CN110615885A - Ultraviolet-curable waterborne polyurethane emulsion and preparation method and application thereof - Google Patents
Ultraviolet-curable waterborne polyurethane emulsion 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/348—Hydroxycarboxylic acids
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- C08G18/6633—Compounds of group C08G18/42
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- C08G18/67—Unsaturated compounds having active hydrogen
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The invention belongs to the technical field of new polymer materials, and particularly relates to an ultraviolet-curable aqueous polyurethane emulsion, and a preparation method and application thereof. The invention adopts the polypropylene carbonate dihydric alcohol, the diisocyanate and the reactive monomer as main raw materials, and introduces the ultraviolet curing double bond group, so that the acrylate resin and the polyurethane resin are connected by chemical bonds, and the organic unification of the excellent performances of the two resins is effectively realized. In addition, the raw materials of the ultraviolet-curable waterborne polyurethane emulsion do not need organic solvents, acetone does not need to be used as a solvent in the preparation process to reduce the viscosity of the system, the reactive monomer can reduce the viscosity of the system, the use of the organic solvents is avoided, the discharge problem of VOC is further solved, and the pollution to the environment and the harm to the health are reduced.
Description
Technical Field
The invention belongs to the technical field of new polymer materials, and particularly relates to an ultraviolet-curable aqueous polyurethane emulsion, and a preparation method and application thereof.
Background
The attention on environmental protection is a common trend of social development, and new environment-friendly materials such as ultraviolet light curing polyurethane paint and the like gradually replace the traditional solvent type polyurethane material to enter the market for application and gradually replace the traditional product. In addition, because the ultraviolet light curing polyurethane coating has the characteristics of high efficiency and energy conservation such as quick curing, no need of heating and baking and the like, the ultraviolet light curing polyurethane coating is very suitable for assembly line operation, the market development of the ultraviolet light curing polyurethane coating is gradually increased year by year, the ultraviolet light curing polyurethane coating is more and more applied to the industrial production of commodities, and a new revolution is brought to the whole surface coating industry.
The water-based ultraviolet curing system combines a plurality of advantages of the traditional photocuring coating and the water-based coating, and compared with the traditional solvent type polyurethane material, the water-based ultraviolet curing coating has low VOC content and little smell, and belongs to an environment-friendly material. However, the solid content of the existing water-based polyurethane material on the market is generally about 305-35%, and the water-based system has the defects of low curing speed, poor paint film performance and the like in the use process due to high moisture content. The traditional ultraviolet light curing waterborne polyurethane mainly takes isocyanate and polymer polyol as raw materials, wherein the most commonly used polymer polyol is polyester polyol and polyether polyol. However, ester bonds of polyester-based waterborne polyurethanes are easily hydrolyzed and have poor water resistance; the polyether type waterborne polyurethane has low strength and hardness, is not scratch-resistant and has poor product performance.
Therefore, how to improve the water resistance, corrosion resistance, hardness and scratch resistance of the water-based polyurethane becomes a technical problem to be solved urgently by the technical personnel in the field.
Disclosure of Invention
In view of the above, the invention provides an ultraviolet-curable aqueous polyurethane emulsion, and a preparation method and an application thereof, which are used for improving the water resistance, the corrosion resistance, the hardness and the scratch resistance of aqueous polyurethane.
The specific technical scheme of the invention is as follows:
an ultraviolet-curable aqueous polyurethane emulsion comprises the following raw materials: the preparation method comprises the following steps of (1) poly (propylene carbonate) dihydric alcohol, diisocyanate, hydrophilic functional monomers, a catalyst, a chain extender, reactive monomers, a polymerization inhibitor, a neutralizer and deionized water;
the reactive monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and epoxy modified acrylates.
According to the invention, the polypropylene carbonate dihydric alcohol, the diisocyanate and the reactive monomer are used as main raw materials, and the ultraviolet light curing double bond group is introduced, so that the acrylate resin and the polyurethane resin are connected through a chemical bond, and the organic unification of the excellent performances of the two resins is effectively realized, so that the film cured by the ultraviolet light curing aqueous polyurethane emulsion has better hardness, has good fullness, water resistance, corrosion resistance, wear resistance, scratch resistance and higher mechanical strength, and improves the practical application value of the ultraviolet light curing aqueous polyurethane emulsion. In addition, the raw materials of the ultraviolet-curable waterborne polyurethane emulsion do not need organic solvents, acetone does not need to be used as a solvent in the preparation process to reduce the viscosity of the system, the reactive monomer can reduce the viscosity of the system, the use of the organic solvents is avoided, the discharge problem of VOC is further solved, and the pollution to the environment and the harm to the health are reduced.
Preferably, the raw materials comprise, by mass: 60 parts of polypropylene carbonate dihydric alcohol, 20-40 parts of diisocyanate, 2-10 parts of hydrophilic functional monomer, 0.12-0.36 part of catalyst, 1-10 parts of chain extender, 10-50 parts of reactive monomer, 0.2-0.5 part of polymerization inhibitor, 2-10 parts of neutralizer and 10-30 parts of deionized water.
Preferably, the molecular weight of the polypropylene carbonate dihydric alcohol is 1000-3000;
the hydroxyl functionality of the polypropylene carbonate diol is 2;
the mole fraction of carbonate groups in the molecule of the polypropylene carbonate dihydric alcohol is 0.3-0.4.
According to the invention, the poly (propylene carbonate) polyol is synthesized by taking carbon dioxide as an initial raw material, adding an initiator and carrying out catalytic copolymerization with propylene oxide, has good mechanical properties and low cost, can relieve the greenhouse effect by consuming carbon dioxide gas in large-scale production, saves energy sources such as petroleum and the like, and has great significance for environmental protection, energy conservation and emission reduction.
In the invention, the diisocyanate is aliphatic diisocyanate, so that the yellowing resistance of the film photocured by the ultraviolet-curable aqueous polyurethane emulsion is better than that of the film photocured by the aromatic aqueous polyurethane emulsion, and the chain extender is a non-hydrophilic chain extender.
Preferably, the diisocyanate is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate;
the hydrophilic functional monomer is selected from one or more of dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), pyromellitic dianhydride (BPDA), 1, 2-propylene glycol-3-sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt, and is preferably dimethylolpropionic acid;
the catalyst is selected from one or more of stannous octoate, di-n-butyltin dilaurate and tin acetate;
the chain extender is selected from one or more of ethylene glycol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, glycerol, trimethylolpropane, ethylenediamine, 1, 6-hexamethylenediamine, ethanolamine and diethanolamine, and more preferably 1, 4-butanediol.
Preferably, the polymerization inhibitor is selected from one or more of 2,2,6, 6-tetramethylpiperidine oxide (TEMPO), hydroquinone and 2,6 di-tert-butyl-4-methylphenol;
the neutralizing agent is one or more selected from triethylamine, tripropylamine, tributylamine, sodium hydroxide and ammonia water.
The invention also provides a preparation method of the ultraviolet-curable waterborne polyurethane emulsion, which comprises the following steps:
a) carrying out a first reaction on polypropylene carbonate dihydric alcohol, diisocyanate and a hydrophilic functional monomer under the action of a catalyst to obtain an intermediate;
b) adding a chain extender into the intermediate to carry out a second reaction to obtain a polyurethane prepolymer;
c) adding a reactive monomer and a polymerization inhibitor into the polyurethane prepolymer for a third reaction, adding a neutralizing agent for neutralization reaction, and adding deionized water for emulsification to obtain an ultraviolet-curable aqueous polyurethane emulsion;
wherein the reactive monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and epoxy modified acrylates.
In the invention, the polypropylene carbonate dihydric alcohol, the diisocyanate and the reactive monomer are used as main raw materials, the reactive monomer can react with the terminal group (-NCO) of the polyurethane prepolymer, and the obtained ultraviolet light curable aqueous polyurethane emulsion is acrylate-terminated aqueous polyurethane acrylate emulsion. The film cured by the ultraviolet-curable aqueous polyurethane emulsion has better hardness, good fullness, water resistance, corrosion resistance, wear resistance, scratch resistance and higher mechanical strength, and improves the practical application value of the ultraviolet-curable aqueous polyurethane emulsion. In addition, the raw materials of the ultraviolet-curable waterborne polyurethane emulsion do not need organic solvents, acetone does not need to be used as a solvent in the preparation process to reduce the viscosity of the system, the reactive monomer can reduce the viscosity of the system, the use of the organic solvents is avoided, the discharge problem of VOC is further solved, and the pollution to the environment and the harm to the health are reduced.
Preferably, the temperature of the first reaction in the step a) is 70-90 ℃;
the time of the first reaction is 2-6 h.
Preferably, the temperature of the second reaction in the step b) is 40-70 ℃;
the time of the second reaction is 1 to 2 hours, and more preferably 1 hour.
Preferably, the temperature of the third reaction in the step c) is 70-80 ℃, and the time of the third reaction is 1-3 h;
the temperature of the neutralization reaction is 40-50 ℃, and the time of the neutralization reaction is 5-30 min;
the emulsifying temperature is 10-25 ℃, and the emulsifying time is 10-60 min.
In the invention, after the emulsification in the step c), the mixture is preferably stirred, emulsified and dispersed for 30min at the speed of 400rpm, and the mixture is cooled to obtain the ultraviolet-curable aqueous polyurethane emulsion, wherein the solid content of the ultraviolet-curable aqueous polyurethane emulsion is 80-90%.
The invention also provides the application of the ultraviolet-curable aqueous polyurethane emulsion in the technical scheme and/or the ultraviolet-curable aqueous polyurethane emulsion prepared by the preparation method in the technical scheme in coating.
In summary, the invention provides an ultraviolet-curable aqueous polyurethane emulsion, which comprises the following raw materials: the preparation method comprises the following steps of (1) poly (propylene carbonate) dihydric alcohol, diisocyanate, hydrophilic functional monomers, a catalyst, a chain extender, reactive monomers, a polymerization inhibitor, a neutralizer and deionized water; the reactive monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and epoxy modified acrylates. According to the invention, the polypropylene carbonate dihydric alcohol, the diisocyanate and the reactive monomer are used as main raw materials, and the ultraviolet light curing double bond group is introduced, so that the acrylate resin and the polyurethane resin are connected through a chemical bond, and the organic unification of the excellent performances of the two resins is effectively realized, so that the film cured by the ultraviolet light curing aqueous polyurethane emulsion has better hardness, has good fullness, water resistance, corrosion resistance, wear resistance, scratch resistance and higher mechanical strength, and improves the practical application value of the ultraviolet light curing aqueous polyurethane emulsion. In addition, the raw materials of the ultraviolet-curable waterborne polyurethane emulsion do not need organic solvents, acetone does not need to be used as a solvent in the preparation process to reduce the viscosity of the system, the reactive monomer can reduce the viscosity of the system, the use of the organic solvents is avoided, the discharge problem of VOC is further solved, and the pollution to the environment and the harm to the health are reduced.
Detailed Description
The invention provides an ultraviolet-curable waterborne polyurethane emulsion, and a preparation method and application thereof, which are used for improving the water resistance, corrosion resistance, hardness and scratch resistance of waterborne polyurethane.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In this example, the preparation of the uv-curable aqueous polyurethane emulsion includes the following steps:
1) taking 60 parts by mass of polypropylene carbonate dihydric alcohol with the molecular weight of 2000 and the hydroxyl functionality of 2, dehydrating in vacuum at high temperature, adding 25 parts of isophorone diisocyanate, 4.5 parts of dimethylolpropionic acid and 0.12 part of stannous octoate, and carrying out a first reaction at 85 ℃ for 4 hours to obtain an intermediate.
2) And cooling to 70 ℃, adding 1.9 parts of chain extender 1, 4-butanediol into the intermediate, and carrying out a second reaction for 0.5 hour under the condition of heat preservation to obtain the polyurethane prepolymer.
3) And (2) cooling to 65 ℃, adding 16 parts of reactive monomer hydroxyethyl methacrylate and 0.02 part of 2,2,6, 6-tetramethylpiperidine oxide (TEMPO) into the polyurethane prepolymer, carrying out a third reaction for 2 hours under the condition of heat preservation, cooling to 45 ℃, adding 3.5 parts of neutralizing agent triethylamine, carrying out a third reaction for 10 minutes, adding 10 parts of deionized water, and emulsifying at 15 ℃ for 30 minutes to obtain the ultraviolet-curable waterborne polyurethane emulsion with the functionality of 2.
Example 2
In this example, the preparation of the uv-curable aqueous polyurethane emulsion includes the following steps:
1) taking 60 parts by mass of polypropylene carbonate dihydric alcohol with the molecular weight of 2000 and the hydroxyl functionality of 2, dehydrating in vacuum at high temperature, adding 25 parts of isophorone diisocyanate, 4.5 parts of dimethylolpropionic acid and 0.12 part of stannous octoate, and carrying out a first reaction at 85 ℃ for 4 hours to obtain an intermediate.
2) And cooling to 70 ℃, adding 1.9 parts of chain extender 1, 4-butanediol into the intermediate, and carrying out a second reaction for 0.5 hour under the condition of heat preservation to obtain the polyurethane prepolymer.
3) And (2) cooling to 65 ℃, adding 11 parts of reactive monomer glyceryl dimethacrylate and 0.02 part of polymerization inhibitor into the polyurethane prepolymer, carrying out a third reaction for 2 hours under the condition of heat preservation, cooling to 45 ℃, adding 3.5 parts of neutralizing agent triethylamine, carrying out a third reaction for 10 minutes, adding 10 parts of deionized water, and emulsifying at 15 ℃ for 30 minutes to obtain the ultraviolet-curable waterborne polyurethane emulsion with the functionality of 4.
Example 3
In this example, the preparation of the uv-curable aqueous polyurethane emulsion includes the following steps:
1) taking 60 parts by mass of polypropylene carbonate dihydric alcohol with the molecular weight of 2000 and the hydroxyl functionality of 2, dehydrating in vacuum at high temperature, adding 25 parts of isophorone diisocyanate, 4.5 parts of dimethylolpropionic acid and 0.12 part of stannous octoate, and carrying out a first reaction at 85 ℃ for 4 hours to obtain an intermediate.
2) And cooling to 70 ℃, adding 1.9 parts of chain extender 1, 4-butanediol into the intermediate, and carrying out a second reaction for 0.5 hour under the condition of heat preservation to obtain the polyurethane prepolymer.
3) And (2) cooling to 65 ℃, adding 14 parts of reactive monomer pentaerythritol triacrylate and 0.02 part of polymerization inhibitor into the polyurethane prepolymer, carrying out a third reaction for 2 hours under the condition of heat preservation, cooling to 45 ℃, adding 3.5 parts of neutralizing agent triethylamine, carrying out a third reaction for 10 minutes, adding 10 parts of deionized water, and emulsifying at 15 ℃ for 30 minutes to obtain the ultraviolet-curable waterborne polyurethane emulsion with the functionality of 6.
Comparative example 1
The preparation of the ultraviolet-curable aqueous polyurethane emulsion in the comparative example comprises the following steps:
1) taking 60 parts by mass of polyether glycol (PPG) with the molecular weight of 2000 and the hydroxyl functionality of 2, dehydrating at high temperature in vacuum, adding 25 parts of isophorone diisocyanate, 4.5 parts of dimethylolpropionic acid and 0.12 part of stannous octoate, and reacting at 85 ℃ for 4 hours to obtain an intermediate.
2) And cooling to 70 ℃, adding 1.9 parts of chain extender 1, 4-butanediol into the intermediate, and carrying out heat preservation for 0.5 hour to react to obtain the polyurethane prepolymer.
3) And (2) cooling to 65 ℃, adding 16 parts of reactive monomer hydroxyethyl methacrylate and 0.02 part of polymerization inhibitor into the polyurethane prepolymer, carrying out a third reaction for 2 hours under heat preservation, cooling to 45 ℃, adding 3.5 parts of neutralizing agent triethylamine, carrying out a reaction for 10 minutes, adding 10 parts of deionized water, and emulsifying at 15 ℃ for 30 minutes to obtain the ultraviolet-curable waterborne polyurethane emulsion with the functionality of 2.
Comparative example 2
The preparation of the ultraviolet-curable aqueous polyurethane emulsion in the comparative example comprises the following steps:
1) taking 60 parts by mass of polyester diol (PBA) with the molecular weight of 2000 and the hydroxyl functionality of 2, dehydrating the mixture at high temperature in vacuum, adding 25 parts of isophorone diisocyanate, 4.5 parts of dimethylolpropionic acid and 0.12 part of stannous octoate, and reacting the mixture at 85 ℃ for 4 hours to obtain an intermediate.
2) And cooling to 70 ℃, adding 1.9 parts of chain extender 1, 4-butanediol into the intermediate, and carrying out heat preservation for 0.5 hour to react to obtain the polyurethane prepolymer.
3) And (2) cooling to 65 ℃, adding 16 parts of reactive monomer hydroxyethyl methacrylate and 0.02 part of polymerization inhibitor into the polyurethane prepolymer, carrying out a third reaction for 2 hours under heat preservation, cooling to 45 ℃, adding 3.5 parts of neutralizing agent triethylamine, carrying out a reaction for 10 minutes, adding 10 parts of deionized water, and emulsifying at 15 ℃ for 30 minutes to obtain the ultraviolet-curable waterborne polyurethane emulsion with the functionality of 2.
Example 4
And (3) carrying out performance tests on the ultraviolet-curable aqueous polyurethane emulsions in the examples 1-3 and the comparative examples 1-2, wherein the performance tests comprise a storage stability test and an emulsion particle size test, the storage stability test is that the ultraviolet-curable aqueous polyurethane emulsion is filled into a plastic bottle according to the test of the method of GBT23999-2009, the plastic bottle is sealed and then placed in a constant-temperature oven at 50 ℃, the plastic bottle is taken out after 7 days, and the emulsion is stirred without agglomeration, so that the storage is considered to be abnormal. Emulsion particle size test the emulsion was tested by diluting it to 0.05% with deionized water using a ZETA potentiostat from beckmann coulter.
Respectively adding a photoinitiator UV2959 (accounting for 3.5 percent of the total mass of the whole curing system) into the UV-curable aqueous polyurethane emulsion in the embodiments 1-3 and the comparative examples 1-2, controlling the thickness of the coating to be 20 microns, standing for 6 hours under a natural air drying condition, curing by illumination under a 200W (UV wavelength 365mm) ultraviolet lamp, and keeping the distance between a light source and the coating to be 20cm to prepare the photocured film for testing the hardness of the swing rod and the tensile strength and elongation at break.
Testing the hardness of the oscillating bar: testing a swing rod hardness tester, wherein the number of standard swing rods is n, and adjusting the swing rod hardness tester to enable n to be within an interval of 250 +/-10. The prepared latex sample for the pendulum bar was placed on a glass plate, the test result was recorded as n1, the hardness ratio was calculated as R, and the hardness ratio was calculated according to the following formula 1-1:
tensile strength and elongation at break test: and cutting the film paved on the HDPE board into a dumbbell shape, measuring the thickness by using a thickness gauge, and testing the tensile strength and the elongation at break of the adhesive film at room temperature according to GB/T1040.3-2006. The test temperature was 25 ℃ and the drawing speed was 200 mm/min.
The results refer to table 1, and the results show that compared with the photocured film prepared by the polyether polyester type aqueous polyurethane emulsion of comparative examples 1-2, the photocured film prepared by the ultraviolet-curable aqueous polyurethane emulsion of examples 1-3 of the present invention has more excellent hardness, elongation at break and tensile strength, and the ultraviolet-curable aqueous polyurethane emulsion of examples 1-3 of the present invention is suitable for the fields of ultraviolet-curable adhesives, ultraviolet-curable coatings, etc.
Table 1 Performance test results of ultraviolet-curable aqueous polyurethane emulsions of examples 1 to 3 and comparative examples 1 to 2
| Test items | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Appearance of the product | Blue light transparent | Blue light transparent | Blue light transparent | Blue light transparent | Blue light transparent |
| Particle size | 40-70nm | 40-70nm | 40-70nm | 40-70nm | 40-70nm |
| Storage stability | No abnormality | No abnormality | No abnormality | No abnormality | No abnormality |
| hardness/S of pendulum bar | 95 | 115 | 145 | 85 | 110 |
| Elongation at break | 70％ | 80％ | 65％ | 55％ | 48％ |
| Tensile strength | 12 | 16 | 15 | 6 | 12 |
Example 5
Adding 30 g of the ultraviolet-curable aqueous polyurethane emulsion obtained in the embodiments 1-3 and the comparative examples 1-2 into a mixing container, adding 1.4 g of photoinitiator UV2959 and 60 g of deionized water, stirring until the mixture is uniformly mixed to obtain an ultraviolet-curable aqueous polyurethane coating, irradiating the ultraviolet-curable aqueous polyurethane coating by a 1000W mercury lamp for 10-15 seconds to obtain a photocuring film, wherein the curing effect meets the national standard, the photocuring film has no harm to human bodies and the environment, and the photocuring film is subjected to a solvent resistance test according to the national standards GB/T6739-1996 and GB/T23999-2009. The results refer to table 2, which shows that compared with the ultraviolet-curable aqueous polyurethane emulsions of comparative examples 1 to 2, the photocuring films prepared from the ultraviolet-curable aqueous polyurethane emulsions of examples 1 to 3 have excellent ethanol resistance and boiling water resistance, water resistance and corrosion resistance, and can be used in the coating fields of aqueous wood lacquer and the like.
Table 2 Performance test results of photocured films prepared from UV-curable aqueous polyurethane emulsions according to examples 1 to 3 and comparative examples 1 to 2
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An ultraviolet-curable aqueous polyurethane emulsion is characterized in that the raw materials of the ultraviolet-curable aqueous polyurethane emulsion comprise: the preparation method comprises the following steps of (1) poly (propylene carbonate) dihydric alcohol, diisocyanate, hydrophilic functional monomers, a catalyst, a chain extender, reactive monomers, a polymerization inhibitor, a neutralizer and deionized water;
the reactive monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and epoxy modified acrylates.
2. The ultraviolet-curable aqueous polyurethane emulsion according to claim 1, wherein the raw materials comprise, in parts by mass: 60 parts of polypropylene carbonate dihydric alcohol, 20-40 parts of diisocyanate, 2-10 parts of hydrophilic functional monomer, 0.12-0.36 part of catalyst, 1-10 parts of chain extender, 10-50 parts of reactive monomer, 0.2-0.5 part of polymerization inhibitor, 2-10 parts of neutralizer and 10-30 parts of deionized water.
3. The ultraviolet-curable aqueous polyurethane emulsion according to claim 1, wherein the molecular weight of the polypropylene carbonate diol is 1000 to 3000;
the hydroxyl functionality of the polypropylene carbonate diol is 2;
the mole fraction of carbonate groups in the molecule of the polypropylene carbonate dihydric alcohol is 0.3-0.4.
4. The UV-curable aqueous polyurethane emulsion according to claim 1, wherein the diisocyanate is one or more selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, and hydrogenated diphenylmethane diisocyanate;
the hydrophilic functional monomer is selected from one or more of dimethylol propionic acid, dimethylol butyric acid, pyromellitic dianhydride, 1, 2-propylene glycol-3-sodium sulfonate, 1, 4-butanediol-2-sodium sulfonate and 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt;
the catalyst is selected from one or more of stannous octoate, di-n-butyltin dilaurate and tin acetate;
the chain extender is one or more selected from ethylene glycol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol, glycerol, trimethylolpropane, ethylenediamine, 1, 6-hexamethylenediamine, ethanolamine and diethanolamine.
5. The UV-curable aqueous polyurethane emulsion according to claim 1, wherein the polymerization inhibitor is one or more selected from the group consisting of 2,2,6, 6-tetramethylpiperidinyloxy free radical, hydroquinone and 2,6 di-tert-butyl-4-methylphenol;
the neutralizing agent is one or more selected from triethylamine, tripropylamine, tributylamine, sodium hydroxide and ammonia water.
6. A preparation method of an ultraviolet-curable aqueous polyurethane emulsion is characterized by comprising the following steps:
a) carrying out a first reaction on polypropylene carbonate dihydric alcohol, diisocyanate and a hydrophilic functional monomer under the action of a catalyst to obtain an intermediate;
b) adding a chain extender into the intermediate to carry out a second reaction to obtain a polyurethane prepolymer;
c) adding a reactive monomer and a polymerization inhibitor into the polyurethane prepolymer for a third reaction, adding a neutralizing agent for neutralization reaction, and adding deionized water for emulsification to obtain an ultraviolet-curable aqueous polyurethane emulsion;
wherein the reactive monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and epoxy modified acrylates.
7. The method of claim 6, wherein the temperature of the first reaction in step a) is 70 ℃ to 90 ℃;
the time of the first reaction is 2-6 h.
8. The method of claim 6, wherein the temperature of the second reaction in step b) is 40 ℃ to 70 ℃;
the time of the second reaction is 1-2 h.
9. The preparation method according to claim 6, wherein the temperature of the third reaction in step c) is 70-80 ℃, and the time of the third reaction is 1-3 h;
the temperature of the neutralization reaction is 40-50 ℃, and the time of the neutralization reaction is 5-30 min;
the emulsifying temperature is 10-25 ℃, and the emulsifying time is 10-60 min.
10. The use of the ultraviolet-curable aqueous polyurethane emulsion according to any one of claims 1 to 5 and/or the ultraviolet-curable aqueous polyurethane emulsion prepared by the preparation method according to any one of claims 6 to 9 in an ultraviolet-curable adhesive or an ultraviolet-curable coating.
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