CN105505197A - Ultraviolet curing coating and preparation method thereof - Google Patents

Ultraviolet curing coating and preparation method thereof Download PDF

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Publication number
CN105505197A
CN105505197A CN201511025483.1A CN201511025483A CN105505197A CN 105505197 A CN105505197 A CN 105505197A CN 201511025483 A CN201511025483 A CN 201511025483A CN 105505197 A CN105505197 A CN 105505197A
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vulcabond
ultraviolet
reaction solution
preparation
curing paint
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CN105505197B (en
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刘键
姚志刚
景梅
张军华
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LENGINE DEFENSE TECHNOLOGY GROUP Co.,Ltd.
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Zhongwu Function Material Institute Co Ltd
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    • 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
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    • C08G18/67—Unsaturated compounds having active hydrogen
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Abstract

The invention relates to an ultraviolet curing coating and a preparation method thereof. The preparation method of the ultraviolet curing coating comprises the following steps: enabling diisocyanate to react with 1,4-cyclohexyl dimethyl carbinol to obtain modified diisocyanate; enabling the modified diisocyanate to react with diol to obtain a first reaction liquid; adding polyhydroxyl carboxylic acid and a catalyst into the first reaction liquid to obtain a second reaction liquid; mixing the second reaction liquid with a chain extender for reaction to obtain a third reaction liquid; adding hydroxyl acrylate and a polymerization inhibitor into the third reaction liquid for reaction to obtain a fourth reaction liquid; adding triethylamine into the fourth reaction liquid for reaction to obtain a polyurethane acrylate prepolymer; adding deionized water into the polyurethane acrylate prepolymer to obtain a polyurethane acrylate dispersion; mixing the polyurethane acrylate dispersion with a filler, a photoinitiator, a leveling agent, an antifoaming agent and a dispersing agent; and stirring and dispersing to obtain the ultraviolet curing coating. The ultraviolet curing coating prepared by the method has relatively high performance.

Description

Ultraviolet-curing paint and preparation method thereof
Technical field
The present invention relates to paint field, particularly a kind of ultraviolet-curing paint and preparation method thereof.
Background technology
Water-borne coatings have nontoxic, pollution-free, non-stimulated, film performance is excellent, save the advantage such as the energy, production safety, has responded the themes of the times of 21st century efficient, energy-conservation, green and environmental protection.At present, water-borne coatings adopts linear polymer as main raw mostly, and linear polymer has the performance of many excellences, but there is the slow shortcoming of curing speed.
Water-borne coatings and photo-cured coating combine with technique are got up, effectively can utilize the advantage that photocuring technology curing speed is fast, obtain easy construction, properties preferably UV-curable waterborne coatings.
But, existing UV-curable waterborne coatings because of under exposure in sunshine out of doors, the very fast xanthochromia of paint film, efflorescence; If in architectural use UV-curable waterborne coatings, also can cause the exposed corrosion of building surface, thus reduce the weather resistance of buildings.
Summary of the invention
Based on this, be necessary to provide a kind of method can preparing the ultraviolet-curing paint with good performance.
In addition, a kind of ultraviolet-curing paint is also provided.
Under the environment of protective gas, mixed by vulcabond with Isosorbide-5-Nitrae-cyclohexane dimethanol, in 60 ~ 80 DEG C of reactions 1 ~ 3 hour, obtain the vulcabond of modification, wherein, the mol ratio of described Isosorbide-5-Nitrae-cyclohexane dimethanol and described vulcabond was 1: 2;
In the vulcabond of described modification, add dibasic alcohol, in 60 ~ 80 DEG C of stirring reactions 2 ~ 4 hours, obtain the first reaction solution, wherein, the mol ratio of the vulcabond of described dibasic alcohol and described modification was 1: 2 ~ 6;
In described first reaction solution, add multi-hydroxy carboxy acid and catalyzer, in 70 ~ 80 DEG C of stirring reactions 1 ~ 2 hour, obtain the second reaction solution, wherein, the mol ratio of the vulcabond of described multi-hydroxy carboxy acid and described modification was 0.1 ~ 0.3: 1;
Under the condition of 50 ~ 60 DEG C, by described second reaction solution and chainextender mixing, carry out chain extending reaction 2 ~ 3 hours, obtain the 3rd reaction solution, wherein, the mol ratio of the vulcabond of described chainextender and described modification is 0.1 ~ 0.3: 1;
Under the condition of 50 ~ 60 DEG C, hydroxy acrylate is added and stopper carries out end-blocking in described 3rd reaction solution, react after 1 hour, be warming up to 70 ~ 85 DEG C, then add acetone, continue reaction 2 hours, obtain the 4th reaction solution, wherein, the mol ratio of the vulcabond of described hydroxy acrylate and described modification is 0.2 ~ 0.6: 1; And
Under the condition of 40 ~ 50 DEG C, in described 4th reaction solution, add triethylamine, react 0.5 ~ 1.0 hour, then 30 ~ 40 DEG C are cooled to, obtain polyurethane acrylate prepolymer, wherein, the mol ratio of described triethylamine and described multi-hydroxy carboxy acid is 1 ~ 1.5: 1;
Under the condition of Keep agitation, deionized water is joined in described polyurethane acrylate prepolymer, continue stirring and emulsifying dispersion 30 ~ 40 minutes, through cooling, obtain urethane acrylate dispersoid, wherein, the mass ratio of described polyurethane acrylate prepolymer and described deionized water is 30 ~ 50: 40 ~ 60;
Following component is comprised: described urethane acrylate dispersoid 75 ~ 90 parts, filler 5 ~ 20 parts, light trigger 2 ~ 6 parts, flow agent 0.1 ~ 1 part, dispersion agent 0.1 ~ 1 part and defoamer 0.1 ~ 1 part according to mass fraction; And
Described urethane acrylate dispersoid, described filler, described light trigger, described flow agent, described dispersion agent and described defoamer are mixed, dispersed with stirring 15 ~ 30 minutes, obtains ultraviolet-curing paint.
Wherein in an embodiment, described vulcabond is selected from least one in Xylene Diisocyanate, dicyclohexyl methane diisocyanate, '-diphenylmethane diisocyanate, terephthalylidene vulcabond, hexamethylene diisocyanate and isophorone diisocyanate.
Wherein in an embodiment, described dibasic alcohol is selected from least one in polyether Glycols, polycaprolactone diols and PCDL.
Wherein in an embodiment, described multi-hydroxy carboxy acid is at least one in dimethylol propionic acid and dimethylolpropionic acid.
Wherein in an embodiment, described catalyzer is dibutyl tin laurate; Wherein, the mass ratio of described catalyzer and described multi-hydroxy carboxy acid is 0.1 ~ 1: 3 ~ 8.
Wherein in an embodiment, described hydroxy acrylate is selected from least one in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, pentaerythritol triacrylate, Rocryl 410, Propylene glycol monoacrylate and trimethylolpropane diacrylate; Described stopper is p methoxy phenol, and the mass ratio of described stopper and described hydroxy acrylate is for being 0.1 ~ 0.5: 20 ~ 60.
Wherein in an embodiment, also comprise the preparation process of described chainextender:
Pentaerythritol triacrylate, methoxyphenol and acetone are mixed, under the condition of 45 DEG C, adds isophorone diisocyanate and dibutyl tin laurate, then in 50 ~ 60 DEG C of reactions 1 ~ 3 hour, obtain the first mixed solution; The acetone soln of TriMethylolPropane(TMP) is added in described first mixed solution, in 60 ~ 75 DEG C of reactions until isocyano ion disappears, obtain double bond containing glycol monomer, wherein, the mol ratio of described pentaerythritol triacrylate, described isophorone diisocyanate and described TriMethylolPropane(TMP) is 1: 1: 1.
Wherein in an embodiment, described filler is selected from least one in silicon-dioxide, titanium dioxide, aluminium sesquioxide, talcum powder and mica powder.
Wherein in an embodiment, be set forth in the condition of 50 ~ 60 DEG C under, described hydroxy acrylate is added and described stopper carries out end-blocking in described 3rd reaction solution, react after 1 hour, be warming up to 70 ~ 85 DEG C, then add in the step of described acetone, the interpolation quality of described acetone is 3 ~ 10% of the total mass of described 3rd reaction solution, described hydroxy acrylate and described stopper.
A kind of ultraviolet-curing paint prepared by the preparation method of above-mentioned ultraviolet-curing paint.
The preparation method of above-mentioned ultraviolet-curing paint is simple to operate, is easy to suitability for industrialized production.Above-mentioned ultraviolet-curing paint is by 1,4-cyclohexane dimethanol is to vulcabond modification, 1 is introduced in polyurethane molecular chain, 4 cyclohexane dimethanol are to vulcabond modification, continue and dibasic alcohol, multi-hydroxy carboxy acid, hydroxy-acrylate monomer reacts, synthesize a kind of novel urethane acrylate, due to 1, the structural symmetry of 4 cyclohexane dimethanol, and cooperation adds chainextender, above-mentioned ultraviolet-curing paint is made to have the advantages such as good thermal stability, the transparency, shock-resistance, wear-resisting trauma and good hardness.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the ultraviolet-curing paint of an embodiment.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments ultraviolet-curing paint and preparation method thereof is described in further detail below.
As shown in Figure 1, the preparation method of the ultraviolet-curing paint of an embodiment, comprises the steps:
Step S110: under the environment of protective gas, mixes vulcabond with Isosorbide-5-Nitrae-cyclohexane dimethanol, in 60 ~ 80 DEG C of reactions 1 ~ 3 hour, obtains the vulcabond of modification.
Wherein, the mol ratio of Isosorbide-5-Nitrae-cyclohexane dimethanol and vulcabond is 1: 2.
Wherein, protective gas can be nitrogen or rare gas element.
Wherein, vulcabond is selected from least one in dicyclohexyl methane diisocyanate, '-diphenylmethane diisocyanate, terephthalylidene vulcabond, hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexyl methane diisocyanate.
Step S120: add dibasic alcohol in the vulcabond of modification, in 60 ~ 80 DEG C of stirring reactions 2 ~ 4 hours, obtains the first reaction solution.
Wherein, dibasic alcohol is selected from least one in polyether Glycols, polycaprolactone diols and PCDL.
Wherein, the mol ratio of the vulcabond of dibasic alcohol and modification is 1: 2 ~ 6.
Step S130: add multi-hydroxy carboxy acid and catalyzer in the first reaction solution, in 70 ~ 80 DEG C of stirring reactions 1 ~ 2 hour, obtains the second reaction solution.
Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.1 ~ 0.3: 1.
Wherein, multi-hydroxy carboxy acid is selected from least one in dimethylol propionic acid and dimethylolpropionic acid.
Wherein, catalyzer is dibutyl tin laurate.Wherein, the mass ratio of catalyzer and multi-hydroxy carboxy acid is 0.1 ~ 1: 3 ~ 8.
Step S140: under the condition of 50 ~ 60 DEG C, by the second reaction solution and chainextender mixing, carry out chain extending reaction 2 ~ 3 hours, obtain the 3rd reaction solution, wherein, the mol ratio of the vulcabond of described chainextender and described modification is 0.1 ~ 0.3: 1;
Wherein, chainextender is double bond containing glycol monomer.
Concrete, chainextender prepares by following preparation process: pentaerythritol triacrylate, methoxyphenol and acetone are mixed, under the condition of 45 DEG C, add isophorone diisocyanate (IPDI) and dibutyl tin laurate (DBTAL), then in 50 ~ 60 DEG C of reactions 1 ~ 3 hour, the first mixed solution is obtained; The acetone soln of TriMethylolPropane(TMP) (TMP) is added in the first mixed solution, in 60 ~ 75 DEG C of reactions until isocyano ion disappears, obtains double bond containing glycol monomer.Wherein, the mol ratio of pentaerythritol triacrylate, isophorone diisocyanate and TriMethylolPropane(TMP) is 1: 1: 1.
Wherein, the quality of methoxyphenol and the mass ratio of pentaerythritol triacrylate are 0.5: 100.
Wherein, the mass ratio of dibutyl tin laurate and isophorone diisocyanate is 0.08: 100.
Wherein, the mol ratio of the vulcabond of chainextender and modification is 0.1 ~ 0.3: 1.
Step S150: under the condition of 50 ~ 60 DEG C, adds hydroxy acrylate in the 3rd reaction solution and stopper carries out end-blocking, reacts after 1 hour, is warming up to 70 ~ 85 DEG C, then adds acetone, continues reaction 2 hours, obtains the 4th reaction solution.
Wherein, the mol ratio of the isocyanic ester of hydroxy acrylate and modification is 0.2 ~ 0.6: 1: 1.
Wherein, hydroxy acrylate is selected from least one in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, pentaerythritol triacrylate, Rocryl 410, Propylene glycol monoacrylate and trimethylolpropane diacrylate.
Wherein, stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 0.1 ~ 0.5: 20 ~ 60.
Wherein, in step S150, the interpolation quality of acetone is 5 ~ 15% of the total mass of the second reaction solution, hydroxy acrylate and stopper.
Step S160: under the condition of 40 ~ 50 DEG C, adds triethylamine in the 4th reaction solution, reacts and obtains polyurethane acrylate prepolymer in 0.5 ~ 1.0 hour.
Wherein, the mol ratio of triethylamine and multi-hydroxy carboxy acid is 1 ~ 1.5: 1.
Step S170: under the condition of Keep agitation, joins deionized water in polyurethane acrylate prepolymer, continues stirring and emulsifying dispersion 30 ~ 40 minutes, through cooling, obtains urethane acrylate dispersoid.
Wherein, the mass ratio of polyurethane acrylate prepolymer and deionized water is 30 ~ 50: 40 ~ 60.
In step S170, it is 300 ~ 400 revs/min in the speed of the condition of Keep agitation; Continuing the stirring and emulsifying dispersion stirring velocity of 30 ~ 40 minutes is 400 ~ 600 revs/min.
Step S180: comprise following component according to mass fraction: urethane acrylate dispersoid 75 ~ 90 parts, filler 5 ~ 20 parts, light trigger 2 ~ 6 parts, flow agent 0.1 ~ 1 part, dispersion agent 0.1 ~ 1 part and defoamer 0.1 ~ 1 part.
Wherein, dispersion agent is selected from least one in TEGO192, PCE and PL-20.
Wherein, flow agent is selected from least one in BYK346, BYK333, TEGO425 and TEGO450.
Wherein, defoamer is selected from least one in BYK028, BYK093, BYK024 and BYK022.
Wherein, light trigger is selected from least one in 819,184,1173,2959 and KIP160.
Wherein, filler is selected from least one in silicon-dioxide, titanium dioxide, aluminium sesquioxide, talcum powder and mica powder.
Step S180: urethane acrylate dispersoid, filler light trigger, flow agent, dispersion agent and defoamer are mixed, dispersed with stirring 15 ~ 30 minutes, obtains ultraviolet-curing paint.
Wherein, after the step S190 dispersed with stirring step of 15 ~ 30 minutes, the step of 200 ~ 400 mesh sieves was also comprised.
The preparation method of above-mentioned ultraviolet-curing paint is simple to operate, is easy to suitability for industrialized production.Above-mentioned ultraviolet-curing paint is by 1,4-cyclohexane dimethanol is to vulcabond modification, 1 is introduced in polyurethane molecular chain, 4 cyclohexane dimethanol are to vulcabond modification, continue and dibasic alcohol, multi-hydroxy carboxy acid, acrylate monomers reacts, synthesize a kind of novel urethane acrylate, due to 1, the structural symmetry of 4 cyclohexane dimethanol, and cooperation adds chainextender, above-mentioned ultraviolet-curing paint is made to have the advantages such as good thermal stability, the transparency, shock-resistance, wear-resisting trauma and good hardness.
Above-mentioned ultraviolet-curing paint does not need additional emulsifying agent and reactive thinner, energy-conserving and environment-protective, has high rigidity and good thermal stability, can be used for, on the products such as automobile, electronic product, furniture, having broad application prospects.
A kind of ultraviolet-curing paint prepared by the preparation method of above-mentioned ultraviolet-curing paint.Because this ultraviolet-curing paint adopts above-mentioned preparation method to prepare, above-mentioned ultraviolet-curing paint is made to have good performance.
Be below specific embodiment part:
Embodiment 1
The preparation process of the ultraviolet-curing paint of the present embodiment is as follows:
(1) preparation of chainextender: pentaerythritol triacrylate and methoxyphenol (MEHQ) are proceeded to the acetone of 10g in the there-necked flask that thermometer, prolong and agitator are housed, wherein, the quality of methoxyphenol and the mass ratio of pentaerythritol triacrylate are then be placed in 45 DEG C waters bath with thermostatic control at 0.5: 100, constant pressure funnel is utilized dropwise to be joined in there-necked flask by isophorone diisocyanate, add dibutyl tin laurate (DBTAL) simultaneously and carry out catalysis, then in 50 DEG C of reactions 1 hour, the first mixed solution is obtained.The acetone soln constant voltage of TriMethylolPropane(TMP) is instilled in the first reaction solution, in 60 DEG C of reactions until isocyano ion disappears, discharging, obtain colourless or lurid double bond containing glycol monomer, be chainextender, wherein, the mass ratio of dibutyl tin laurate and isophorone diisocyanate is 0.08: 100; The mol ratio of pentaerythritol triacrylate, isophorone diisocyanate and TriMethylolPropane(TMP) is 1: 1: 1.
(2) preparation of urethane acrylate dispersoid:
1, under logical nitrogen protection condition; to in the four mouthfuls of round reaction flasks being placed with thermometer, prolong, stirring rod; add vulcabond; be placed in the water bath with thermostatic control of 60 DEG C; utilize constant pressure funnel by 1; 4-cyclohexane dimethanol is added drop-wise in four mouthfuls of reaction flasks, and insulation reaction 3 hours, obtains the vulcabond of modification.Wherein, the mol ratio of Isosorbide-5-Nitrae-cyclohexane dimethanol and vulcabond is 1: 2.Vulcabond is selected from dicyclohexyl methane diisocyanate.
2, in the vulcabond of modification, add dibasic alcohol, in 60 DEG C of stirring reactions 4 hours, obtain the first reaction solution.Wherein, dibasic alcohol is selected from polyether Glycols.Wherein, the mol ratio of the vulcabond of dibasic alcohol and modification is 1: 6.
3, in the first reaction solution, add multi-hydroxy carboxy acid and catalyzer, in 70 DEG C of stirring reactions 2 hours, obtain the second reaction solution.Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.3: 1, and multi-hydroxy carboxy acid is dimethylol propionic acid, and catalyzer is dibutyl tin laurate, and the mass ratio of catalyzer and multi-hydroxy carboxy acid is 0.1: 3.
4, be cooled to 50 DEG C, adopt constant pressure funnel to add in the second reaction solution by chainextender prepared by step (1), carry out chain extending reaction 2 hours, obtain the 3rd reaction solution.Wherein, the mol ratio of the vulcabond of chainextender and modification is 0.3: 1.
5, under the condition of 50 DEG C, in the 3rd reaction solution, add hydroxy acrylate and stopper carries out end-blocking, react after 1 hour, be warming up to 70 DEG C, then add acetone, continue reaction 2 hours, obtain the 4th reaction solution.Wherein, the mol ratio of the isocyanic ester of hydroxy acrylate and modification is 0.6: 1.Hydroxy acrylate is selected from hydroxyethyl methylacrylate.Stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 0.1: 20.The interpolation quality of acetone is 5% of the total mass of the second reaction solution, hydroxy acrylate and stopper.
6, under the condition of 40 DEG C, in the 4th reaction solution, add triethylamine, react 0.5 hour, obtain transparent polyurethane acrylate prepolymer.Wherein, the mol ratio of triethylamine and multi-hydroxy carboxy acid is 1: 1.
7, under the condition of the Keep agitation of 300 revs/min, deionized water is joined in polyurethane acrylate prepolymer, continue to disperse 30 minutes with the speed stirring and emulsifying of 400 revs/min, through cooling, obtain urethane acrylate dispersoid.
(3) preparation of ultraviolet-curing paint:
1, following component is taken according to mass fraction:
Wherein, filler is selected from silicon-dioxide.
2, according to said ratio, urethane acrylate dispersoid, filler, light trigger, flow agent, dispersion agent and defoamer are added in dispersion cylinder, dispersed with stirring 15 minutes, cross 200 mesh sieves, namely obtain ultraviolet-curing paint.Wherein, dispersion agent is selected from TEGO192.Flow agent is selected from BYK346.Defoamer is selected from BYK028.Light trigger is selected from 819.
The performance of the ultraviolet-curing paint of test the present embodiment, obtains the performance of the ultraviolet-curing paint of the present embodiment in table 1.
Embodiment 2
The preparation process of the ultraviolet-curing paint of the present embodiment is as follows:
(1) preparation of chainextender: pentaerythritol triacrylate and methoxyphenol (MEHQ) are proceeded to the acetone of 10g in the there-necked flask that thermometer, prolong and agitator are housed, wherein, the quality of methoxyphenol and the mass ratio of pentaerythritol triacrylate are then be placed in 45 DEG C waters bath with thermostatic control at 0.5: 100, constant pressure funnel is utilized dropwise to be joined in there-necked flask by isophorone diisocyanate, add dibutyl tin laurate (DBTAL) simultaneously and carry out catalysis, then in 60 DEG C of reactions 3 hours, the first mixed solution is obtained.The acetone soln constant voltage of TriMethylolPropane(TMP) is instilled in the first reaction solution, in 75 DEG C of reactions until isocyano ion disappears, discharging, obtain colourless or lurid double bond containing glycol monomer, be chainextender, wherein, the mass ratio of dibutyl tin laurate and isophorone diisocyanate is 0.08: 100; The mol ratio of pentaerythritol triacrylate, isophorone diisocyanate and TriMethylolPropane(TMP) is 1: 1: 1.
(2) preparation of urethane acrylate dispersoid:
1, under logical nitrogen protection condition; to in the four mouthfuls of round reaction flasks being placed with thermometer, prolong, stirring rod; add vulcabond; be placed in the water bath with thermostatic control of 80 DEG C; utilize constant pressure funnel by 1; 4-cyclohexane dimethanol is added drop-wise in four mouthfuls of reaction flasks, and insulation reaction 1 hour, obtains the vulcabond of modification.Wherein, the mol ratio of Isosorbide-5-Nitrae-cyclohexane dimethanol and vulcabond is 1: 2.Vulcabond is selected from '-diphenylmethane diisocyanate.
2, in the vulcabond of modification, add dibasic alcohol, in 80 DEG C of stirring reactions 2 hours, obtain the first reaction solution.Wherein, dibasic alcohol is selected from polycaprolactone diols.Wherein, the mol ratio of the vulcabond of dibasic alcohol and modification is 1: 6.
3, in the first reaction solution, add multi-hydroxy carboxy acid and catalyzer, in 80 DEG C of stirring reactions 1 hour, obtain the second reaction solution.Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.3: 1, and multi-hydroxy carboxy acid is dimethylol propionic acid, and catalyzer is dibutyl tin laurate, and the mass ratio of catalyzer and multi-hydroxy carboxy acid is 1: 8-.
4, be cooled to 60 DEG C, adopt constant pressure funnel to add in the second reaction solution by chainextender prepared by step (1), carry out chain extending reaction 3 hours, obtain the 3rd reaction solution.Wherein, the mol ratio of the vulcabond of chainextender and modification is 0.3: 1.
5, under the condition of 60 DEG C, in the 3rd reaction solution, add hydroxy acrylate and stopper carries out end-blocking, react after 1 hour, be warming up to 85 DEG C, then add acetone, continue reaction 2 hours, obtain the 4th reaction solution.Wherein, the mol ratio entering hydroxy acrylate and isocyanic ester is 0.6: 1.Hydroxy acrylate is selected from pentaerythritol triacrylate.Stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 0.5: 60.The interpolation quality of acetone is 10% of the total mass of the second reaction solution, hydroxy acrylate and stopper.
6, under the condition of 50 DEG C, in the 4th reaction solution, add triethylamine, react 1.0 hours, be then cooled to 40 DEG C, obtain transparent polyurethane acrylate prepolymer.Wherein, the mol ratio of triethylamine and multi-hydroxy carboxy acid is 1.5: 1.
7, under the condition of the Keep agitation of 400 revs/min, deionized water joins in polyurethane acrylate prepolymer, continues to disperse 40 minutes with the speed stirring and emulsifying of 600 revs/min, through cooling, obtains urethane acrylate dispersoid.
(3) preparation of ultraviolet-curing paint:
1, following component is taken according to mass fraction:
Wherein, filler is selected from titanium dioxide.
2, according to said ratio, urethane acrylate dispersoid, filler, light trigger, flow agent, dispersion agent and defoamer are added in dispersion cylinder, dispersed with stirring 30 minutes, cross 400 mesh sieves, namely obtain ultraviolet-curing paint.Wherein, dispersion agent is selected from PCE.Flow agent is selected from BYK333.Defoamer is selected from BYK093.Light trigger is selected from 184.
The identical testing method of embodiment 1 is adopted to obtain the performance of the purple ultraviolet-curing paint of the present embodiment in table 1.
Embodiment 3
The preparation process of the ultraviolet-curing paint of the present embodiment is as follows:
(1) preparation of chainextender: pentaerythritol triacrylate and methoxyphenol (MEHQ) are proceeded to the acetone of 10g in the there-necked flask that thermometer, prolong and agitator are housed, wherein, the quality of methoxyphenol and the mass ratio of pentaerythritol triacrylate are then be placed in 45 DEG C waters bath with thermostatic control at 0.5: 100, constant pressure funnel is utilized dropwise to be joined in there-necked flask by isophorone diisocyanate, add dibutyl tin laurate (DBTAL) simultaneously and carry out catalysis, then in 50 DEG C of reactions 2 hours, the first mixed solution is obtained.The acetone soln constant voltage of TriMethylolPropane(TMP) is instilled in the first reaction solution, in 70 DEG C of reactions until isocyano ion disappears, discharging, obtain colourless or lurid double bond containing glycol monomer, be chainextender, wherein, the mass ratio of dibutyl tin laurate and isophorone diisocyanate is 0.08: 100; The mol ratio of pentaerythritol triacrylate, isophorone diisocyanate and TriMethylolPropane(TMP) is 1: 1: 1.
(2) preparation of urethane acrylate dispersoid:
1, under logical nitrogen protection condition; to in the four mouthfuls of round reaction flasks being placed with thermometer, prolong, stirring rod; add vulcabond; be placed in the water bath with thermostatic control of 70 DEG C; utilize constant pressure funnel by 1; 4-cyclohexane dimethanol is added drop-wise in four mouthfuls of reaction flasks, and insulation reaction 2 hours, obtains the vulcabond of modification.Wherein, the mol ratio of Isosorbide-5-Nitrae-cyclohexane dimethanol and vulcabond is 1: 2.Vulcabond is selected from terephthalylidene vulcabond.
2, in the vulcabond of modification, add dibasic alcohol, in 70 DEG C of stirring reactions 3 hours, obtain the first reaction solution.Wherein, dibasic alcohol is selected from polycaprolactone diols.Wherein, the mol ratio of the vulcabond of dibasic alcohol and modification is 1: 4.
3, in the first reaction solution, add multi-hydroxy carboxy acid and catalyzer, in 75 DEG C of stirring reactions 1.5 hours, obtain the second reaction solution.Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.3: 1, multi-hydroxy carboxy acid is at least one in dimethylol propionic acid and dimethylolpropionic acid, and catalyzer is dibutyl tin laurate, and the mass ratio of catalyzer and multi-hydroxy carboxy acid is 1: 8.
4, be cooled to 55 DEG C, adopt constant pressure funnel to add in the second reaction solution by chainextender prepared by step (1), carry out chain extending reaction 2.5 hours, obtain the 3rd reaction solution.Wherein, the mol ratio of the vulcabond of chainextender and modification is 0.3: 1.
5, under the condition of 55 DEG C, in the 3rd reaction solution, add hydroxy acrylate and stopper carries out end-blocking, react after 1 hour, be warming up to 80 DEG C, then add acetone, continue reaction 2 hours, obtain the 4th reaction solution.Wherein, the mol ratio of the isocyanic ester of hydroxy acrylate and modification is 0.3: 1.Hydroxy acrylate is selected from trimethylolpropane diacrylate.Stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 0.2: 30.The interpolation quality of acetone is 10% of the total mass of the second reaction solution, hydroxy acrylate and stopper.
6, under the condition of 45 DEG C, in the 4th reaction solution, add triethylamine, react 0.8 hour, obtain transparent polyurethane acrylate prepolymer.Wherein, the mol ratio of triethylamine and multi-hydroxy carboxy acid is 1.2: 1.
7, under the condition of the Keep agitation of 350 revs/min, deionized water is joined in polyurethane acrylate prepolymer, continue to disperse 30 minutes with the speed stirring and emulsifying of 500 revs/min, through cooling, obtain urethane acrylate dispersoid.
(3) preparation of ultraviolet-curing paint:
1, following component is taken according to mass fraction:
Wherein, filler is selected from aluminium sesquioxide.
2, according to said ratio, urethane acrylate dispersoid, filler, light trigger, flow agent, dispersion agent and defoamer are added in dispersion cylinder, dispersed with stirring 20 minutes, cross 300 mesh sieves, namely obtain ultraviolet-curing paint.Wherein, dispersion agent is selected from PL-20.Flow agent is selected from TEGO425.Defoamer is selected from BYK024.Light trigger is selected from 2959.
The identical testing method of embodiment 1 is adopted to obtain the performance of the purple ultraviolet-curing paint of the present embodiment in table 1.
Embodiment 4
The preparation process of the ultraviolet-curing paint of the present embodiment is as follows:
(1) preparation of chainextender: pentaerythritol triacrylate and methoxyphenol (MEHQ) are proceeded to the acetone of 10g in the there-necked flask that thermometer, prolong and agitator are housed, wherein, the quality of methoxyphenol and the mass ratio of pentaerythritol triacrylate are then be placed in 45 DEG C waters bath with thermostatic control at 0.5: 100, constant pressure funnel is utilized dropwise to be joined in there-necked flask by isophorone diisocyanate, add dibutyl tin laurate (DBTAL) simultaneously and carry out catalysis, then in 60 DEG C of reactions 2 hours, the first mixed solution is obtained.The acetone soln constant voltage of TriMethylolPropane(TMP) is instilled in the first reaction solution, in 70 DEG C of reactions until isocyano ion disappears, discharging, obtain colourless or lurid double bond containing glycol monomer, be chainextender, wherein, the mass ratio of dibutyl tin laurate and isophorone diisocyanate is 0.08: 100; The mol ratio of pentaerythritol triacrylate, isophorone diisocyanate and TriMethylolPropane(TMP) is 1: 1: 1.
(2) preparation of urethane acrylate dispersoid:
1, under logical nitrogen protection condition; to in the four mouthfuls of round reaction flasks being placed with thermometer, prolong, stirring rod; add vulcabond; be placed in the water bath with thermostatic control of 75 DEG C; utilize constant pressure funnel by 1; 4-cyclohexane dimethanol is added drop-wise in four mouthfuls of reaction flasks, and insulation reaction 2 hours, obtains the vulcabond of modification.Wherein, the mol ratio of Isosorbide-5-Nitrae-cyclohexane dimethanol and vulcabond is 1: 2.Vulcabond is selected from, terephthalylidene vulcabond.
2, in the vulcabond of modification, add dibasic alcohol, in 70 DEG C of stirring reactions 3 hours, obtain the first reaction solution.Wherein, dibasic alcohol is selected from PCDL.Wherein, the mol ratio of the vulcabond of dibasic alcohol and modification is 1: 5.
3, in the first reaction solution, add multi-hydroxy carboxy acid and catalyzer, in 75 DEG C of stirring reactions 1 ~ 2 hour, obtain the second reaction solution.Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.2: 1, multi-hydroxy carboxy acid is at least one in dimethylol propionic acid and dimethylolpropionic acid, and catalyzer is dibutyl tin laurate, and the mass ratio of catalyzer and multi-hydroxy carboxy acid is 1: 6.
4, be cooled to 60 DEG C, adopt constant pressure funnel to add in the second reaction solution by chainextender prepared by step (1), carry out chain extending reaction 3 hours, obtain the 3rd reaction solution.Wherein, the mol ratio of the vulcabond of chainextender and modification is 0.3: 1.
5, under the condition of 60 DEG C, in the 3rd reaction solution, add hydroxy acrylate and stopper carries out end-blocking, react after 1 hour, be warming up to 85 DEG C, then add acetone, continue reaction 2 hours, obtain the 4th reaction solution.Wherein, the mol ratio of the isocyanic ester of hydroxy acrylate and modification is 0.5: 1.Hydroxy acrylate is selected from Rocryl 410.Stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 0.4: 50.The interpolation quality of acetone is 8% of the total mass of the second reaction solution, hydroxy acrylate and stopper.
6, under the condition of 50 DEG C, in the 4th reaction solution, add triethylamine, react 1.0 hours, obtain transparent polyurethane acrylate prepolymer.Wherein, the mol ratio of triethylamine and multi-hydroxy carboxy acid is 1.5: 1.
7, under the condition of the Keep agitation of 400 revs/min, deionized water joins in polyurethane acrylate prepolymer, continues to disperse 40 minutes with the speed stirring and emulsifying of 600 revs/min, through cooling, obtains urethane acrylate dispersoid.
(3) preparation of ultraviolet-curing paint:
1, following component is taken according to mass fraction:
Wherein, filler is selected from talcum powder.
2, according to said ratio, urethane acrylate dispersoid, filler, light trigger, flow agent, dispersion agent and defoamer are added in dispersion cylinder, dispersed with stirring 15 minutes, cross 200 mesh sieves, namely obtain ultraviolet-curing paint.Wherein, dispersion agent is selected from PL-20.Flow agent is selected from TEGO450.Defoamer is selected from BYK022.Light trigger is selected from KIP160.
The identical testing method of embodiment 1 is adopted to obtain the performance of the purple ultraviolet-curing paint of the present embodiment in table 1.
What table 1 represented is the performance of the ultraviolet-curing paint of embodiment 1 ~ 4.
Obviously, above-mentioned ultraviolet-curing paint has good performance.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a preparation method for ultraviolet-curing paint, is characterized in that, comprises the steps:
Under the environment of protective gas, mixed by vulcabond with Isosorbide-5-Nitrae-cyclohexane dimethanol, in 60 ~ 80 DEG C of reactions 1 ~ 3 hour, obtain the vulcabond of modification, wherein, the mol ratio of described Isosorbide-5-Nitrae-cyclohexane dimethanol and described vulcabond was 1: 2;
In the vulcabond of described modification, add dibasic alcohol, in 60 ~ 80 DEG C of stirring reactions 2 ~ 4 hours, obtain the first reaction solution, wherein, the mol ratio of the vulcabond of described dibasic alcohol and described modification was 1: 2 ~ 6;
In described first reaction solution, add multi-hydroxy carboxy acid and catalyzer, in 70 ~ 80 DEG C of stirring reactions 1 ~ 2 hour, obtain the second reaction solution, wherein, the mol ratio of the vulcabond of described multi-hydroxy carboxy acid and described modification was 0.1 ~ 0.3: 1;
Under the condition of 50 ~ 60 DEG C, by described second reaction solution and chainextender mixing, carry out chain extending reaction 2 ~ 3 hours, obtain the 3rd reaction solution, wherein, the mol ratio of the vulcabond of described chainextender and described modification is 0.1 ~ 0.3: 1;
Under the condition of 50 ~ 60 DEG C, in described 3rd reaction solution, add hydroxy acrylate and stopper carries out end-blocking, react after 1 hour, be warming up to 70 ~ 85 DEG C, then add acetone, continue reaction 2 hours, obtain the 4th reaction solution; Wherein, the mol ratio of the vulcabond of described hydroxy acrylate and described modification is 0.2 ~ 0.6: 1; And
Under the condition of 40 ~ 50 DEG C, in described 4th reaction solution, add triethylamine, react 0.5 ~ 1.0 hour, obtain polyurethane acrylate prepolymer, wherein, the mol ratio of described triethylamine and described multi-hydroxy carboxy acid is 1 ~ 1.5: 1;
Under the condition of Keep agitation, deionized water is joined in described polyurethane acrylate prepolymer, continue stirring and emulsifying dispersion 30 ~ 40 minutes, through cooling, obtain urethane acrylate dispersoid, wherein, the mass ratio of described polyurethane acrylate prepolymer and described deionized water is 30 ~ 50: 40 ~ 60;
Following component is comprised: described urethane acrylate dispersoid 75 ~ 90 parts, filler 5 ~ 20 parts, light trigger 2 ~ 6 parts, flow agent 0.1 ~ 1 part, dispersion agent 0.1 ~ 1 part and defoamer 0.1 ~ 1 part according to mass fraction; And
Described urethane acrylate dispersoid, described filler, described light trigger, described flow agent, described dispersion agent and described defoamer are mixed, dispersed with stirring 15 ~ 30 minutes, obtains ultraviolet-curing paint.
2. the preparation method of ultraviolet-curing paint according to claim 1, it is characterized in that, described vulcabond is selected from least one in Xylene Diisocyanate, dicyclohexyl methane diisocyanate, '-diphenylmethane diisocyanate, terephthalylidene vulcabond, hexamethylene diisocyanate and isophorone diisocyanate.
3. the preparation method of ultraviolet-curing paint according to claim 1, is characterized in that, described dibasic alcohol is selected from least one in polyether Glycols, polycaprolactone diols and PCDL.
4. the preparation method of ultraviolet-curing paint according to claim 1, is characterized in that, described multi-hydroxy carboxy acid is at least one in dimethylol propionic acid and dimethylolpropionic acid.
5. the preparation method of the ultraviolet-curing paint according to claim 1 or 4, is characterized in that, described catalyzer is dibutyl tin laurate; Wherein, the mass ratio of described catalyzer and described multi-hydroxy carboxy acid is 0.1 ~ 1: 3 ~ 8.
6. the preparation method of ultraviolet-curing paint according to claim 1, it is characterized in that, described hydroxy acrylate is selected from least one in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, pentaerythritol triacrylate, Rocryl 410, Propylene glycol monoacrylate and trimethylolpropane diacrylate; Described stopper is p methoxy phenol, and the mass ratio of described stopper and described hydroxy acrylate is 0.1 ~ 0.5: 20 ~ 60.
7. the preparation method of ultraviolet-curing paint according to claim 1, is characterized in that, also comprises the preparation process of described chainextender:
Pentaerythritol triacrylate, methoxyphenol and acetone are mixed, under the condition of 45 DEG C, adds isophorone diisocyanate and dibutyl tin laurate, then in 50 ~ 60 DEG C of reactions 1 ~ 3 hour, obtain the first mixed solution; The acetone soln of TriMethylolPropane(TMP) is added in described first mixed solution, in 60 ~ 75 DEG C of reactions until isocyano ion disappears, obtain double bond containing glycol monomer, wherein, the mol ratio of described pentaerythritol triacrylate, described isophorone diisocyanate and described TriMethylolPropane(TMP) is 1: 1: 1.
8. the preparation method of ultraviolet-curing paint according to claim 1, is characterized in that, described filler is selected from least one in silicon-dioxide, titanium dioxide, aluminium sesquioxide, talcum powder and mica powder.
9. the preparation method of ultraviolet-curing paint according to claim 1, it is characterized in that, be set forth in the condition of 50 ~ 60 DEG C under, described hydroxy acrylate is added and described stopper carries out end-blocking in described 3rd reaction solution, react after 1 hour, be warming up to 70 ~ 85 DEG C, then add in the step of described acetone, the interpolation quality of described acetone is 3 ~ 10% of the total mass of described 3rd reaction solution, described hydroxy acrylate and described stopper.
10. the ultraviolet-curing paint for preparing of the preparation method of a ultraviolet-curing paint as claimed in any one of claims 1 to 9 wherein.
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CN112724822A (en) * 2021-01-28 2021-04-30 汕头市鑫源化工科技有限公司 UV-cured high-gloss coating and preparation method thereof
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CN104530898A (en) * 2014-12-25 2015-04-22 湖州南浔双林振森实木加工厂 Ultraviolet-curing paint and preparation method thereof
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CN112457768A (en) * 2020-11-26 2021-03-09 上海颜钛实业有限公司 Photocuring spray paint and preparation method thereof
CN112457768B (en) * 2020-11-26 2021-10-29 上海颜钛实业有限公司 Photocuring spray paint and preparation method thereof
CN112831016A (en) * 2020-12-31 2021-05-25 东胜化学(上海)有限公司 Polyurethane resin and preparation method thereof
CN112851902A (en) * 2021-01-11 2021-05-28 北京化工大学 Nano calcium carbonate modified waterborne polyurethane acrylate with photosensitive group and preparation method thereof
CN112851902B (en) * 2021-01-11 2022-05-03 北京化工大学 Nano calcium carbonate modified waterborne polyurethane acrylate with photosensitive group and preparation method thereof
CN112724822A (en) * 2021-01-28 2021-04-30 汕头市鑫源化工科技有限公司 UV-cured high-gloss coating and preparation method thereof

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