CN113387826A - Water-based ultraviolet curing resin and preparation method and application thereof - Google Patents

Water-based ultraviolet curing resin and preparation method and application thereof Download PDF

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CN113387826A
CN113387826A CN202110554184.6A CN202110554184A CN113387826A CN 113387826 A CN113387826 A CN 113387826A CN 202110554184 A CN202110554184 A CN 202110554184A CN 113387826 A CN113387826 A CN 113387826A
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aqueous
ultraviolet curing
methanol
acrylate
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CN113387826B (en
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罗青宏
张栋祺
刘晓暄
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Guangdong University of Technology
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    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/16—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids
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    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Abstract

The invention discloses a water-based ultraviolet curing resin and a preparation method and application thereof. The water-based ultraviolet curing resin provided by the invention has two ammonium salt hydrophilic groups, water can be directly diluted by adding the water, the water dilutability effect is excellent, the dilution viscosity is low, an acrylate double bond functional group is introduced, a photoinitiator and a small amount of water are added, the mixture is uniformly stirred, and the product with higher hardness can be formed by ultraviolet irradiation curing for 1-3 s, and the curing speed is high. The transparent solution of the water-based ultraviolet curing resin prepared by the invention is an effective resin component with acrylate double bonds and capable of being cured, and redundant solvent is removed in the reaction, so that 100 percent of full solid content can be realized, and the water-based ultraviolet curing resin can be widely applied to ultraviolet curing coatings, printing ink and additive manufacturing.

Description

Water-based ultraviolet curing resin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to a water-based ultraviolet curing resin, and a preparation method and application thereof.
Background
With the increasing awareness of environmental protection, the attention is paid to solvent-free and water-based products of end-use coatings, adhesives, inks, and the like. In recent years, due to the implementation of national environmental protection policies, more and more enterprises have paid attention to and participated in the development of aqueous resins/coatings/inks. However, the existing water-based UV resin products contain a large amount of water, so that the drying speed of the products is slow, the solid content is low, and meanwhile, the volatilization of the water can generate energy consumption. In addition, the existing aqueous UV resin also has the defects of high construction difficulty and the like caused by poor water dilutability, the traditional long-chain aqueous polyurethane or aqueous polymer has certain hydrophilicity, but the hydrophilicity is limited, when water is added, the resin is firstly swelled (the viscosity is not reduced but increased), after water is continuously added into the resin, a resin-water system is slowly converted from 'water in oil' into 'oil in water' and then into emulsion, then the water is added, the viscosity of the resin is reduced, and the water dilutability cannot meet the requirements of an application end. Therefore, the application end puts demands on high solid content and good water dilutability on the aqueous UV resin.
CN112321842A discloses an ultraviolet light cured hyperbranched acrylic resin and a manufacturing method thereof, the manufacturing method of the ultraviolet light cured hyperbranched acrylic resin specifically comprises the following steps: (1) adding multifunctional acrylate and polymerization inhibitor into a reaction bottle, and stirring; (2) adding polyamine diluted by a solvent into a dropping funnel according to a certain proportion, slowly dropping, slowly heating to 60 ℃ step by step after dropping for about one hour, and reacting for three hours; (3) and (3) after the reaction is finished, carrying out reduced pressure distillation, and removing all the solvent to obtain the solvent-free hyperbranched acrylic resin. The ultraviolet light curing hyperbranched acrylate resin does not provide a good solution for the high solid content and good water dilutability of the water-based resin aiming at the improvement of the curing speed and the reduction of the viscosity of the resin. CN110615885A discloses a water-based ultraviolet-curing polyurethane resin, a preparation method and an application thereof, the prepared water-based polyurethane resin is a water-based polyurethane emulsion capable of being cured by UV, but the solid content is low, generally the solid content is 30-45%, and the requirement of high solid content even full solid content cannot be met.
Disclosure of Invention
The invention aims to overcome the defect that the solid content and the hydrophilicity of the existing waterborne ultraviolet curing resin can not meet the requirements of related terminal application, and provides the waterborne ultraviolet curing resin which contains hydrophilic ammonium salt substances, has good water solubility, low dilution viscosity and high curing speed, can realize 100 percent of total solid content, has higher film-forming hardness and is scratch resistant.
The invention further aims to provide a preparation method of the water-based ultraviolet curing resin.
The invention also aims to provide application of the water-based ultraviolet curing resin in ultraviolet curing coatings, printing ink and additive manufacturing.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the structure of the water-based ultraviolet curing resin is shown as the formula I:
Figure RE-GDA0003186781980000021
wherein R is1、R2、R3、R4Is composed of
Figure RE-GDA0003186781980000022
(pentaerythritol triacrylate),
Figure RE-GDA0003186781980000023
(pentaerythrityl)Alcohol tetraacrylate),
Figure RE-GDA0003186781980000024
(1, 6-hexanediol diacrylate),
Figure RE-GDA0003186781980000025
(dipropylene glycol diacrylate or tripropylene glycol diacrylate),
Figure RE-GDA0003186781980000026
(trimethylolpropane triacrylate),
Figure RE-GDA0003186781980000027
(hydroxyethyl acrylate),
Figure RE-GDA0003186781980000028
One or more of (hydroxyethyl methacrylate); r5is-Cl-CH3COO、-CH2CH2COO or a plurality of COOs.
From the general formula I, the waterborne ultraviolet curing resin has a hyperbranched structure, has lower viscosity than a resin with a long-chain structure, and is convenient for subsequent construction operation. In addition, each molecule of the resin has two ammonium salt hydrophilic groups, so that water can be used as a good solvent of the resin, namely when water is added into the resin, the resin is directly diluted, and the water dilutability effect is excellent.
The water-based ultraviolet curing resin is transparent and uniform liquid at room temperature, acrylate double bond functional groups are introduced, the photoinitiator and a small amount of water are added, the mixture is uniformly stirred, the curing speed is high through ultraviolet irradiation curing, and a product with high hardness can be formed within 1-3 s.
The aqueous ultraviolet curing resin disclosed by the invention is neutralized into salt by using hydrochloric acid or carboxylic acid, the dispersion medium is water during application, the emission of a volatile organic solvent is greatly reduced, and the resin is environment-friendly, has higher acrylate double bond content, high photocuring speed, low energy consumption, convenience in construction and higher economic benefit.
Further preferably, wherein, R1And R2Is composed of
Figure RE-GDA0003186781980000031
Figure RE-GDA0003186781980000032
Figure RE-GDA0003186781980000033
R3Is composed of
Figure RE-GDA0003186781980000034
Figure RE-GDA0003186781980000035
R4Is composed of
Figure RE-GDA0003186781980000036
Figure RE-GDA0003186781980000037
R5is-Cl.
Further, the water-based ultraviolet curing resin has structural formulas II to VI:
Figure RE-GDA0003186781980000041
the invention also discloses a preparation method of the water-based ultraviolet curing resin, which comprises the following steps:
s1, adding methanol or ethanol into an acrylate monomer containing a polymerization inhibitor, and uniformly mixing to prepare a methanol or ethanol solution of acrylate;
s2, mixing and activating methanol or ethanol and ethylenediamine to obtain an activated ethylenediamine/methanol solution;
s3, adding the activated ethylenediamine/methanol solution into methanol or ethanol solution of acrylic ester, keeping the temperature constant at 40-50 ℃ in the adding process, adding an end capping agent for end capping reaction after finishing dropwise adding, and continuing to react for 5-6 h to ensure complete reaction to obtain a reaction product;
and S4, adding a salt forming agent into the reaction product of the S3, continuously reacting for 1-1.5 h at normal temperature, ensuring that the tertiary amine and the salt forming agent are completely reacted to obtain a transparent solution, and removing the methanol solution to prepare the aqueous ultraviolet curing resin.
Among them, it should be noted that:
the salt forming agent is one or more of hydrochloric acid, acetic acid and acrylic acid.
In order to ensure the purity of the product, the ethylenediamine is analytically pure.
In order to ensure the purity of the product, the solvent methanol is analytically pure and is subjected to molecular sieve drying and water removal treatment.
The methanol solution activated by the ethylenediamine also has the function of a catalyst, and can be used for accelerating the reaction speed of the Michael addition reaction of the ethylenediamine and the acrylic substance.
The end capping agent of the invention is: hydroxyethyl methacrylate or hydroxyethyl acrylate.
The transparent solution obtained by the preparation method of the water-based ultraviolet curing resin is an effective resin component which has acrylate double bonds and can be cured, and redundant solvent is removed in the reaction, so the solid content of the water-based ultraviolet curing resin is 100 percent.
Preferably, the mass ratio of the acrylate to the ethylenediamine to the salt forming agent to the end capping agent is 20-45: 1.5-4: 2-8: 10-30.
Wherein the acrylate, the ethylenediamine, the salt forming agent and the end capping agent are as follows: the mass ratio of the methanol to the polymerization inhibitor is 20-45: 1.5-4: 2-8: 10-30: 40-55: 0.05-0.08.
More preferably, the mass ratio of the acrylate to the ethylenediamine to the salt forming agent to the end capping agent is 25-35: 1.8-2.5: 2-4: 15-25.
Wherein the mass ratio of the acrylate to the ethylenediamine to the salt forming agent to the blocking agent to the methanol to the polymerization inhibitor is 25-35: 1.8-2.5: 2-4: 15-25: 45-50: 0.05-0.08.
Preferably, the acrylate in S1 is one or more of pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, or hydroxyethyl acrylate.
Preferably, the polymerization inhibitor in S1 is tert-butyl hydroquinone, p-hydroxyanisole or 2-methoxyhydroquinone.
Meanwhile, the invention also specifically protects the application of the water-based ultraviolet curing resin in ultraviolet curing coatings, printing ink and additive manufacturing.
In practical application, the material containing the water-based ultraviolet curing resin is cured by ultraviolet light, and is cured by ultraviolet light irradiation with the power of 80-100W/cm, wherein the curing time is 1-3 s.
And further preferably, the water-based ultraviolet curing resin can be diluted by adding water in the application, the adding amount of the water is 5-10% of the mass of the water-based ultraviolet curing resin, and the water-based ultraviolet curing resin has good hydrophilic dilutability.
The waterborne ultraviolet curing resin disclosed by the invention contains an ammonium chloride salt structure, has good hydrophilicity and an excellent water dilutability effect, only a proper amount of water (5-10%) needs to be added, the viscosity is rapidly reduced, and the construction viscosity can reach 100-300 cP.
Specific application modes can be referred to as follows:
the viscosity of the water-based ultraviolet curing resin is adjusted by using reactive diluent monomer or water, and the photoinitiator is added for even stirring. The prepared coating liquid is scraped on a glass plate by a four-side coater with the surface of 90 mu m, and the film can be completely cured, has higher hardness and is scratch-resistant by irradiating for 1-3 s through ultraviolet light with the power of an ultraviolet lamp of 80-100W/cm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a water-based ultraviolet curing resin which has two ammonium salt hydrophilic groups, water can be directly diluted by adding the water, the water dilutability effect is excellent, the dilution viscosity is low, and the construction viscosity requirement of 100-300 cP can be met by adding water with the resin content of 5-10%.
(2) The waterborne ultraviolet curing resin provided by the invention introduces acrylate double bond functional groups, is added with a photoinitiator and a small amount of water, is uniformly stirred, and is cured by ultraviolet irradiation for 1-3 s to form a product with higher hardness, the curing speed is high, the hardness can reach 2-3H, and the product is scratch-resistant.
(3) The transparent solution of the water-based ultraviolet curing resin is an effective resin component which has acrylate double bonds and can be cured, and redundant solvent is removed in the reaction, so that 100 percent of full solid content can be realized.
Drawings
Fig. 1 is an infrared spectrum of the aqueous uv curable resin of example 1.
Fig. 2 is an infrared spectrum of the aqueous uv curable resin of example 2.
Fig. 3 is an infrared spectrum of the aqueous uv curable resin of example 3.
Fig. 4 is an infrared spectrum of the aqueous uv curable resin of example 4.
Fig. 5 is an infrared spectrum of the aqueous uv curable resin of example 5.
Fig. 6 is a fully solid aqueous uv curable acrylate resin.
Fig. 7 is a 40% solids aqueous uv curable acrylate resin.
Fig. 8 is a 20% solids aqueous uv curable acrylate resin.
Fig. 9 is a diagram of an aqueous uv-curable acrylate resin from full solids to 80%, 60%, 40% and 20% solids.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the patent.
Example 1
The structure of the water-based ultraviolet curing resin is as follows:
Figure RE-GDA0003186781980000071
the structure of the water-based ultraviolet curing resin is detected and identified by infrared, and a specific infrared spectrum is shown in figure 1.
The preparation method of the water-based ultraviolet curing resin comprises the following steps:
s1, adding 29.92 parts by mass of pentaerythritol triacrylate (PETA) into a four-neck flask, adding 0.08 part by mass of polymerization inhibitor p-hydroxyanisole (MEHQ), installing the four-neck flask and a reflux condenser tube on a mechanical stirrer, and stirring at room temperature to dissolve the four-neck flask and the MEHQ; then, adding 45 parts by mass of Methanol (MEOH) into the four-neck flask, and stirring uniformly; then adding 7.77 parts by mass of weighed hydroxyethyl acrylate (HEA) to obtain Methanol (MEOH) of pentaerythritol triacrylate (PETA) and a hydroxyethyl acrylate (HEA) solution I (methanol solution of acrylate);
s2, weighing 5 parts by mass of a proper amount of Methanol (MEOH) into a beaker, adding 2.01 parts by mass of weighed ethylenediamine, uniformly stirring, and pouring the mixture into a constant-pressure funnel to obtain an activated ethylenediamine solution II;
s3, under the conditions of room temperature and mechanical stirring, dropwise adding an ethylene diamine solution II activated by Methanol (MEOH) into a Methanol (MEOH) and hydroxyethyl acrylate (HEA) solution I of pentaerythritol triacrylate (PETA), observing heat release, and cooling with ice water at the temperature of over 50 ℃; immediately adding 7.78 parts by mass of hydroxyethyl acrylate (HEA) after dropwise adding the ethylenediamine solution II activated by Methanol (MEOH), carrying out end-capping reaction, and reacting for 6 hours at room temperature under the condition of mechanical stirring to obtain a reaction product;
s4, slowly adding 2.44 parts by mass of a salt forming agent hydrochloric acid into a four-neck flask under the conditions of room temperature and mechanical stirring, continuously stirring for 1h with heat release when the solution in the four-neck flask becomes turbid, obtaining a transparent solution, pouring the transparent solution in the four-neck flask into a single-neck flask, and evaporating a solvent Methanol (MEOH) at 60 ℃ and under the negative pressure of 0.1KPa by using a rotary evaporator to obtain the aqueous ultraviolet curing acrylate resin.
Example 2
The structure of the water-based ultraviolet curing resin is as follows:
Figure RE-GDA0003186781980000081
the structure of the water-based ultraviolet curing resin is detected and identified by infrared, and a specific infrared spectrum is shown in figure 2.
The preparation method of the water-based ultraviolet curing resin comprises the following steps:
s1, adding 27.69 parts by mass of trimethylolpropane triacrylate (TMPTA) into a four-neck flask, adding 0.08 part by mass of polymerization inhibitor p-hydroxyanisole (MEHQ), installing the four-neck flask and a reflux condenser tube on a mechanical stirrer, and stirring at room temperature to dissolve the materials; then, 46 parts by mass of Methanol (MEOH) is added into the four-neck flask, and the mixture is stirred uniformly; then adding 7.24 parts by weight of weighed hydroxyethyl acrylate (HEA) to obtain Methanol (MEOH) of trimethylolpropane triacrylate (TMPTA) and a hydroxyethyl acrylate (HEA) solution I (methanol solution of acrylate);
s2, weighing a proper amount of Methanol (MEOH)4 parts by mass in a beaker, adding weighed 1.87 parts by mass of ethylenediamine, uniformly stirring, and pouring the mixture into a constant-pressure funnel to obtain an activated ethylenediamine solution II;
s3, dropwise adding an ethylenediamine solution II activated by Methanol (MEOH) into a Methanol (MEOH) and hydroxyethyl acrylate (HEA) solution I of trimethylolpropane triacrylate (TMPTA) at room temperature under the condition of mechanical stirring, observing heat release, and cooling with ice water at the temperature of over 50 ℃; immediately adding 10.85 parts by mass of hydroxyethyl acrylate (HEA) after dropwise adding the ethylenediamine solution II activated by Methanol (MEOH), carrying out end-capping reaction, and reacting for 6 hours at room temperature under the condition of mechanical stirring;
s4, slowly adding 2.27 parts by mass of a salt forming agent acetic acid into the four-neck flask under the condition of room temperature and mechanical stirring, wherein the solution in the four-neck flask becomes turbid and is stirred for 1 hour continuously along with heat release to obtain a transparent solution. Pouring the transparent solution in the four-neck flask into the single-neck flask, and evaporating out the solvent Methanol (MEOH) by using a rotary evaporator at 60 ℃ and under the negative pressure of 0.1KPa to obtain the aqueous ultraviolet curing acrylate resin.
Example 3
The structure of the water-based ultraviolet curing resin is as follows:
Figure RE-GDA0003186781980000091
the structure of the water-based ultraviolet curing resin is detected and identified by infrared, and a specific infrared spectrum is shown in figure 3.
The preparation method of the water-based ultraviolet curing resin comprises the following steps:
s1, adding 31.65 parts by mass of trimethylolpropane triacrylate (TMPTA) into a four-neck flask, adding 0.08 part by mass of polymerization inhibitor p-hydroxyanisole (MEHQ), installing the four-neck flask and a reflux condenser tube on a mechanical stirrer, and stirring at room temperature to dissolve the materials; then, 42 parts by mass of Methanol (MEOH) is added into the four-neck flask, and the mixture is stirred uniformly; then adding 9.27 parts by weight of weighed hydroxyethyl methacrylate (HEMA) to obtain Methanol (MEOH) of trimethylolpropane triacrylate (TMPTA) and a hydroxyethyl methacrylate (HEMA) solution I (methanol solution of acrylate);
s2, weighing 3 parts by mass of Methanol (MEOH) in a beaker, adding 2.14 parts by mass of weighed ethylenediamine, uniformly stirring, and pouring the mixture into a constant-pressure funnel to obtain an activated ethylenediamine solution II;
s3, under the conditions of room temperature and mechanical stirring, dropwise adding an ethylenediamine solution II activated by Methanol (MEOH) into a Methanol (MEOH) and hydroxyethyl methacrylate (HEMA) solution I of trimethylolpropane triacrylate (TMPTA), observing heat release, and cooling with ice water at the temperature of over 50 ℃; immediately adding 9.26 parts by mass of hydroxyethyl methacrylate (HEMA) after dropwise adding the ethylenediamine solution II activated by Methanol (MEOH), carrying out end-capping reaction, and reacting for 6 hours at room temperature under the condition of mechanical stirring;
s4, slowly adding 2.60 parts by mass of a salt forming agent hydrochloric acid into the four-neck flask under the condition of room temperature and mechanical stirring, wherein the solution in the four-neck flask becomes turbid and is stirred for 1 hour continuously along with heat release, and a transparent solution is obtained. Pouring the transparent solution in the four-neck flask into the single-neck flask, and evaporating out the solvent Methanol (MEOH) by using a rotary evaporator at 60 ℃ and under the negative pressure of 0.1KPa to obtain the aqueous ultraviolet curing acrylate resin.
Example 4
The structure of the water-based ultraviolet curing resin is as follows:
Figure RE-GDA0003186781980000111
the structure of the water-based ultraviolet curing resin is detected and identified by infrared, and a specific infrared spectrum is shown in figure 4.
The preparation method of the water-based ultraviolet curing resin comprises the following steps:
s1, adding 31.65 parts by mass of 1, 6-hexanediol diacrylate into a four-neck flask, adding 0.08 part by mass of polymerization inhibitor p-hydroxyanisole (MEHQ), installing the four-neck flask and a reflux condenser pipe on a mechanical stirrer, and stirring at room temperature to dissolve the mixture; then, 42 parts by mass of Methanol (MEOH) is added into the four-neck flask, and the mixture is stirred uniformly; then adding 9.27 parts by weight of weighed hydroxyethyl methacrylate (HEMA) to obtain Methanol (MEOH) of 1, 6-hexanediol diacrylate and a hydroxyethyl methacrylate (HEMA) solution I (methanol solution of acrylate);
s2, weighing 3 parts by mass of Methanol (MEOH) in a beaker, adding 2.14 parts by mass of weighed ethylenediamine, uniformly stirring, and pouring the mixture into a constant-pressure funnel to obtain an activated ethylenediamine solution II;
s3, dropwise adding an ethylenediamine solution II activated by Methanol (MEOH) into a Methanol (MEOH) and hydroxyethyl methacrylate (HEMA) solution I of 1, 6-hexanediol diacrylate at room temperature under the condition of mechanical stirring, observing heat release, and cooling with ice water at the temperature of over 50 ℃; immediately adding 9.26 parts by mass of hydroxyethyl methacrylate (HEMA) after dropwise adding the ethylenediamine solution II activated by Methanol (MEOH), carrying out end-capping reaction, and reacting for 6 hours at room temperature under the condition of mechanical stirring;
s4, slowly adding 2.60 parts by mass of a salt forming agent hydrochloric acid into the four-neck flask under the condition of room temperature and mechanical stirring, wherein the solution in the four-neck flask becomes turbid and is stirred for 1 hour continuously along with heat release, and a transparent solution is obtained. Pouring the transparent solution in the four-neck flask into the single-neck flask, and evaporating out the solvent Methanol (MEOH) by using a rotary evaporator at 60 ℃ and under the negative pressure of 0.1KPa to obtain the aqueous ultraviolet curing acrylate resin.
Example 5
The structure of the water-based ultraviolet curing resin is as follows:
Figure RE-GDA0003186781980000121
the structure of the aqueous ultraviolet curing resin is identified by infrared detection, and a specific infrared spectrum is shown in figure 5.
The preparation method of the water-based ultraviolet curing resin comprises the following steps:
s1, adding 31.65 parts by mass of tripropylene glycol diacrylate into a four-neck flask, adding 0.08 part by mass of polymerization inhibitor p-hydroxyanisole (MEHQ), installing the four-neck flask and a reflux condenser pipe on a mechanical stirrer, and stirring at room temperature to dissolve the tripropylene glycol diacrylate; then, 42 parts by mass of Methanol (MEOH) is added into the four-neck flask, and the mixture is stirred uniformly; then adding 9.27 parts by weight of weighed hydroxyethyl methacrylate (HEMA) to obtain Methanol (MEOH) of 1, 6-hexanediol diacrylate and a hydroxyethyl methacrylate (HEMA) solution I (methanol solution of acrylate);
s2, weighing 3 parts by mass of Methanol (MEOH) in a beaker, adding 2.14 parts by mass of weighed ethylenediamine, uniformly stirring, and pouring the mixture into a constant-pressure funnel to obtain an activated ethylenediamine solution II;
s3, dropwise adding an ethylenediamine solution II activated by Methanol (MEOH) into a Methanol (MEOH) and hydroxyethyl methacrylate (HEMA) solution I of 1, 6-hexanediol diacrylate at room temperature under the condition of mechanical stirring, observing heat release, and cooling with ice water at the temperature of over 50 ℃; immediately adding 9.26 parts by mass of hydroxyethyl methacrylate (HEMA) after dropwise adding the ethylenediamine solution II activated by Methanol (MEOH), carrying out end-capping reaction, and reacting for 6 hours at room temperature under the condition of mechanical stirring;
s4, slowly adding 2.60 parts by mass of a salt forming agent hydrochloric acid into the four-neck flask under the condition of room temperature and mechanical stirring, wherein the solution in the four-neck flask becomes turbid and is stirred for 1 hour continuously along with heat release, and a transparent solution is obtained. Pouring the transparent solution in the four-neck flask into the single-neck flask, and evaporating out the solvent Methanol (MEOH) by using a rotary evaporator at 60 ℃ and under the negative pressure of 0.1KPa to obtain the aqueous ultraviolet curing acrylate resin.
Example 6
When the aqueous ultraviolet curing acrylate resin is applied as a coating, the process is implemented according to the following proportion and conditions:
Figure RE-GDA0003186781980000131
10 parts by mass of each of the aqueous ultraviolet-curable acrylate resins obtained in examples 1 to 5 was added with 0.15 part by mass of a photoinitiator TPO to prepare a coating solution. And scraping the prepared coating liquid on a plane glass plate by using a four-side coater with a 90-micron surface, irradiating for 1-3 s by using a UV-LED ultraviolet lamp, and curing to form a film.
The pencil hardness of the uv curable acrylate resin after the above curing was tested. The test results are given in table 1 below:
TABLE 1
Figure RE-GDA0003186781980000132
As can be seen from the data in Table 1, the UV-curable acrylate resin of the present invention has high hardness, which can reach 2H-3H, and has good example 7
Mixing the water-based ultraviolet curing acrylate resin obtained in the example 1 with deionized water according to the following mixture ratio in parts by weight in the following table 2:
TABLE 2
Figure RE-GDA0003186781980000133
Figure RE-GDA0003186781980000141
As can be seen from Table 2, when 1.5 parts by mass of deionized water is added, the viscosity of the resin is immediately reduced from 11540cP to 200cP, so that the dilution and viscosity reduction effects of water on the resin are obvious, and the application construction viscosity can be achieved by adding 5-10% of deionized water.
TABLE 3
Solid content 100％ 95％ 90％ 80％ 60％
Resin composition 15 14.25 13.5 12 9
Deionized water 0 0.75 1.5 3 6
Example 2 viscosity (cP/25 ℃ C.) 11320 300 205 100 90
Example 3 viscosity (cP/25 ℃ C.) 11000 297 210 115 88
Example 4 viscosity (cP/25 ℃ C.) 11810 250 150 100 97
Example 5 viscosity (cP/25 ℃ C.) 10960 278 148 95 86
Among them, fig. 6 to 8 are experimental results of the compatibility between the aqueous uv-curable acrylate resin of the present invention and water, and fig. 9 shows that the aqueous uv-curable acrylate resin of the present invention has good compatibility with water, when the appearance changes from water-in-oil (transparent) to oil-in-water (emulsion) from full solid content to 80% solid content, 60% solid content, 40% solid content and 20% solid content.
Example 8
The all-solid-content water-dilutable waterborne ultraviolet-curing acrylate resin obtained in example 1, example 2 and example 3 is placed in an oven at 60 ℃ for heat storage stability test, and the resin stability is shown in the following table 1:
TABLE 4
Numbering Example 1 resin Example 2 resin Example 3 resin
Thermal storage stability at 60 ℃ More than 15 days More than 15 days More than 15 days
From the above results, it is clear that the aqueous ultraviolet-curable acrylate resin of the present invention does not cause curing blocking during thermal action and has good thermal stability.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The water-based ultraviolet curing resin is characterized by having a structure shown in a formula I:
Figure FDA0003076441550000011
wherein R is1、R2、R3、R4Is composed of
Figure FDA0003076441550000012
Figure FDA0003076441550000013
Figure FDA0003076441550000014
One or more of (a), (b), (c), (d); r5is-Cl-CH3COO、-CH2CH2COO or a plurality of COOs.
2. The aqueous UV curable resin according to claim 1, wherein R is R1And R2Is composed of
Figure FDA0003076441550000015
Figure FDA0003076441550000016
R3Is composed of
Figure FDA0003076441550000017
Figure FDA0003076441550000018
R4Is composed of
Figure FDA0003076441550000021
Figure FDA0003076441550000022
R5is-Cl.
3. The aqueous ultraviolet-curable resin of claim 2, wherein the aqueous ultraviolet-curable resin has structural formulas ii to vi:
Figure FDA0003076441550000023
4. a method for preparing the aqueous uv curable resin according to claim 1 or 2, comprising the steps of:
s1, adding methanol or ethanol into an acrylate monomer containing a polymerization inhibitor, and uniformly mixing to prepare a methanol or ethanol solution of acrylate;
s2, mixing and activating methanol or ethanol and ethylenediamine to obtain an activated ethylenediamine/methanol solution;
s3, adding the activated ethylenediamine/methanol solution into methanol or ethanol solution of acrylic ester, keeping the temperature constant at 40-50 ℃ in the adding process, adding an end capping agent for end capping reaction after finishing dropwise adding, and continuing to react for 5-6 h to ensure complete reaction to obtain a reaction product;
and S4, adding a salt forming agent into the reaction product of the S3, continuously reacting for 1-1.5 h at normal temperature, ensuring that the tertiary amine and the salt forming agent are completely reacted to obtain a transparent solution, and removing the methanol solution to prepare the aqueous ultraviolet curing resin.
5. The preparation method of the aqueous ultraviolet curing resin according to claim 4, wherein the mass ratio of the acrylate, the ethylenediamine, the salt forming agent and the end capping agent is 20-45: 1.5-4: 2-8: 10-30.
6. The method for preparing the aqueous ultraviolet curing resin according to claim 5, wherein the mass ratio of the acrylate, the ethylenediamine, the salt forming agent and the end capping agent is 25-35: 1.8-2.5: 2-4: 15-25.
7. The method for preparing the aqueous UV curable resin according to claim 4, wherein the acrylate is one or more of pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, or hydroxyethyl acrylate.
8. Use of the aqueous UV-curable resin according to any one of claims 1 to 3 in UV-curable coatings, inks and additive manufacturing.
9. The application of claim 8, wherein the application is cured by ultraviolet irradiation with power of 80-100W/cm for 1-3 s.
10. The use according to claim 8, wherein the aqueous UV-curable resin is diluted with water in an amount of 5-10% by mass of the aqueous UV-curable resin.
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