CN108003322B - Self-emulsifying type waterborne polyurethane acrylate oligomer and preparation method thereof - Google Patents

Self-emulsifying type waterborne polyurethane acrylate oligomer and preparation method thereof Download PDF

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CN108003322B
CN108003322B CN201711257945.1A CN201711257945A CN108003322B CN 108003322 B CN108003322 B CN 108003322B CN 201711257945 A CN201711257945 A CN 201711257945A CN 108003322 B CN108003322 B CN 108003322B
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self
acrylate oligomer
urethane acrylate
aqueous urethane
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CN108003322A (en
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吴小浩
黄立标
黄杰良
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Shenzhen Giantechem Technology Co ltd
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Abstract

A self-emulsifying aqueous polyurethane acrylate oligomer and a preparation method thereof, wherein the preparation method comprises the following steps of (S1) synthesizing a trihydroxy unsaturated monomer A with a phosphate group; (S2) synthesis of a hexahydroxy monomer B; (S3) synthesis of polymer C; (S4) synthesis of self-initiating self-emulsifying aqueous urethane acrylate oligomer; and (S3) cooling the polymer C synthesized in the step (S3) to 35-40 ℃, adding triethylamine for neutralization, adding deionized water with the solid content of 122-150% of that of the polymer C for shearing and emulsification, decompressing to 0.03-0.05MPa, and removing acetone to obtain the water-based ultraviolet curing polyurethane acrylate oligomer with the solid content of 40-45%. The invention has the advantages of simpler synthetic process, lower cost, higher film hardness and glossiness and capability of effectively reducing the yellowing of the film.

Description

Self-emulsifying type waterborne polyurethane acrylate oligomer and preparation method thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to a self-emulsifying waterborne polyurethane acrylate oligomer and a preparation method thereof.
Background
The ultraviolet curing coating technology refers to a surface treatment technology, which is characterized in that a photoinitiator or a photosensitizer is irradiated by ultraviolet light to generate free radicals so as to initiate polymerization reaction of active monomers, oligomers or resins. Thus obtaining a crosslinked compact paint film. Since the 21 st century, with the increasing emphasis on environmental protection, aqueous photocurable coatings are favored by people because they inherit the traditional photocuring technology and have the advantages of no VOC emission and no monomer residue, and are environmentally friendly.
The photocureable coating prepared from the polyurethane acrylate oligomer has the advantages of both polyurethane coatings and polyacrylate coatings: has excellent mechanical wear resistance, flexibility, chemical resistance and good high temperature resistance and low temperature resistance, thereby being distinguished from a plurality of oligomeric species. However, compared with the traditional oil-based urethane acrylate oligomer, the waterborne urethane acrylate oligomer also has the problems of long molecular chain segment, high resin viscosity, low double bond density on the molecular chain and the like, the resin viscosity is high, so that more solvent is needed to reduce the system viscosity to facilitate later emulsification, the low double bond density on the molecular chain can cause low crosslinking density, the hardness of a paint film is influenced, the molecular weight is higher, the paint film is easy to yellow, the color of the paint film is influenced, and the final performance of the waterborne urethane acrylate resin is influenced by the factors. Therefore, research on the aqueous urethane acrylate resin with better performance is focused. For example, chinese patent document CN 101475679 discloses an aqueous urethane acrylate resin and a preparation method thereof, wherein toluene diisocyanate is reacted with polycarbonate diol and self-made carboxyl modified polycaprolactone diol, and then the reaction product is extended with dimethylol propionic acid and a dihydroxy chain extender with an unsaturated group, and finally the end of the reaction product is terminated with a polyfunctional monomer with hydroxyl group such as pentaerythritol triacrylate, so as to prepare an aqueous urethane acrylate oligomer with higher unsaturated double bonds. Anila Asif et al reported that hyperbranched aliphatic polyester polyol was reacted with acid anhydride first to introduce carboxyl groups into the polyester molecules, then reacted with the reaction product of HEA and diisocyanate, and neutralized with triethylamine to obtain unsaturated double-bond hyperbranched aqueous urethane acrylate resin.
The synthesis of the two waterborne polyurethane acrylate resins has the problems of complicated synthesis process and high cost, and the batch synthesis cost is high, so that the synthesis is not beneficial to popularization; in addition, the waterborne polyurethane acrylate resin synthesized by the two methods has lower paint film hardness, more serious paint film yellowing and poorer fluorescent ultraviolet aging resistance.
Disclosure of Invention
In order to overcome the problems, the invention provides a method for preparing the self-emulsifying waterborne polyurethane acrylate oligomer which has simpler synthesis process, higher paint film hardness, better fluorescence ultraviolet aging resistance and can effectively reduce paint film yellowing for society.
The invention also provides a self-emulsifying waterborne polyurethane acrylate oligomer which has simpler synthetic process, higher paint film hardness and can effectively reduce paint film yellowing for society.
The technical scheme of the invention is as follows: provides a preparation method of self-emulsifying water-based polyurethane acrylate oligomer, which comprises the following steps,
(S1) Synthesis of Trihydroxyl unsaturated monomer A having phosphate group:
adding 15-21% of phosphoric acid, 77-83% of glycidyl methacrylate, 0.9-1% of triphenylphosphine and 0.8-1% of polymerization inhibitor into a reactor by mass percent, introducing nitrogen, heating to 90-100 ℃ for reaction, and stopping the reaction when the acid value is 1% of the initial acid value within 5-6 hours to obtain a trihydroxy unsaturated monomer A with a phosphate group;
(S2) Synthesis of hexahydroxy monomer B:
putting 40-61% of diisocyanate trimer and 9-17% of dimethylamide into a reactor according to the mass percentage, cooling to 0-15 ℃, slowly dripping 27-51% of diethanolamine, reacting for 2-3 hours, and stopping the reaction when the measured isocyanate group value is 0-0.1%; then heating to 80-85 ℃, decompressing to 0.03-0.05MPa to remove dimethyl amide and obtain a hexahydroxy monomer B;
(S3) Synthesis of Polymer C:
putting 1.6-5% of hexahydroxy monomer B, 4-8.5% of trihydroxy unsaturated monomer A, 16-39% of dihydric alcohol and 0.02-0.03% of polymerization inhibitor into a reaction kettle, adding 7-10% of acetone, heating to 40-45 ℃, introducing nitrogen, dropwise adding a mixture mixed with 0-0.26% of catalyst and 19-31% of diisocyanate, finishing dropwise within 0.5-1 hour, reacting for 1.5-2 hours, measuring isocyanate groups to a theoretical value, heating to 65-70 ℃, dropwise adding a mixed solution dissolved with 3-4% of dimethylolpropionic acid, 4-7% of polyether dihydric alcohol and 3-4% of diformamide, dropwise adding for 0.5-1 hour, reacting for 1.5-2 hours, measuring the isocyanate groups to the theoretical value, dropwise adding 16-23% of pentaerythritol triacrylate, 0.2-0.3% of catalyst, and stirring to obtain a mixture, 0.14-0.20% of polymerization inhibitor, dropping for 0.5-1 hour, reacting for 3.5-5 hours, stopping reaction when the content of isocyanate group is 0% -0.1%, obtaining polymer C;
(S4) Synthesis of self-emulsifiable aqueous urethane acrylate oligomer
And (S3) cooling the polymer C synthesized in the step (S3) to 35-40 ℃, adding triethylamine for neutralization, adding deionized water with the solid content of 122-150% of that of the polymer C for shearing emulsification, decompressing to 0.03-0.05MPa, and removing acetone to obtain the self-emulsifying waterborne polyurethane acrylate oligomer with the solid content of 40-45%.
As an improvement of the invention, the polymerization inhibitor is hydroquinone or p-hydroxymethylphenol.
As an improvement of the present invention, the diisocyanate trimer is toluene diisocyanate trimer, isophorone diisocyanate trimer or 1, 6-hexamethylene diisocyanate trimer.
As an improvement of the invention, the dihydric alcohol is one or any two of polycarbonate dihydric alcohol with molecular weight of 500-1000, polycaprolactone dihydric alcohol with molecular weight of 500-1000, polytetrahydrofuran ether dihydric alcohol with molecular weight of 500-1000, polyester dihydric alcohol with molecular weight of 500-1000, ethylene glycol, 1, 3-propanediol and 1, 4-butanediol.
As an improvement of the invention, the molar ratio of the small molecular diol to the long-chain diol is 1:3-2:1, and the molar ratio of the long-chain diols is 1:1-9: 1.
As an improvement of the invention, the diisocyanate is one or more of 2, 4-toluene diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate;
as a modification of the invention, the molar ratio of the 2, 4-toluene diisocyanate, isophorone diisocyanate, and 1, 6-hexamethylene diisocyanate is in the range of 0:4:0 to 1:2: 1.
As an improvement to the present invention, the catalyst is dibutyltin dilaurate, stannous octoate or organic bismuth.
As an improvement of the invention, the polyether glycol is polyethylene glycol with a molecular weight of 600-1000 or polypropylene glycol with a molecular weight of 600-1000.
The other technical scheme of the invention is as follows: a self-emulsifying aqueous urethane acrylate oligomer prepared by the above method is provided.
According to the water-based ultraviolet-curing polyurethane acrylate resin, the polyhydroxy monomer with carbamido high branching and the trihydroxy unsaturated monomer are introduced into part of the structure of the resin, so that the main resin has a part of hyperbranched structure, the molecular weight can be improved, the system viscosity can be effectively reduced, the crosslinking density can be improved, high gloss and high hardness can be obtained, and meanwhile, the phosphate group is introduced, so that the adhesive force to a substrate can be effectively increased; on the premise of ensuring the stability of the emulsified system, the invention adopts a nonionic and anionic double-emulsion system in the selection of the grafted hydrophilic group, so that the dosage of the added neutralizing amine can be effectively reduced, and the yellowing property of the final paint film is reduced. Compared with the prior art, the synthesis process is simpler, and the cost is lower, so that the method has the advantages of simpler synthesis process, lower cost, higher paint film hardness and glossiness, and capability of effectively reducing paint film yellowing.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
In the description of the present invention, it is to be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; either directly or indirectly through intervening media, or may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood in specific cases to those skilled in the art. In addition, in the description of the present invention, "a plurality" or "a plurality" means two or more unless otherwise specified.
Referring to fig. 1, a method for preparing a self-emulsifying aqueous urethane acrylate oligomer comprises the following steps,
(S1) Synthesis of Trihydroxyl unsaturated monomer A having phosphate group:
adding 17-19% of phosphoric acid, 76-84% of glycidyl methacrylate, 0.9-1% of triphenylphosphine and 0.8-1% of polymerization inhibitor into a reactor by mass percent, introducing nitrogen, heating to 90-100 ℃ for reaction, and stopping the reaction after 5-6 hours until the acid value is 1% of the initial acid value to obtain a trihydroxy unsaturated monomer A with a phosphate group;
(S2) Synthesis of hexahydroxy monomer B:
putting 40-61% of diisocyanate trimer and 9-17% of dimethylamide into a reactor according to the mass percentage, cooling to 0-15 ℃, slowly dripping 27-51% of diethanolamine, reacting for 2-3 hours, and stopping the reaction when the measured isocyanate group value is 0-0.1%; then heating to 80-85 ℃, decompressing to 0.03-0.05MPa to remove dimethyl amide and obtain a hexahydroxy monomer B;
(S3) Synthesis of Polymer C:
putting 2-6% of hexahydroxy monomer B, 4-9% of trihydroxy unsaturated monomer A, 17-39% of dihydric alcohol and 0.02-0.03% of polymerization inhibitor into a reaction kettle, adding 7-10% of acetone, heating to 40-45 ℃, introducing nitrogen, dropwise adding a mixture containing 0-0.26% of catalyst and 19-31% of diisocyanate, finishing dropwise within 0.5-1 hour, reacting for 1.5-2 hours, measuring isocyanate groups to a theoretical value, heating to 65-70 ℃, dropwise adding a mixed solution containing 3-4% of dimethylolpropionic acid, 4-7% of polyether glycol and 3-4% of diformamide, dropwise adding for 0.5-1 hour, reacting for 1.5-2 hours, measuring isocyanate groups to a theoretical value, dropwise adding 16-23% of pentaerythritol triacrylate and 0.2-0.3% of catalyst, 0.14-0.20% of polymerization inhibitor, dropping for 0.5-1 hour, reacting for 3.5-5 hours, stopping reaction when the content of isocyanate group is 0% -0.1%, obtaining polymer C;
(S4) Synthesis of self-emulsifiable aqueous urethane acrylate oligomer
And (S3) cooling the polymer C synthesized in the step (S3) to 35-40 ℃, adding triethylamine for neutralization, adding deionized water with the solid content of 122-150% of that of the polymer C for shearing emulsification, decompressing to 0.03-0.05MPa, and removing acetone to obtain the self-emulsifying waterborne polyurethane acrylate oligomer with the solid content of 40-45%.
In the present invention, it is preferable that the polymerization inhibitor is hydroquinone or p-hydroxymethylphenol.
In the present invention, it is preferable that the diisocyanate trimer is toluene diisocyanate trimer, isophorone diisocyanate trimer or 1, 6-hexamethylene diisocyanate trimer.
In the invention, the dihydric alcohol is preferably one or two of polycarbonate dihydric alcohol with molecular weight of 500-1000, polycaprolactone dihydric alcohol with molecular weight of 500-1000, polytetrahydrofuran ether dihydric alcohol with molecular weight of 500-1000, polyester dihydric alcohol with molecular weight of 500-1000, ethylene glycol, 1, 3-propylene glycol and 1, 4-butanediol; in order to avoid the shrinkage and brittleness of the paint film after curing caused by excessively high crosslinking density, the diol with the molecular weight of 500-1000 is selected from the diol.
In the present invention, it is preferable that the molar ratio of the small molecule diol to the long chain diol is 1:3 to 2:1, and the molar ratio of the long chain diols is 1:1 to 9: 1.
In the present invention, preferably, the diisocyanate is one or more of 2, 4-toluene diisocyanate, isophorone diisocyanate, and 1, 6-hexamethylene diisocyanate;
in the present invention, the molar ratio of the 2, 4-tolylene diisocyanate, the isophorone diisocyanate, and the 1, 6-hexamethylene diisocyanate is preferably in the range of 0:4:0 to 1:2: 1.
In the present invention, preferably, the catalyst is dibutyltin dilaurate, stannous octoate or organic bismuth.
In the present invention, it is preferable that the polyether glycol is polyethylene glycol having a molecular weight of 600-1000 or polypropylene glycol having a molecular weight of 600-1000.
The invention also provides the self-emulsifying water-based polyurethane acrylate oligomer prepared by the method.
In the invention, the triethylamine is added according to the molar quantity of carboxyl in dimethylolpropionic acid.
In the invention, the calculation method of the theoretical value reached by the isocyanate group comprises the following steps: theoretical value = moles of total isocyanate groups-moles of hydroxyl groups in the reaction, calculated by determining moles of isocyanate groups by the di-n-butylamine method.
Example 1
A preparation method of self-emulsifying water-based polyurethane acrylate oligomer comprises the following steps,
(S1) Synthesis of Trihydroxyl unsaturated monomer A having phosphate group:
adding 17% of phosphoric acid, 81% of glycidyl methacrylate, 1% of triphenylphosphine and 1% of polymerization inhibitor into a reactor according to mass percentage, introducing nitrogen, heating to 90-100 ℃ for reaction, and stopping the reaction after 5-6 hours until the acid value is 1% of the initial acid value to obtain a trihydroxy unsaturated monomer A with a phosphate group;
(S2) Synthesis of hexahydroxy monomer B:
putting 40% of diisocyanate trimer and 17% of dimethylamide into a reactor according to the mass percentage, cooling to 0-15 ℃, slowly dripping 43% of diethanolamine, reacting for 2-3 hours, and stopping the reaction when the measured isocyanate group value is 0.1%; then heating to 80-85 ℃, decompressing to 0.03-0.05MPa to remove dimethyl amide and obtain a hexahydroxy monomer B;
(S3) Synthesis of Polymer C:
putting 4 percent of hexahydroxy monomer B, 5 percent of trihydroxy unsaturated monomer A, 28.37 percent of dihydric alcohol and 0.03 percent of polymerization inhibitor into a reaction kettle, adding 9 percent of acetone, heating to 40-45 ℃, introducing nitrogen, dripping a mixture mixed with 0.26 percent of catalyst and 26 percent of diisocyanate after 0.5-1 hour of dripping, reacting for 1.5-2 hours, measuring the isocyanate group to the theoretical value, heating to 65-70 ℃, dripping a mixed solution dissolved with 3 percent of dimethylolpropionic acid, 3.5 percent of polyether dihydric alcohol and 3 percent of diformylamide for 0.5-1 hour, reacting for 1.5-2 hours, measuring the isocyanate group to the theoretical value, dripping a mixed solution of 17.5 percent of pentaerythritol triacrylate, 0.2 percent of catalyst and 0.14 percent of polymerization inhibitor for 0.5-1 hour, reacting for 3.5-5 hours, stopping the reaction when the content of the isocyanate group is measured to be 0.1 percent to obtain a polymer C;
(S4) Synthesis of self-emulsifiable aqueous urethane acrylate oligomer
And (S3) cooling the polymer C synthesized in the step (S3) to 35-40 ℃, adding triethylamine for neutralization, adding deionized water with the solid content of 122-150% of that of the polymer C for shearing emulsification, decompressing to 0.03-0.05MPa, and removing acetone to obtain the self-emulsifying waterborne polyurethane acrylate oligomer with the solid content of 40-45%.
Example 2
A preparation method of self-emulsifying water-based polyurethane acrylate oligomer comprises the following steps,
(S1) Synthesis of Trihydroxyl unsaturated monomer A having phosphate group:
adding 18.25% of phosphoric acid, 80% of glycidyl methacrylate, 0.95% of triphenylphosphine and 0.8% of polymerization inhibitor into a reactor by mass percent, introducing nitrogen, heating to 90-100 ℃ for reaction, and stopping the reaction when the acid value is 1% of the initial acid value within 5-6 hours to obtain a trihydroxy unsaturated monomer A with a phosphate group;
(S2) Synthesis of hexahydroxy monomer B:
putting 61% of diisocyanate tripolymer and 12% of dimethylamide into a reactor according to the mass percentage, cooling to 0-15 ℃, slowly dripping 27% of diethanolamine, reacting for 2-3 hours, and stopping the reaction when the measured isocyanate group value is 0.1%; then heating to 80-85 ℃, decompressing to 0.03-0.05MPa to remove dimethyl amide and obtain a hexahydroxy monomer B;
(S3) Synthesis of Polymer C:
putting 4.9% of hexahydroxy monomer B, 6% of trihydroxy unsaturated monomer A, 18.04% of dihydric alcohol and 0.02% of polymerization inhibitor into a reaction kettle, adding 10% of acetone, heating to 40-45 ℃, introducing nitrogen, dripping a mixture mixed with 0.1% of catalyst and 25% of diisocyanate after 0.5-1 hour of dripping, reacting for 1.5-2 hours, measuring isocyanate groups to reach a theoretical value, heating to 65-70 ℃, dripping a mixed solution dissolved with 3.8% of dimethylolpropionic acid, 7% of polyether dihydric alcohol and 3.8% of diformylamide for 0.5-1 hour, reacting for 1.5-2 hours, measuring isocyanate groups to reach a theoretical value, dripping a mixed solution of 21% of pentaerythritol triacrylate, 0.2% of catalyst and 0.14% of polymerization inhibitor for 0.5-1 hour, reacting for 3.5-5 hours, stopping the reaction when the content of the isocyanate group is measured to be 0 to obtain a polymer C;
(S4) Synthesis of self-emulsifiable aqueous urethane acrylate oligomer
And (S3) cooling the polymer C synthesized in the step (S3) to 35-40 ℃, adding triethylamine for neutralization, adding deionized water with the solid content of 122-150% of that of the polymer C for shearing emulsification, decompressing to 0.03-0.05MPa, and removing acetone to obtain the self-emulsifying waterborne polyurethane acrylate oligomer with the solid content of 40-45%.
Example 3
A preparation method of self-emulsifying water-based polyurethane acrylate oligomer comprises the following steps,
(S1) Synthesis of Trihydroxyl unsaturated monomer A having phosphate group:
adding 19% of phosphoric acid, 79% of glycidyl methacrylate, 1% of triphenylphosphine and 1% of polymerization inhibitor into a reactor according to mass percentage, introducing nitrogen, heating to 90-100 ℃ for reaction, and stopping the reaction after 5-6 hours until the acid value is 1% of the initial acid value to obtain a trihydroxy unsaturated monomer A with a phosphate group;
(S2) Synthesis of hexahydroxy monomer B:
putting 40% of diisocyanate trimer and 9% of dimethylamide into a reactor according to the mass percentage, cooling to 0-15 ℃, slowly dripping 51% of diethanolamine, reacting for 2-3 hours, and stopping the reaction when the measured isocyanate group value is 0; then heating to 80-85 ℃, decompressing to 0.03-0.05MPa to remove dimethyl amide and obtain a hexahydroxy monomer B;
(S3) Synthesis of Polymer C:
putting 3.83 percent of hexahydroxy monomer B, 5 percent of trihydroxy unsaturated monomer A, 28.6 percent of dihydric alcohol and 0.02 percent of polymerization inhibitor into a reaction kettle, adding 8 percent of acetone, heating to 40-45 ℃, introducing nitrogen, dripping into 25.4 percent of diisocyanate, finishing dripping within 0.5-1 hour, reacting for 1.5-2 hours, measuring isocyanate group to a theoretical value, heating to 65-70 ℃, dissolving a mixed solution of 3 percent of dimethylolpropionic acid, 5.7 percent of polyether dihydric alcohol and 3 percent of diformamide, dripping for 0.5-1 hour, reacting for 1.5-2 hours, measuring isocyanate group to the theoretical value, dripping into a mixed solution of 17 percent of pentaerythritol triacrylate, 0.25 percent of catalyst and 0.2 percent of polymerization inhibitor for 0.5-1 hour, reacting for 3.5-5 hours, stopping the reaction when the measured isocyanate group content is 0, obtaining a polymer C;
(S4) Synthesis of self-emulsifiable aqueous urethane acrylate oligomer
And (S3) cooling the polymer C synthesized in the step (S3) to 35-40 ℃, adding triethylamine for neutralization, adding deionized water with the solid content of 122-150% of that of the polymer C for shearing emulsification, decompressing to 0.03-0.05MPa, and removing acetone to obtain the self-emulsifying waterborne polyurethane acrylate oligomer with the solid content of 40-45%.
Example 4
A preparation method of self-emulsifying water-based polyurethane acrylate oligomer comprises the following steps,
(S1) Synthesis of Trihydroxyl unsaturated monomer A having phosphate group:
adding 18.19% of phosphoric acid, 80% of glycidyl methacrylate, 0.9% of triphenylphosphine and 0.95% of polymerization inhibitor into a reactor by mass percent, introducing nitrogen, heating to 90-100 ℃ for reaction, and stopping the reaction when the acid value is 1% of the initial acid value within 5-6 hours to obtain a trihydroxy unsaturated monomer A with a phosphate group;
(S2) Synthesis of hexahydroxy monomer B:
putting 50% of diisocyanate tripolymer and 10% of dimethylamide into a reactor according to the mass percentage, cooling to 0-15 ℃, slowly dripping 40% of diethanolamine, reacting for 2-3 hours, and stopping the reaction when the measured isocyanate group value is 0; then heating to 80-85 ℃, decompressing to 0.03-0.05MPa to remove dimethyl amide and obtain a hexahydroxy monomer B;
(S3) Synthesis of Polymer C:
putting 1.7 percent of hexahydroxy monomer B, 4.2 percent of trihydroxy unsaturated monomer A, 36.8 percent of dihydric alcohol and 0.03 percent of polymerization inhibitor into a reaction kettle, adding 7 percent of acetone, heating to 40-45 ℃, introducing nitrogen, dripping a mixture mixed with 0.2 percent of catalyst and 24 percent of diisocyanate after dripping for 0.5-1 hour, reacting for 1.5-2 hours, measuring isocyanate groups to a theoretical value, heating to 65-70 ℃, dripping a mixed solution dissolved with 3 percent of dimethylolpropionic acid, 3.3 percent of polyether dihydric alcohol and 3 percent of diformamide, dripping for 0.5-1 hour, reacting for 1.5-2 hours, measuring isocyanate groups to a theoretical value, dripping a mixed solution of 16.4 percent of pentaerythritol triacrylate, 0.2 percent of catalyst and 0.17 percent of polymerization inhibitor for 0.5-1 hour, reacting for 3.5-5 hours, stopping the reaction when the content of the isocyanate group is measured to be 0 to obtain a polymer C;
(S4) Synthesis of self-emulsifiable aqueous urethane acrylate oligomer
And (S3) cooling the polymer C synthesized in the step (S3) to 35-40 ℃, adding triethylamine for neutralization, adding deionized water with the solid content of 122-150% of that of the polymer C for shearing emulsification, decompressing to 0.03-0.05MPa, and removing acetone to obtain the self-emulsifying waterborne polyurethane acrylate oligomer with the solid content of 40-45%.
Example 5
A preparation method of self-emulsifying water-based polyurethane acrylate oligomer comprises the following steps,
(S1) Synthesis of Trihydroxyl unsaturated monomer A having phosphate group:
adding 17% of phosphoric acid, 81% of glycidyl methacrylate, 1% of triphenylphosphine and 1% of polymerization inhibitor into a reactor according to mass percentage, introducing nitrogen, heating to 90-100 ℃ for reaction, and stopping the reaction after 5-6 hours until the acid value is 1% of the initial acid value to obtain a trihydroxy unsaturated monomer A with a phosphate group;
(S2) Synthesis of hexahydroxy monomer B:
putting 61% of diisocyanate tripolymer and 12% of dimethylamide into a reactor according to the mass percentage, cooling to 0-15 ℃, slowly dripping 27% of diethanolamine, reacting for 2-3 hours, and stopping the reaction when the measured isocyanate group value is 0.1%; then heating to 80-85 ℃, decompressing to 0.03-0.05MPa to remove dimethyl amide and obtain a hexahydroxy monomer B;
(S3) Synthesis of Polymer C:
putting 2.6 percent of hexahydroxy monomer B, 6.6 percent of trihydroxy unsaturated monomer A, 28.0 percent of dihydric alcohol and 0.02 percent of polymerization inhibitor into a reaction kettle, adding 8.48 percent of acetone, heating to 40-45 ℃, introducing nitrogen, dripping into 25.2 percent of diisocyanate, finishing dripping within 0.5-1 hour, reacting for 1.5-2 hours, measuring the isocyanate group to the theoretical value, heating to 65-70 ℃, dripping into a mixed solution in which 3 percent of dimethylolpropionic acid, 5.6 percent of polyether dihydric alcohol and 3 percent of diformamide are dissolved, dripping for 0.5-1 hour, reacting for 1.5-2 hours, measuring the isocyanate group to the theoretical value, dripping into a mixed solution of 17 percent of pentaerythritol triacrylate, 0.3 percent of catalyst and 0.20 percent of polymerization inhibitor, dripping for 0.5-1 hour, reacting for 3.5-5 hours, stopping the reaction when the measured isocyanate group content is 0.1 percent, obtaining a polymer C;
(S4) Synthesis of self-emulsifiable aqueous urethane acrylate oligomer
And (S3) cooling the polymer C synthesized in the step (S3) to 35-40 ℃, adding triethylamine for neutralization, adding deionized water with the solid content of 122-150% of that of the polymer C for shearing emulsification, decompressing to 0.03-0.05MPa, and removing acetone to obtain the self-emulsifying waterborne polyurethane acrylate oligomer with the solid content of 40-45%.
The test process comprises the following steps:
for comparison of paint film properties, control sample 1 was synthesized as provided in patent CN 101475679, and control sample 2 was synthesized as reported by AnilaAsif, as follows:
wherein control sample 1 was synthesized according to example 3 of patent CN 101475679: a nitrogen-purged reaction vessel was charged with 135.9g of TDI, 0.012g of BHT, 0.01324g of DBTDL, and 20ml of methyl ethyl ketone. The temperature was raised to 70 ℃. A mixture of 18g of polycarbonate diol (1000 molecular weight) and 20ml of butanone was added thereto and the mixture was dropped over 10 minutes. And (3) carrying out heat preservation reaction, measuring the NCO content, adding a catalyst after the NCO content of the system is 39%, adding 6.3g of DMPA and 50ml of butanone, and enabling the NCO content to reach 18.6% after 5 hours. 0.045g of MQ and a mixture of 45g of TMPTE and 50ml of butanone are added dropwise in one hour. When the NCO content of the system is below 0.35, 5g of a mixture consisting of pentaerythritol triacrylate, pentaerythritol triallyl ether and trimethylolpropane diallyl ether blocking agent is added, and when the NCO content of the system reaches 0.1%, 2g of anhydrous methanol is added for reaction for 30 minutes. Adding triethanolamine to neutralize and form salt, adding metered deionized water, and uniformly stirring to obtain a control sample 1.
Wherein control sample 2 was prepared according to the synthetic method reported in the Anila Asif et al literature: firstly, adding PEL and DMPA into a four-neck flask according to the mass ratio of 1: 4, heating to 140-160 ℃, adding a proper amount of catalyst p-toluenesulfonic acid under the protection of nitrogen, reacting for 2.5H, and vacuumizing until the acid value is less than 20 mg KOH/g to obtain first-generation hyperbranched polyester H10 (HB-PE); adding H10 and succinic anhydride in a certain ratio and a proper amount of catalyst Sn Cl 2.2H2O into a four-neck flask provided with a mechanical stirring thermometer condenser tube, dissolving with 50 g of 1, 4-dioxane, heating to 100 ℃, reacting at constant temperature for 24 hours, removing the solvent and water by reduced pressure distillation, dissolving with 1, 4-dioxane, and cooling to obtain succinic anhydride modified H10. Adding TDI, 10.6 g of 1, 4-dioxane and a small amount of DBTDL in a certain ratio into a four-neck flask provided with a mechanical stirring device, a thermometer and a constant pressure funnel, stirring and dissolving, placing in an ice-water bath until the temperature reaches 0-4 ℃, dropwise adding HPA, reacting for 2 hours, then using the water bath, keeping the temperature at 30 ℃ for 4 hours, then heating to 40 ℃, dropwise adding H10 modified by succinic anhydride, and reacting until the NCO content of the system is lower than 0.1. Then, TEA is dripped for neutralization, and deionized water is dripped for emulsification to obtain the aqueous hyperbranched polyurethane emulsion, wherein the solid content is controlled to be about 40%.
The self-emulsifying aqueous urethane acrylate oligomer prepared in examples 1 to 5 of the present invention, the control sample 1 and the control sample 2 were prepared into a coating material according to the following formulation, the viscosity was adjusted to 10 seconds/rock field NK-2 cup with deionized water, a gravity spray gun having a bore diameter of 1.0mm and an air pressure of 0.4MPa were used, and the coating material was sprayed on white PC (polycarbonate)Acid ester plastic) substrate, baking at 60 deg.C for 30 min, and curing with UV radiation at a radiation dose of 800mJ/cm2Paint films with the paint film thickness of 18-22 microns are prepared, and the paint films are placed for 24 hours and then are subjected to comparative tests:
the coating formula comprises:
formulation A Formulation B Formulation E Formulation F Formulation G Formulation H Formulation I
Example 1 80
Example 2 80
Example 3 80
Example 4 80
Example 5 80
Sample 1 80
Sample 2 80
Leveling agent 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Photoinitiator 3 3 3 3 3 3 3
Cosolvent 8 8 8 8 8 8 8
Deionized water 9.5 9.5 9.5 9.5 9.5 9.5 9.5
Description of the drawings: the leveling agent is German winning tego 410, the photoinitiator is German BASF Irgacure 1173, and the cosolvent is Dow chemical DPM.
The following table is a paint film property test:
Figure 79693DEST_PATH_IMAGE002
the appearance of the paint film is as follows: and (4) observing the leveling property and the fullness by visual measurement under natural light.
Film thickness: and (5) testing by a film thickness meter. The contrast gloss is ensured at the same film thickness.
Adhesion force: determined according to GB/T9286-1998.
Pencil hardness: measured according to GB/T6739-2006.
Gloss: measured according to GB/T9754-2007.
Color difference b value: and when the color difference meter is used for testing, the larger the b value is, the more obvious the yellow phase of the paint film is. The selected white PC substrate has no coating, the test b value is as follows: -2.02
B after fluorescent ultraviolet aging1The value: and b value measured by a color difference meter after the test according to the GB/T23987 + 2009 method is used as a standard of the fluorescent ultraviolet aging resistance. Test b uncoated white PC substrate selected1Comprises the following steps: -0.85
From the above data, it can be seen that: (1) in the paint film appearance, the appearance of the formulation A, the formulation B, the formulation E, the formulation F, the formulation G and the formulation H was flat and bright, and the orange peel of the formulation I was severe, so that the appearance of the self-emulsifiable aqueous urethane acrylate oligomer-based paints prepared in examples 1 to 5 and the comparative sample 1 was better. That is, the paint films formed from the coatings formulated from the self-emulsifying aqueous urethane acrylate oligomer prepared in examples 1 to 5 and sample 1 of the present invention showed better paint film appearance, as compared with sample 2.
(2) In terms of the thickness of the paint film, the thickness of the paint films formed by the paints formulated from the self-emulsifying aqueous urethane acrylate oligomer prepared in examples 1 to 5, and samples 1 and 2 were not very different from each other because the thickness of the paint films prepared in formula A, formula B, formula E, formula F, formula G, formula H and formula I was 20 μm to 22 μm.
(3) In terms of pencil hardness, the hardness of each of the formula A, the formula B, the formula E, the formula F and the formula G was 3H, and the hardness of each of the formula H and the formula I was H and 2H, and it can be seen that the hardness of the paint film formed by the paint formulated by the formula A, the formula B, the formula E, the formula F and the formula G was greater than the hardness of the paint film formed by the paint formulated by the formula H and the formula I. That is, the coating materials formulated from the self-emulsifiable aqueous urethane acrylate oligomer prepared in examples 1 to 5 of the present invention exhibited a greater hardness of the formed coating film as compared with samples 1 and 2.
(4) In terms of gloss, the gloss values for formula a, formula B, formula E, formula F and formula G were between 90 ° and 92 °, while the gloss values for formula H and formula I were 88 ° and 78 °. It can be seen that the coatings formulated from the self-emulsifying aqueous urethane acrylate oligomer prepared in examples 1 to 5 of the present invention exhibited better gloss in the formed paint film than those of samples 1 and 2.
(5) In terms of color difference, the B-value of the color difference between formula A, formula B, formula E, formula F and formula G is (-1.11) - (-1.01), while the B-value of the color difference between formula H and formula I is 0.5 and 0.8, and the larger the B-value, the more significant the yellow phase of the paint film is, so that the yellow phase of the paint film formed by the paint prepared from the self-emulsifying aqueous polyurethane acrylate oligomer prepared in examples 1-5 of the present invention is less significant and the yellowing degree is lower compared with sample 1 and sample 2.
(6) B for formulation A, B, E, F and G for resistance to fluorescent UV aging1A value of between 0.06 and 0.15, and b of formula H and formula I1Values of 2.67 and 1.82, b1The larger the value, the more severe the resistance of the paint film to fluorescent UV aging, from which it is understood that the self-emulsifiable aqueous polyurethane polypropylenes prepared in examples 1 to 5 of the present invention are comparable to those of samples 1 and 2The fluorescent ultraviolet aging resistance of a paint film formed by the paint prepared from the olefine acid ester oligomer is more remarkable.

Claims (9)

1. A preparation method of a self-emulsifying waterborne polyurethane acrylate oligomer is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
(S1) Synthesis of Trihydroxyl unsaturated monomer A having phosphate group:
adding 17-19% of phosphoric acid, 79-81% of glycidyl methacrylate, 0.9-1% of triphenylphosphine and 0.8-1% of polymerization inhibitor into a reactor according to mass percent, introducing nitrogen, heating to 90-100 ℃ for reaction, and stopping the reaction when the acid value is 1% of the initial acid value within 5-6 hours to obtain a trihydroxy unsaturated monomer A with a phosphate group;
(S2) Synthesis of hexahydroxy monomer B:
putting 40-61% of diisocyanate trimer and 9-17% of dimethylamide into a reactor according to the mass percentage, cooling to 0-15 ℃, slowly dripping 27-51% of diethanolamine, reacting for 2-3 hours, and stopping the reaction when the measured isocyanate group value is 0-0.1%; then heating to 80-85 ℃, decompressing to 0.03-0.05MPa to remove dimethyl amide and obtain a hexahydroxy monomer B;
(S3) Synthesis of Polymer C:
according to the mass percent, putting 1.7-4.9 percent of hexahydroxy monomer B, 4.2-6.6 percent of trihydroxy unsaturated monomer A, 18.04-36.8 percent of dihydric alcohol and 0.02-0.03 percent of polymerization inhibitor into a reaction kettle, adding 7-10 percent of acetone, heating to 40-45 ℃, introducing nitrogen, dripping a mixture of 0-0.26 percent of catalyst and 24-26 percent of diisocyanate, reacting for 1.5-1 hour, measuring isocyanate groups to a theoretical value, heating to 65-70 ℃, dripping a mixed solution of 3-3.8 percent of dimethylolpropionic acid, 3.3-7 percent of polyether dihydric alcohol and 3-3.8 percent of diformylamide, reacting for 0.5-1 hour, reacting for 1.5-2 hours, measuring the isocyanate groups to the theoretical value, dripping 16.4-21 percent of pentaerythritol triacrylate and 0.2-0.3 percent of catalyst into the reaction kettle, and measuring the isocyanate groups to the theoretical value, 0.14-0.20% of polymerization inhibitor, dropping for 0.5-1 hour, reacting for 3.5-5 hours, stopping reaction when the content of isocyanate group is 0% -0.1%, obtaining polymer C;
(S4) synthesis of self-emulsifying aqueous urethane acrylate oligomer:
and (S3) cooling the polymer C synthesized in the step (S3) to 35-40 ℃, adding triethylamine for neutralization, adding deionized water with the solid content of 122-150% of that of the polymer C for shearing and emulsification, decompressing to 0.03-0.05MPa, and removing acetone to obtain the water-based ultraviolet curing polyurethane acrylate oligomer with the solid content of 40-45%.
2. The method for preparing a self-emulsifying aqueous urethane acrylate oligomer according to claim 1, wherein: the polymerization inhibitor is hydroquinone or p-hydroxymethylphenol.
3. The method for preparing a self-emulsifying aqueous urethane acrylate oligomer according to claim 1, wherein: the diisocyanate trimer is toluene diisocyanate trimer, isophorone diisocyanate trimer or 1, 6-hexamethylene diisocyanate trimer.
4. The method for preparing a self-emulsifying aqueous urethane acrylate oligomer according to claim 1, wherein: the dihydric alcohol is one or two of polytetrahydrofuran ether dihydric alcohol with the molecular weight of 500-1000, polyester dihydric alcohol with the molecular weight of 500-1000, ethylene glycol, 1, 3-propylene glycol and 1, 4-butanediol.
5. The method for preparing a self-emulsifying aqueous urethane acrylate oligomer according to claim 1, wherein: the diisocyanate is one or more of 2, 4-toluene diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate.
6. The method for preparing a self-emulsifying aqueous urethane acrylate oligomer according to claim 5, wherein: the molar ratio of the 2, 4-toluene diisocyanate, isophorone diisocyanate and 1, 6-hexamethylene diisocyanate is in the range of 0:4:0-1:2: 1.
7. The method for preparing a self-emulsifying aqueous urethane acrylate oligomer according to claim 1, wherein: the catalyst is dibutyltin dilaurate, stannous octoate or organic bismuth.
8. The method for preparing a self-emulsifying aqueous urethane acrylate oligomer according to claim 1, wherein: the polyether glycol is polyethylene glycol with a molecular weight of 600-1000 or polypropylene glycol with a molecular weight of 600-1000.
9. A self-emulsifying aqueous urethane acrylate oligomer prepared by the method for preparing the self-emulsifying aqueous urethane acrylate oligomer according to any one of claims 1 to 8.
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