CN113583202A - Thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin - Google Patents

Thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin Download PDF

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CN113583202A
CN113583202A CN202110901009.XA CN202110901009A CN113583202A CN 113583202 A CN113583202 A CN 113583202A CN 202110901009 A CN202110901009 A CN 202110901009A CN 113583202 A CN113583202 A CN 113583202A
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led
water
hetx
thioxanthone
acid
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陆明
许钧强
匡民明
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Yingde Kedi Pigment Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

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Abstract

The invention relates to thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin and a preparation method thereof, the LED-UV water-based resin contains two active groups and a thioxanthone photoinitiation group, and has the following characteristics: 1) energy migration and intermolecular reaction in a polymer chain are easier, and the self-initiation activity is high under the irradiation of an LED-UV lamp; 2) the space between the photoactive group and the main chain is shortened, and the photosensitivity is improved; 3) excellent system compatibility; 4) the defects caused by a micromolecular photoinitiator are overcome; the LED-UV water-based paint prepared by the invention has excellent adhesive force, water resistance, aging resistance, chemical resistance and odor purification effect, has the characteristics of high gloss, high wear resistance, high fullness, impact resistance, good flexibility and the like, and is widely used for LED colored perfume bottle paint, LED wood paint, LED alloy paint, LED circuit board ink, LED plastic paint and the like.

Description

Thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin
Technical Field
The invention relates to a water-based light-cured resin, in particular to a thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin and a preparation method thereof, belonging to the technical field of synthetic resins.
Background
In recent years, environmental friendly coatings, including high solids and solventless coatings, waterborne coatings, powder coatings and photocurable coatings, have been rapidly developed. The ultraviolet curing has the advantages of fast reaction, room temperature operation, low energy consumption, no solvent, little pollution and the like. The photocuring technology has the advantages of fast curing, high production efficiency, energy conservation, environmental protection, high quality, economy, suitability for various base materials and the like, and is widely applied to various industries such as printing, packaging, advertising, building materials, decoration, electronics, communication, computers, shops, automobiles, aviation, aerospace, instruments and meters, sports, sanitation and the like.
The water-based UV resin is mainly applied to UV coating and UV printing ink, and comprises water-based UV paper gloss oil, water-based UV wood paint, water-based UV metal paint, water-based UV flexo printing ink, water-based UV gravure printing ink, water-based UV silk-screen printing ink and the like. Part of the aqueous UV resin product can meet the requirements of automobile coatings, such as automobile priming paint, finishing varnish and the like. With the intensive research on the aqueous light curing system, the variety of the aqueous UV resin is more diversified, and the application field is continuously expanded.
The water-based UV coating inherits and develops the characteristics of the traditional UV coating and the water-based coating, and has the advantages of safety, environmental protection, energy conservation, high efficiency, adjustable viscosity, capability of realizing thin-layer spraying, lower cost and the like. In addition, the aqueous UV resin is a high molecular weight aqueous dispersion, the viscosity of the aqueous UV resin can be adjusted by water, so that the harm of an active diluent is avoided, the contradiction that the hardness and the flexibility of the traditional UV coating are difficult to be considered is solved, and in recent years, the rapid development of the aqueous UV coating becomes a main direction for the development of the coating.
The water-based epoxy acrylate has the advantages of low price, high coating hardness, good adhesion, high glossiness, good chemical resistance and the like, but also has the defects of poor brittleness, poor yellowing resistance and the like of the traditional bisphenol A epoxy resin. And the aliphatic epoxy resin with excellent physical and mechanical properties and yellowing resistance is selected to replace the traditional bisphenol A epoxy resin to be used as a matrix of the waterborne UV epoxy acrylate, so that the comprehensive properties of the resin are greatly improved. Generally, the epoxy resin is esterified by adopting acrylic acid to obtain Epoxy Acrylate (EA), hydroxyl in the epoxy acrylate is utilized to react with anhydride (such as maleic anhydride, trimellitic anhydride and the like) to introduce hydrophilic groups, and then organic amine is utilized to neutralize to obtain the waterborne epoxy acrylate resin (EB). The waterborne polyurethane acrylate has the advantages of good wear resistance, chemical resistance, low temperature resistance, flexibility and the like, and is the most commercialized waterborne UV resin at present; in recent years, the performance of the water-based UV polyurethane acrylate makes a major breakthrough, the product performance meets the requirements of automobile coatings, and the water-based UV polyurethane acrylate can be used for automobile primers, finishing coats, finishing varnishes and the like.
The water-based epoxy acrylate has the characteristics of high hardness, good adhesive force, high glossiness, good chemical resistance and the like, but has poor flexibility and high brittleness. The waterborne polyurethane acrylate has the characteristics of good wear resistance, good flexibility and the like, but has poor weather resistance. The two resins are effectively compounded by adopting methods of chemical modification, physical blending and hybrid grafting, and the advantages of the two resins are exerted, so that the development of a high-performance photocuring epoxy acrylate/polyurethane acrylate composite system with the advantages of the two resins is the key direction of the research of the water-based UV system.
The aqueous UV system mainly comprises aqueous UV resin, a photoinitiator and water, the photoinitiator is mostly organic micromolecules, is poor in yellowing resistance and migration resistance, has certain toxicity, can generate harmful photodecomposition products (such as benzaldehyde), can generate adverse effects on environment and human health, and restricts the application of an ultraviolet curing technology in the fields of printing ink, food packaging and the like, so that the ultraviolet curing oligomer with the self-initiation function is more and more emphasized.
The oligomer products with photoinitiating function on the market at present are Drewrad series products developed by Ashland company in the United states, a type of oligomer containing beta ketoester self-initiating function; another class of oligomers contains photoinitiator groups (benzoin, 1173, 184, 2959). Bomar corporation, USA, incorporates a macromolecular photoinitiator group into an oligomer molecule. However, these self-initiating UV systems require the use of reactive diluents and are not suitable for aqueous systems.
Chinese patent CN107602851A discloses an aqueous self-initiated visible light unsaturated polyester amide urea resin and a preparation method thereof, which comprises the steps of mixing dibasic acid, dihydric alcohol and urea, heating and reacting at 160-210 ℃ for 200-600 min under the protection of nitrogen, distilling to remove water, adding pentaerythritol triallyl ether, heating and reacting at 160-210 ℃ for 60-120 min, adding cinnamic acid, heating and reacting at 160-210 ℃ for 60-120 min, and cooling to obtain the product; the unsaturated polyester amide urea resin disclosed by the invention not only has self-initiation property, but also has water solubility and visible light curing, and is applied to preparation of a water-based self-initiation visible light curing coating.
Chinese patent CN107254251A discloses a waterborne UV polyurethane acrylate dispersion with self-initiation function and a preparation method thereof, wherein the waterborne UV polyurethane acrylate dispersion comprises the following components: 10-20 parts of polyester polyol or polyether polyol; 10-30 parts of diisocyanate; 2-10 parts of polyhydroxycarboxylic acid; 0.04-0.2 part of a catalyst; 5-15 parts of an organic solvent; 1-5 parts of hydroxyurea; 0.1-0.6 part of polymerization inhibitor; 10-30 parts of monohydroxy acrylate monomer; 15-35 parts of oligomer containing photoinitiation groups and terminal hydroxyl groups; 1-5 parts of organic amine; 140-180 parts of deionized water. The photoinitiating group is one or the combination of hydroxyl-containing photoinitiator Darocur 1173, Irgacure 184, Irgacure 2959, Irgacure 1000 or benzoin; the water-based UV polyurethane acrylate dispersoid has a self-initiation function or a co-initiation function under the action of a trace initiator, has high resin curing efficiency, can be deeply cured, and has good surface scratch resistance, high hardness, excellent weather resistance and excellent chemical resistance of an adhesive film.
The Thioxanthone (TX) photoinitiator is a hydrogen abstraction type free radical photoinitiator, has strong absorption between 370 and 385nm, has a wavelength close to that emitted by UV-LED light of 355 to 410nm, has high photoinitiation efficiency, and has long ultraviolet absorption without being influenced by color, so the thioxanthone initiator is suitable for a pigment-containing system. Currently commercially available are 2-Chlorothianthrone (CTX), 2-Isopropylthioxanthone (ITX), 2-Hydroxythioxanthone (HTX), 2, 4-dimethylthioxanthone (RTX) and 2, 4-Diethylthioxanthone (DETX), but the TX photoinitiators are poorly soluble in both oligomers and reactive diluents.
Disclosure of Invention
The invention aims to provide thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin and a preparation method thereof.
The invention introduces thioxanthone macromolecule photoinitiating group into the molecular chain of the water-based UV resin, and has the following characteristics: 1) energy migration and intermolecular reaction in a polymer chain become easier, and the polymer has high photoinitiation activity under UV-LED light; 2) the distance between the photoactive group and the main chain is changed, so that the photosensitivity is improved; 3) the solubility and the compatibility with a system are improved; 4) the migration of the photoinitiated groups is limited, and the yellowing and the aging of the coating are prevented; 5) the fragments after photocleavage are still connected on the polymer chain, so that the smell and toxicity of the system can be reduced.
According to the invention, the thioxanthone photoinitiation group is connected to the isocyanate, so that the adhesive force, flexibility, chemical resistance, oil resistance, wear resistance and tensile strength of the epoxy acrylate can be effectively improved.
The thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin has a branched chain structure, contains two functional active groups and a thioxanthone photoinitiating group, and has a molecular structural formula shown as the following formula:
Figure BDA0003198972550000041
in the formula, R is
Figure BDA0003198972550000042
R1Is composed of
Figure BDA0003198972550000043
R2Is H or CH3；R3Is composed of
Figure BDA0003198972550000051
The invention provides a preparation method of thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin, which comprises the following preparation steps of:
a) preparing epoxy acrylate EA: adding epoxy resin into a four-neck flask provided with a reflux condenser pipe, a thermometer, a dropping funnel and a stirrer, slowly dropping a mixture consisting of a carboxyl acrylic monomer, a catalyst and p-hydroxyanisole when the temperature rises to 80 ℃, slowly raising the temperature to 85-90 ℃ after dropping, carrying out heat preservation reaction for 2.5-4 h, then sampling every 30min to detect the acid value of the system, and stopping the reaction when the detected acid value is lower than 5mgKOH/g to obtain epoxy acrylate EA;
b) preparation of 2- (2-hydroxy-) ethoxythioxanthone HETX: adding 98% concentrated sulfuric acid into a reaction bottle provided with a stirring device, a thermometer and a feeding device, cooling to-5-0 ℃ by using an ice salt bath, adding 2, 2' -dithiodibenzoic acid, adding ethylene glycol phenyl ether in batches under stirring, controlling to react for 5-6 h at 0-5 ℃, adding frozen deionized water with the volume of 5-6 times of the concentrated sulfuric acid, stirring for 20min, standing, performing suction filtration, adding deionized water into a filter cake, boiling and refluxing for 2h, cooling, standing, performing suction filtration, washing with water, drying to obtain a crude product, recrystallizing the crude product by using a 1, 4-dioxane-water mixed solvent, stirring, standing, performing suction filtration, and drying to obtain HETX;
c) preparing an isocyanate-thioxanthone functional monomer DI-HETX: adding diisocyanate and dibutyltin dilaurate into a four-neck flask provided with a reflux condenser tube, a thermometer, a dropping funnel and a stirrer, stirring and heating, slowly dropwise adding an acetone solution of HETX at 40-45 ℃, heating to 50-60 ℃ after dropwise adding, continuously reacting for 2-4 h, sampling and detecting an NCO value of a system every 30min, and stopping reaction when the detected NCO value is half of an initial value to prepare an isocyanate-thioxanthone functional monomer DI-HETX;
d) preparing a prepolymer EA-DI-HETX containing a sulfur heteroanthrone group; heating epoxy acrylate EA to 90-100 ℃ while stirring, slowly dropwise adding a mixed solution of DI-HETX, hydroquinone and acetone while stirring, then adding dibutyltin dilaurate, carrying out heat preservation reaction for 2-4 h, then sampling every 30min to detect the NCO value of a system, stopping the reaction when the detected NCO value is half of the initial value, carrying out reduced pressure distillation to remove acetone, and cooling to 50 ℃ to obtain a prepolymer EA-DI-HETX containing thioxanthone groups;
e) preparing the sulfur-containing heteroanthrone LED-UV water-based resin: sequentially adding prepolymer P-DI-HETX, anhydride and P-toluenesulfonic acid into a reaction kettle, heating to 80-85 ℃, melting, adding into the reaction kettle, stirring, heating to 100-110 ℃, reacting for 3-6 h, taking a sample every 0.5h after reacting for 3h, detecting the acid value, cooling to 105 ℃ when the detected acid value meets the specified requirement, adding triethylamine while stirring, adding deionized water, reacting for 0.5-1 h, cooling to 50 ℃ when the pH value is 7.0-8.5, filtering and packaging to obtain the thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin.
Wherein the epoxy resin is one of bisphenol A epoxy resin E-44 or bisphenol A epoxy resin E-51; the carboxyl-containing acrylic monomer is one of acrylic acid or methacrylic acid.
The catalyst is one or two of N, N-dimethylaniline, tetrabutylammonium bromide, N-dimethylethanolamine, N-dimethylformamide and triphenylphosphine; further, it is preferably one of a mixture of N, N-dimethylaniline and tetrabutylammonium bromide in a mass ratio of 1:1 and a mixture of N, N-dimethylethanolamine and N, N-dimethylformamide in a mass ratio of 1: 1.
The diisocyanate is at least one of toluene diisocyanate TDI, isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI and diphenylmethane diisocyanate MDI.
The acid anhydride is one of maleic anhydride, succinic anhydride, methyl succinic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride and itaconic anhydride.
In the step a), the molar ratio of the epoxy resin to the carboxyl-containing acrylic monomer is 1: 2; the addition amount of the catalyst is 1.5-2.5% of the total amount of reactants; the addition amount of the p-hydroxyanisole is 0.1-0.5% of the total amount of reactants.
In the step b), the molar ratio of the 2, 2' -dithiodibenzoic acid to the ethylene glycol phenyl ether is 1: 3; the mass ratio of the concentrated sulfuric acid to the 2, 2' -dithiodibenzoic acid is 5: 1; the volume ratio of the 1, 4-dioxane to water is 1: 4.
In step c), the molar ratio of the diisocyanate to the HETX is 1: 1; the addition amount of the dibutyltin dilaurate is 0.05-0.1% of the amount of diisocyanate.
In the step d), the molar ratio of EA to DI-HETX is 3: 1; the addition amount of the hydroquinone is 0.05-0.1% of the amount of EA; the adding amount of the dibutyltin dilaurate is 0.02-0.1% of the amount of EA.
In the step e), the molar ratio of the acid anhydride to EA-DI-HETX is 1: 1; the addition amount of the p-toluenesulfonic acid is 0.05-0.2% of the total amount of EA-DI-HETX; the molar ratio of the triethylamine to the anhydride is 1: 1-1.05; the deionized water is added in an amount of 55-60% of the total solid content of the product.
The thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin contains two functional groups and a thioxanthone photoinitiating group, and has the following characteristics: 1) energy migration and intermolecular reaction in a polymer chain are easier, and the self-initiation efficiency is high under the illumination of UV-LED light; 2) the space between the photoactive group and the main chain is shortened, and the photosensitivity is improved; 3) excellent system compatibility; 4) the defects caused by a micromolecular photoinitiator are overcome; the thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin prepared by the invention has excellent adhesive force, water resistance, aging resistance, chemical resistance and odor purification effect, has the characteristics of high gloss, high wear resistance, high fullness, strong impact resistance, good flexibility and the like, and is widely used for LED colored perfume bottle coatings, LED woodware coatings, LED alloy coatings, LED circuit board printing ink, LED plastic coatings and the like.
Detailed Description
The preparation of the thioxanthone urethane-modified epoxy acrylate LED-UV waterborne resin of the present invention is further described with reference to the following examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1:
a thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin comprises the following preparation steps:
a) preparation of epoxy acrylate E44A: adding 0.3mol of bisphenol A epoxy resin E-44 into a four-neck flask provided with a reflux condenser pipe, a thermometer, a dropping funnel and a stirrer, slowly dropwise adding a mixture consisting of 0.6mol of acrylic acid, 1.0g N, N-dimethylaniline and 0.3g of p-hydroxyanisole when the temperature rises to 80 ℃, after dropwise adding, slowly heating to 85-90 ℃, carrying out heat preservation reaction for 3 hours, then sampling and detecting the acid value of the system every 40 minutes, and stopping the reaction when the detected acid value is lower than 5mgKOH/g to prepare epoxy acrylate E44A;
b) preparation of 2- (2-hydroxy-) ethoxythioxanthone (HETX): adding 85g of 98% concentrated sulfuric acid into a reaction bottle provided with a stirring device, a thermometer and a feeding device, cooling to-5-0 ℃ by using an ice salt bath, adding 0.1mol of 2, 2' -dithiodibenzoic acid, adding 0.3mol of ethylene glycol phenyl ether in batches under stirring, controlling the temperature to be 0-5 ℃ for reaction for 6h, adding 250mL of frozen deionized water, stirring for 20min, standing, performing suction filtration, adding 120mL of deionized water into a filter cake, boiling and refluxing for 2h, cooling, standing, performing suction filtration, washing with water, drying to obtain a crude product, recrystallizing the crude product by using 100mL of 1, 4-dioxane-water mixed solvent (volume ratio of 4:1), stirring, standing, performing suction filtration, and drying to obtain HETX;
c) preparing isocyanate-thioxanthone functional monomer TDI-HETX: adding 0.1mol of TDI-80 and 0.01 part of DBTDL into a four-neck flask provided with a reflux condenser tube, a thermometer, a dropping funnel and a stirrer, stirring and heating, slowly dropping 0.1mol of HETX and 20.0ml of acetone solution at 40-45 ℃, heating to 50-60 ℃ after dropping, continuing to react for 4 hours, sampling and detecting the NCO value of the system every 30 minutes, and stopping the reaction when the detected NCO value is half of the initial value to prepare the isocyanate-thioxanthone functional monomer TDI-HETX;
d) stirring 0.3mol of epoxy acrylate E44A, heating to 90-95 ℃, slowly dropwise adding a mixed solution of 0.1mol of TDI-HETX, 0.02g of hydroquinone and 20.0ml of acetone while stirring, then adding 0.01 part of DBTDL, carrying out heat preservation reaction for 3 hours, sampling every 30 minutes to detect the NCO value of the system, stopping the reaction when the detected NCO value is half of the initial value, carrying out reduced pressure distillation to remove the acetone, cooling to 50 ℃, and preparing a prepolymer EA-TDI-HETX containing a thioxanthone group;
e) preparing the thioxanthone-containing LED photocuring water-based resin: sequentially adding 0.1mol of prepolymer EA-TDI-HETX, 0.1mol of maleic anhydride and 0.08g of p-toluenesulfonic acid into a reaction kettle, heating to 80-85 ℃ to melt and adding into the reaction kettle, stirring and heating to 100-110 ℃ to react for 3-6 h, taking a sample every 0.5h after reacting for 3h to detect the acid value, cooling to 105 ℃ when the detected acid value meets the specified requirement, adding 0.101mol of triethylamine while stirring, adding 300.0g of deionized water, reacting for 0.5h, cooling to 50 ℃ when the pH value is 7.5-8.0, filtering and packaging to obtain the thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin with the solid content of 44.5%.
Example 2:
a thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin comprises the following preparation steps:
a) preparation of epoxy acrylate E51A: adding 0.3mol of bisphenol A epoxy resin E-51 into a four-neck flask provided with a reflux condenser pipe, a thermometer, a dropping funnel and a stirrer, slowly dropwise adding a mixture consisting of 0.6mol of methacrylic acid, 2.4g of a catalyst (the mass ratio of N, N-dimethylaniline to tetrabutylammonium bromide is 1:1) and 0.3g of p-hydroxyanisole when the temperature rises to 80 ℃, slowly heating to 85-90 ℃ after dropwise adding, carrying out heat preservation reaction for 3 hours, then sampling every 30 minutes to detect the acid value of the system, and stopping the reaction when the detected acid value is lower than 5mgKOH/g to prepare epoxy acrylate E51A;
b) preparation of 2- (2-hydroxy-) ethoxythioxanthone (HETX): adding 85g of 98% concentrated sulfuric acid into a reaction bottle provided with a stirring device, a thermometer and a feeding device, cooling to-5-0 ℃ by using an ice salt bath, adding 0.1mol of 2, 2' -dithiodibenzoic acid, adding 0.3mol of ethylene glycol phenyl ether in batches under stirring, controlling the temperature to be 0-5 ℃ for reaction for 6h, adding 250mL of frozen deionized water, stirring for 20min, standing, performing suction filtration, adding 120mL of deionized water into a filter cake, boiling and refluxing for 2h, cooling, standing, performing suction filtration, washing with water, drying to obtain a crude product, recrystallizing the crude product by using 100mL of 1, 4-dioxane-water mixed solvent (volume ratio of 4:1), stirring, standing, performing suction filtration, and drying to obtain HETX;
c) preparing an isocyanate-thioxanthone functional monomer IPDI-HETX: adding 0.1mol of IPDI and 0.02 part of DBTDL into a four-neck flask provided with a reflux condenser tube, a thermometer, a dropping funnel and a stirrer, stirring and heating, slowly dropping 0.1mol of HETX and 20.0 parts of acetone solution at 40-45 ℃, after dropping, heating to 55-60 ℃, continuing to react for 3.5 hours, then sampling and detecting the NCO value of the system every 30 minutes, and stopping the reaction when the detected NCO value is half of the initial value to prepare the isocyanate-thioxanthone functional monomer IPDI-HETX;
d) stirring 0.3mol of epoxy acrylate E51A, heating to 90-95 ℃, slowly dropwise adding a mixed solution of 0.1mol of IPDI-HETX, 0.02g of hydroquinone and 20.0ml of acetone while stirring, then adding 0.01 part of DBTDL, carrying out heat preservation reaction for 3 hours, sampling every 30 minutes to detect the NCO value of the system, stopping the reaction when the detected NCO value is half of the initial value, carrying out reduced pressure distillation to remove the acetone, cooling to 50 ℃, and preparing a prepolymer EA-IPDI-HETX containing thioxanthone groups;
e) preparing the thioxanthone-containing LED photocuring water-based resin: sequentially adding 0.1mol of prepolymer EA-IPDI-HETX, 0.1mol of itaconic anhydride and 0.09g of p-toluenesulfonic acid into a reaction kettle, heating to 80-85 ℃, melting, adding into the reaction kettle, stirring, heating to 100-110 ℃, reacting for 4 hours, taking a sample every 0.5 hour after reacting for 3 hours, detecting the acid value, cooling to 105 ℃ when the detected acid value meets the specified requirement, adding 0.1mol of triethylamine while stirring, adding 232.0g of deionized water, reacting for 0.5 hour, cooling to 50 ℃ when the pH value is 7.0-7.5, filtering and packaging to obtain the thioxanthone polyurethane modified epoxy acrylate LED-UV waterborne resin with the solid content of 45.2%.
Example 3:
a thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin comprises the following preparation steps:
a) preparation of epoxy acrylate E51A: adding 0.3mol of bisphenol A epoxy resin E-51 into a four-neck flask provided with a reflux condenser pipe, a thermometer, a dropping funnel and a stirrer, slowly dropwise adding a mixture consisting of 0.6mol of methacrylic acid, 2.4g of a catalyst (the mass ratio of N, N-dimethylaniline to tetrabutylammonium bromide is 1:1) and 0.3g of p-hydroxyanisole when the temperature rises to 80 ℃, slowly heating to 85-90 ℃ after dropwise adding, carrying out heat preservation reaction for 3 hours, then sampling every 30 minutes to detect the acid value of the system, and stopping the reaction when the detected acid value is lower than 5mgKOH/g to prepare epoxy acrylate E51A;
b) preparation of 2- (2-hydroxy-) ethoxythioxanthone (HETX): adding 85g of 98% concentrated sulfuric acid into a reaction bottle provided with a stirring device, a thermometer and a feeding device, cooling to-5-0 ℃ by using an ice salt bath, adding 0.1mol of 2, 2' -dithiodibenzoic acid, adding 0.3mol of ethylene glycol phenyl ether in batches under stirring, controlling the temperature to be 0-5 ℃ for reaction for 6h, adding 250mL of frozen deionized water, stirring for 20min, standing, performing suction filtration, adding 120mL of deionized water into a filter cake, boiling and refluxing for 2h, cooling, standing, performing suction filtration, washing with water, drying to obtain a crude product, recrystallizing the crude product by using 100mL of 1, 4-dioxane-water mixed solvent (volume ratio of 4:1), stirring, standing, performing suction filtration, and drying to obtain HETX;
c) preparing an isocyanate-thioxanthone functional monomer MDI-HETX: adding 0.1mol of MDI and 0.02 part of DBTDL into a four-neck flask provided with a reflux condenser tube, a thermometer, a dropping funnel and a stirrer, stirring and heating, slowly dropping 0.1mol of HETX and 20.0 parts of acetone solution at 40-45 ℃, after dropping, heating to 50-60 ℃, continuing to react for 4 hours, then sampling and detecting the NCO value of the system every 30 minutes, and stopping the reaction when the detected NCO value is half of the initial value to prepare the isocyanate-thioxanthone functional monomer MDI-HETX;
d) stirring 0.3mol of epoxy acrylate E51A, heating to 90-95 ℃, slowly dropwise adding a mixed solution of 0.1mol of MDI-HETX, 0.02g of hydroquinone and 20.0ml of acetone while stirring, then adding 0.01 part of DBTDL, carrying out heat preservation reaction for 3 hours, sampling every 30 minutes to detect the NCO value of the system, stopping the reaction when the detected NCO value is half of the initial value, carrying out reduced pressure distillation to remove the acetone, cooling to 50 ℃, and preparing a prepolymer EA-MDI-HETX containing thioxanthone groups;
e) preparing the thioxanthone-containing LED photocuring water-based resin: sequentially adding 0.1mol of prepolymer EA-MDI-HETX, 0.1mol of maleic anhydride and 0.08g of p-toluenesulfonic acid into a reaction kettle, heating to 80-85 ℃ to melt and adding into the reaction kettle, stirring and heating to 100-110 ℃ to react for 4 hours, taking a sample every 0.5 hour after reacting for 3 hours to detect the acid value, cooling to 105 ℃ when the detected acid value meets the specified requirement, adding 0.1mol of triethylamine while stirring, adding 235.0g of deionized water, cooling to 50 ℃ when the pH value is 7.0-7.5 after reacting for 0.5 hour, filtering and packaging to obtain the thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin with the solid content of 44.6%.
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (8)

1. A thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin is characterized in that: the LED-UV water-based resin has a branched chain structure, contains two functional active groups and a thioxanthone photoinitiation group, and has a molecular structural formula shown as the following formula:
Figure FDA0003198972540000011
wherein in the formula, R is
Figure FDA0003198972540000012
R1Is composed of
Figure FDA0003198972540000013
Or- (CH)2)6-；
R2Is H or CH3；R3Is composed of
Figure FDA0003198972540000014
-(CH2)2-、-(CH2)3-、-(CH2)4-、
Figure FDA0003198972540000015
2. The method for preparing the amine-containing thioxanthone polyurethane modified epoxy acrylate LED-UV light curable resin according to claim 1, wherein the method comprises the following steps: the preparation method comprises the following steps:
a) preparing epoxy acrylate EA: adding epoxy resin into a four-neck flask provided with a reflux condenser pipe, a thermometer, a dropping funnel and a stirrer, slowly dropping a mixture consisting of a carboxyl acrylic monomer, a catalyst and p-hydroxyanisole when the temperature rises to 80 ℃, slowly raising the temperature to 85-90 ℃ after dropping, carrying out heat preservation reaction for 2.5-4 h, then sampling every 30min to detect the acid value of the system, and stopping the reaction when the detected acid value is lower than 5mgKOH/g to obtain epoxy acrylate EA;
b) preparation of 2- (2-hydroxy-) ethoxythioxanthone HETX: adding 98% concentrated sulfuric acid into a reaction bottle provided with a stirring device, a thermometer and a feeding device, cooling to-5-0 ℃ by using an ice salt bath, adding 2, 2' -dithiodibenzoic acid, adding ethylene glycol phenyl ether in batches under stirring, controlling to react for 5-6 h at 0-5 ℃, adding frozen deionized water with the volume of 5-6 times of the concentrated sulfuric acid, stirring for 20min, standing, performing suction filtration, adding deionized water into a filter cake, boiling and refluxing for 2h, cooling, standing, performing suction filtration, washing with water, drying to obtain a crude product, recrystallizing the crude product by using a 1, 4-dioxane-water mixed solvent, stirring, standing, performing suction filtration, and drying to obtain HETX;
c) preparing an isocyanate-thioxanthone functional monomer DI-HETX: adding diisocyanate and dibutyltin dilaurate into a four-neck flask provided with a reflux condenser tube, a thermometer, a dropping funnel and a stirrer, stirring and heating, slowly dropwise adding an acetone solution of HETX at 40-45 ℃, heating to 50-60 ℃ after dropwise adding, continuously reacting for 2-4 h, sampling and detecting an NCO value of a system every 30min, and stopping reaction when the detected NCO value is half of an initial value to prepare an isocyanate-thioxanthone functional monomer DI-HETX;
d) preparing a prepolymer EA-DI-HETX containing a sulfur heteroanthrone group; heating epoxy acrylate EA to 90-100 ℃ while stirring, slowly dropwise adding a mixed solution of DI-HETX, hydroquinone and acetone while stirring, then adding dibutyltin dilaurate, carrying out heat preservation reaction for 2-4 h, then sampling every 30min to detect the NCO value of a system, stopping the reaction when the detected NCO value is half of the initial value, carrying out reduced pressure distillation to remove acetone, and cooling to 50 ℃ to obtain a prepolymer EA-DI-HETX containing thioxanthone groups;
e) preparing thioxanthone LED-UV water-based resin: sequentially adding prepolymer P-DI-HETX, anhydride and P-toluenesulfonic acid into a reaction kettle, heating to 80-85 ℃, melting, adding into the reaction kettle, stirring, heating to 100-110 ℃, reacting for 3-6 h, taking a sample every 0.5h after reacting for 3h, detecting the acid value, cooling to 105 ℃ when the detected acid value meets the specified requirement, adding triethylamine while stirring, adding deionized water, reacting for 0.5-1 h, cooling to 50 ℃ when the pH value is 7.0-8.5, filtering and packaging to obtain the thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin;
wherein in step a), the molar ratio of the epoxy resin to the carboxyl-containing acrylic monomer is 1: 2; the adding amount of the catalyst is 1.5-2.5% of the total amount of reactants; the addition amount of the p-hydroxyanisole is 0.1-0.5% of the total amount of reactants;
in step b), the molar ratio of the 2, 2' -dithiodibenzoic acid to the ethylene glycol phenyl ether is 1: 3; the mass ratio of the concentrated sulfuric acid to the 2, 2' -dithiodibenzoic acid is 5: 1; the volume ratio of the 1, 4-dioxane to water is 1: 4;
in step c), the molar ratio of diisocyanate to HETX is 1: 1; the adding amount of the dibutyltin dilaurate is 0.05-0.1% of that of diisocyanate;
in step d), the molar ratio of EA to DI-HETX is 3: 1; the addition amount of the hydroquinone is 0.05-0.1% of the amount of EA; the adding amount of the dibutyltin dilaurate is 0.02-0.1% of the amount of EA;
in step e), the molar ratio of the acid anhydride to EA-DI-HETX is 1: 1; the addition amount of the p-toluenesulfonic acid is 0.05-0.2% of the total amount of EA-DI-HETX; the molar ratio of the triethylamine to the anhydride is 1: 1-1.05; the deionized water is added in an amount of 55-60% of the total solid content of the product.
3. The LED-UV waterborne resin according to claim 1 or 2, wherein: the epoxy resin is one of bisphenol A epoxy resin E-44 or bisphenol A epoxy resin E-51.
4. The LED-UV waterborne resin according to claim 1 or 2, wherein: the diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate.
5. The LED-UV waterborne resin according to claim 1 or 2, wherein: the carboxyl-containing acrylic monomer is one of acrylic acid or methacrylic acid.
6. The LED-UV waterborne resin according to claim 1 or 2, wherein: the catalyst is at least one of N, N-dimethylaniline, tetrabutylammonium bromide, N-dimethylethanolamine, N-dimethylformamide and triphenylphosphine.
7. The LED-UV waterborne resin according to claim 1 or 2, wherein: the catalyst is one of a mixture of N, N-dimethylaniline and tetrabutylammonium bromide in a mass ratio of 1:1 or a mixture of N, N-dimethylethanolamine and N, N-dimethylformamide in a mass ratio of 1: 1.
8. The LED-UV waterborne resin according to claim 1 or 2, wherein: the acid anhydride is one of maleic anhydride, succinic anhydride, methyl succinic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride and itaconic anhydride.
CN202110901009.XA 2021-08-05 2021-08-05 Thioxanthone polyurethane modified epoxy acrylate LED-UV water-based resin Pending CN113583202A (en)

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