 ℃, adding 5 parts of triethylamine and 7 parts of deionized water into the prepolymer for salt forming emulsification, stirring and reacting at the speed of 1300r/min for 1h to obtain the castor oil and epoxy polyurethane modified waterborne UV resin, wherein the pH value is controlled to be about 7.0, and the solid content is 82%.
In the above steps, all the components need to be strictly dewatered.
Example 4
The embodiment of the invention relates to a water-based ultraviolet curing polyurethane resin, which comprises the following raw materials in part by weight:
1) under the protection of nitrogen, 33 parts of isophorone diisocyanate is placed in a four-neck flask provided with a mechanical stirrer, a dropping funnel and a reflux condenser tube, the temperature is increased to 30-40 ℃,2 parts of castor oil and 0.0004 part of dibutyltin dilaurate are dripped, and the reaction is carried out for 1.5-2 hours at 50 +/-2 ℃ after the dripping is finished.
2) At the temperature of 50-55 ℃, dropwise adding 25 parts of polycaprolactone diol (with the molecular weight of 1000g/mol) dissolved with 0.0055 part of dibutyltin dilaurate, within 1h, heating to 75-80 ℃ after dropwise adding, and reacting for 2-2.5 h.
3) And (3) cooling to 40-50 ℃, dropwise adding 3 parts of 1, 4-butanediol and 5 parts of epoxy acrylate dissolved with a small amount of acetone, and finishing dropwise adding within 1 hour. Raising the temperature to 70-75 ℃ and reacting for 1-1.5 h.
4) Cooling to 40-50 ℃, dissolving 6 parts of 2, 2-dimethylolpropionic acid (DMPA) in a small amount of N-methylpyrrolidone, directly adding the mixture into a reaction kettle at one time, raising the temperature to 70-75 ℃ for reaction for 2-2.5 hours, and adding a small amount of acetone in the reaction process to control the viscosity of a reaction system to obtain the carboxyl-containing polyurethane prepolymer.
5) Cooling to 40-50 ℃, dropwise adding 13 parts of pentaerythritol triacrylate (PETA) dissolved with a polymerization inhibitor (hydroquinone, 0.002 part) into the prepolymer while stirring, and dropwise adding within 1 hour; after the dripping is finished, heating to 60-70 ℃, reacting for 2-3 h, adding 0.005 part of small molecular monohydric alcohol (absolute ethyl alcohol) to carry out end capping reaction for 0.5-1 h, then measuring the content of the isocyanic acid radical (by using a di-n-butylamine method), and stopping the reaction when the-NCO content is less than 0.2 wt.% to obtain the unsaturated acrylate end capped castor oil and the epoxy polyurethane modified polyurethane acrylate prepolymer.
6) And (2) cooling to below 40 ℃, adding 6 parts of triethylamine and 6 parts of deionized water into the prepolymer for salt forming emulsification, stirring at the speed of 1100r/min for 1h for reaction to obtain the castor oil and epoxy polyurethane modified waterborne UV resin, wherein the pH value is controlled to be about 7.0, and the solid content is 83%.
In the above steps, all the components need to be strictly dewatered.
Example 5
The embodiment of the invention relates to a water-based ultraviolet curing polyurethane resin, which comprises the following raw materials in part by weight:
1) under the protection of nitrogen, 27 parts of 1, 6-hexamethylene diisocyanate are placed in a four-neck flask provided with a mechanical stirrer, a dropping funnel and a reflux condenser tube, the temperature is increased to 30-40 ℃,2 parts of castor oil and 0.0004 part of dibutyltin dilaurate are dripped, and the reaction is carried out for 1.5-2 hours at 50 +/-2 ℃ after the dripping is finished.
2) At the temperature of 50-55 ℃, 28 parts of polyether glycol (with the molecular weight of 1000g/mol) dissolved with 0.0053 part of dibutyltin dilaurate is dripped, the dripping is finished within 1 hour, the temperature is raised to 75-80 ℃ after the dripping is finished, and the reaction is carried out for 2-2.5 hours.
3) And (3) cooling to 40-50 ℃, dropwise adding 3 parts of 1, 4-butanediol and 6 parts of epoxy acrylate dissolved with a small amount of acetone, and finishing dropwise adding within 1 hour. Raising the temperature to 70-75 ℃ and reacting for 1-1.5 h.
4) Cooling to 40-50 ℃, dissolving 7 parts of 2, 2-dimethylolpropionic acid (DMPA) in a small amount of N-methylpyrrolidone, directly adding the mixture into a reaction kettle at one time, raising the temperature to 70-75 ℃ for reaction for 2-2.5 hours, and adding a small amount of acetone in the reaction process to control the viscosity of a reaction system to obtain the carboxyl-containing polyurethane prepolymer.
5) Cooling to 40-50 ℃, dropwise adding 15 parts of pentaerythritol triacrylate (PETA) dissolved with a polymerization inhibitor (4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxygen radical, 0.004 parts) into the prepolymer while stirring, and dropwise adding within 1 hour; after the dripping is finished, heating to 60-70 ℃, reacting for 2-3 h, adding 0.0045 parts of micromolecule monohydric alcohol (absolute ethyl alcohol) for end capping reaction for 0.5-1 h, then measuring the content of isocyanate (by a di-n-butylamine method), and stopping the reaction when the-NCO content is less than 0.2 wt.% to obtain the castor oil capped with unsaturated acrylate and the epoxy polyurethane modified polyurethane acrylate prepolymer.
6) And (2) cooling to below 40 ℃, adding 5 parts of triethylamine and 7 parts of deionized water into the prepolymer for salt forming emulsification, stirring and reacting at the speed of 1200r/min for 1h to obtain the castor oil and epoxy polyurethane modified waterborne UV resin, wherein the pH value is controlled to be about 7.0, and the solid content is 85%.
In the above steps, all the components need to be strictly dewatered.
Example 6
The embodiment of the invention relates to a water-based ultraviolet curing polyurethane resin, which comprises the following raw materials in part by weight:
1) under the protection of nitrogen, 33 parts of isophorone diisocyanate is placed in a four-neck flask provided with a mechanical stirrer, a dropping funnel and a reflux condenser tube, the temperature is increased to 30-40 ℃,2 parts of castor oil and 0.0004 part of dibutyltin dilaurate are dripped, and the reaction is carried out for 1.5-2 hours at 50 +/-2 ℃ after the dripping is finished.
2) At the temperature of 50-55 ℃, 25 parts of polyether glycol (with the molecular weight of 1000g/mol) with 0.0055 part of dibutyltin dilaurate is dropwise added, the dropwise addition is completed within 1 hour, the temperature is raised to 75-80 ℃ after the dropwise addition is completed, and the reaction is carried out for 2-2.5 hours.
3) And (3) cooling to 40-50 ℃, dropwise adding 3 parts of 1, 4-butanediol and 5 parts of epoxy acrylate dissolved with a small amount of acetone, and finishing dropwise adding within 1 hour. Raising the temperature to 70-75 ℃ and reacting for 1-1.5 h.
4) Cooling to 40-50 ℃, dissolving 6 parts of 2, 2-dimethylolpropionic acid (DMPA) in a small amount of N-methylpyrrolidone, directly adding the mixture into a reaction kettle at one time, raising the temperature to 70-75 ℃ for reaction for 2-2.5 hours, and adding a small amount of acetone in the reaction process to control the viscosity of a reaction system to obtain the carboxyl-containing polyurethane prepolymer.
5) Cooling to 40-50 ℃, dropwise adding 13 parts of pentaerythritol triacrylate (PETA) dissolved with a polymerization inhibitor (hydroquinone, 0.004 part) into the prepolymer while stirring, and dropwise adding within 1 hour; after the dripping is finished, heating to 60-70 ℃, reacting for 2-3 h, adding, sealing and reacting for 0.5-1 h by 0.0045 parts of small molecular monohydric alcohol (absolute ethyl alcohol), then measuring the content of isocyanic acid radical (by a di-n-butylamine method), and stopping the reaction when the-NCO content is less than 0.2 wt.% to obtain the castor oil sealed by unsaturated acrylate and the prepolymer of epoxy polyurethane modified polyurethane acrylate.
6) And (2) cooling to below 40 ℃, adding 6 parts of triethanolamine and 6 parts of deionized water into the prepolymer for salt forming emulsification, stirring and reacting at the speed of 1300r/min for 1h to obtain the castor oil and epoxy polyurethane modified waterborne UV resin, wherein the pH value is controlled to be about 7.0, and the solid content is 82%.
In the above steps, all the components need to be strictly dewatered.
Comparative example 1
This comparative example is an aqueous ultraviolet-curable polyurethane resin, which is similar to example 1 in raw materials and preparation method, except that: the epoxy acrylate was not used.
Comparative example 2
This comparative example is an aqueous ultraviolet-curable polyurethane resin, which is similar to example 1 in raw materials and preparation method, except that: the castor oil was not used.
Example 7
The aqueous ultraviolet-curable polyurethane resins prepared in examples 1 to 6 and comparative examples 1 to 2 were prepared into aqueous polyurethane coatings according to the formulations shown in Table 1, respectively.
TABLE 1
| Raw materials | Dosage of |
| Water-based ultraviolet-curable polyurethane resin/g | 10 |
| Pentaerythritol triacrylate/g | 0.05 |
| Phosphate adhesion promoter/g | 0.15 |
| Photoinitiator 1173/g | 0.4 |
| Leveling agent/g | 0.1 |
| Defoaming agent/g | 0.03 |
| Water/g | 3 |
The preparation method of the waterborne polyurethane coating comprises the following steps: accurately weighing the raw materials of the components according to the formula, and stirring and dispersing to obtain the leveling agent and the defoaming agent, wherein the leveling agent and the defoaming agent can be conventional in the field.
The performance of the waterborne polyurethane coating prepared from the waterborne ultraviolet curing polyurethane resin prepared in the examples 1-6 and the comparative examples 1-2 is detected, and the detection method comprises the following steps: coating the waterborne polyurethane coating on tinplate, placing the tinplate in an oven at 80 ℃ for drying for 10min, and curing the tinplate on a photocuring machine (the light intensity of the curing machine is recommended to be 400 mJ/cm)220m/s speed) to obtain a cured paint film; the test results are shown in table 2:
TABLE 2
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The waterborne polyurethane coating is characterized by comprising the following components in parts by weight:
the water-based ultraviolet curing polyurethane resin comprises the following raw material components in parts by weight:
2. the waterborne polyurethane coating of claim 1, wherein the waterborne ultraviolet-curable polyurethane resin comprises the following raw material components in parts by weight:
3. the aqueous polyurethane coating according to claim 1, wherein the polyol has a molecular weight of 500 to 1500 g/mol.
4. The waterborne polyurethane coating of claim 3, wherein the polyol is one or more of polyether diol, polycaprolactone diol, and polycarbonate diol.
5. The aqueous polyurethane coating according to claim 1, wherein the diisocyanate is one or more of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, and 1, 6-hexamethylene diisocyanate.
6. The waterborne polyurethane coating of claim 1, wherein the epoxy acrylate has a molecular weight of 450-460 g/mol and a solid content of 100%.
7. The aqueous polyurethane coating of any one of claims 1-6, wherein the catalyst is dibutyltin dilaurate.
8. The aqueous polyurethane coating according to any one of claims 1 to 6, wherein the polymerization inhibitor is one or more of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl, and hydroquinone; the end-capping reagent is a monohydric alcohol.
9. The waterborne polyurethane coating of any one of claims 1-6, wherein the waterborne UV-curable polyurethane resin further comprises 4-5 parts by weight of a tertiary amine and 6-8 parts by weight of water.
10. The aqueous polyurethane coating according to any one of claims 1 to 6, wherein the preparation method of the aqueous UV-curable polyurethane resin comprises the following steps:
(1) preparation of carboxyl-containing polyurethane prepolymer:
adding castor oil and a part of catalyst into the diisocyanate, and reacting for 1.5-2 h at 45-55 ℃;
then adding the polyol dissolved with the rest of the catalyst into the reaction solution, heating to 75-80 ℃ and reacting for 2-2.5 h;
then cooling to 40-50 ℃, adding the 1, 4-butanediol and the epoxy acrylate into the reaction solution, and then heating to 70-75 ℃ for reaction for 1-1.5 h;
then cooling to 40-50 ℃, adding the 2, 2-dimethylolpropionic acid into the reaction solution, and then heating to 70-75 ℃ to react for 2-2.5 h to obtain the carboxyl-containing polyurethane prepolymer;
(2) preparation of aqueous ultraviolet light curing polyurethane resin:
cooling the carboxyl-containing polyurethane prepolymer to 40-50 ℃, adding pentaerythritol triacrylate dissolved with the polymerization inhibitor into the reaction liquid, heating to 60-70 ℃, and reacting for 2-3 hours;
and then adding the end-capping reagent, and terminating the reaction when the NCO content is less than 0.2 wt%, thereby obtaining the aqueous ultraviolet curing polyurethane resin.
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| CN108456290A (en) * | 2017-12-28 | 2018-08-28 | 滁州金桥德克新材料有限公司 | A kind of dual cure polyurethane acrylate resin and preparation method thereof |
| CN109942781B (en) * | 2019-04-01 | 2020-05-29 | 东北林业大学 | UV-cured castor oil-based aqueous polyurethane dispersion and preparation method and application thereof |
| CN113683741A (en) * | 2021-08-19 | 2021-11-23 | 中山市钧纬新材料科技有限公司 | Water-based UV resin for UV-Monocoat and preparation method thereof |
| CN114015014B (en) * | 2021-12-09 | 2023-05-05 | 南雄市沃太化工有限公司 | Elastic wiredrawing photo-curing resin, preparation method thereof and elastic wiredrawing glue |
| CN114560993B (en) * | 2022-03-15 | 2023-08-15 | 阜阳师范大学 | Preparation method of chalcone-terminated photosensitive waterborne polyurethane/epoxy acrylate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177553A (en) * | 2007-11-30 | 2008-05-14 | 华南理工大学 | Composite ultraviolet solidified aqueous coating and preparation method thereof |
| CN102585693A (en) * | 2012-03-09 | 2012-07-18 | 常熟市协新冶金材料有限公司 | Method for preparing epoxy acrylate modified waterborne polyurethane coating |
-
2017
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177553A (en) * | 2007-11-30 | 2008-05-14 | 华南理工大学 | Composite ultraviolet solidified aqueous coating and preparation method thereof |
| CN102585693A (en) * | 2012-03-09 | 2012-07-18 | 常熟市协新冶金材料有限公司 | Method for preparing epoxy acrylate modified waterborne polyurethane coating |
Non-Patent Citations (1)
| Title |
|---|
| "Preparation and properties of castor oil/pentaerythritol triacrylate-based UV curable waterborne polyurethane acrylate";Kaibin Li etc.;《Progress in Organic Coatings》;20141012;第78卷;第146-154页 * |
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