CN105440260A - Ultraviolet curing urethane acrylate and preparation method thereof - Google Patents

Ultraviolet curing urethane acrylate and preparation method thereof Download PDF

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Publication number
CN105440260A
CN105440260A CN201511019707.8A CN201511019707A CN105440260A CN 105440260 A CN105440260 A CN 105440260A CN 201511019707 A CN201511019707 A CN 201511019707A CN 105440260 A CN105440260 A CN 105440260A
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reaction solution
vulcabond
polyurethane acrylate
acrylate
hydroxy
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CN105440260B (en
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刘键
姚志刚
景梅
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Shenzhen Li Jian Bona Technology Co., Ltd.
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Zhongwu Function Material Institute Co Ltd
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    • 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

Abstract

The invention relates to ultraviolet curing urethane acrylate and a preparation method thereof. The preparation method comprises the following steps: carrying out a reaction I between diisocyanate and a modifying agent to obtain modified diisocyanate; carrying out a reaction II between modified diisocyanate and divalent alcohol to obtain a first reaction solution; adding polyhydroxy carboxylic acid and a catalyst in the first reaction solution for a reaction III to obtain a second reaction solution; adding 2-ethyl-1,3-hexanediol into the second section solution for a reaction IV to obtain a third reaction solution; adding hydroxyl acrylate and a polymerization inhibitor into the third reaction solution for a reaction V to obtain a fourth reaction solution; adding triethylamine into the fourth reaction solution for a reaction VI to obtain a urethane acrylate prepolymer; adding deionized water into the urethane acrylate prepolymer to prepare ultraviolet curing urethane acrylate. Ultraviolet curing urethane acrylate prepared according to the preparation method is the novel urethane acrylate.

Description

UV-cured polyurethane acrylate and preparation method thereof
Technical field
The present invention relates to paint field, particularly a kind of UV-cured polyurethane acrylate and preparation method thereof.
Background technology
Traditional solvent-borne type UV-cured polyurethane acrylate in the application, need to add esters of acrylic acid reactive thinner to regulate the viscosity of oligomer resin, and these reactive thinners have certain skin irritation and volatility usually, after ultraviolet light polymerization, the complete small molecules of unreacted evaporate in air all can cause serious harm to workmen, user and environment.Along with the raising of people's environmental consciousness and various countries to volatile organic compounds (VOC) containing quantitative limitation, the water-borne UV-curing urethane acrylate product of exploitation low stain environment-friendly type has become everybody common recognition.
Aquosity ultraviolet light (UV) curing system combines traditional photo-cured coating and the plurality of advantages of water-borne coatings, replaces viscosity and the rheological property of reactive thinner regulation system with water, has the advantages such as nonflammable, process operation is convenient.But the solid content of the water borne UV curing resin of report only has 30-50% at present, and when solid content is more than 50%, viscosity sharply increases, and the performance of resin and film sharply reduces.And research focuses mostly in water-dispersion or emulsion system, this type of water-borne coatings is due to washiness in system, moreover evaporation of water enthalpy is higher, volatilization process is very slow, too much water makes to exchange dry and solidification rate faster for sacrifice the energy for cost, this increases energy consumption and time undoubtedly, and hardness is lower.
Summary of the invention
Based on this, be necessary to provide a kind of a kind of method can preparing novel UV-cured polyurethane acrylate.
In addition, a kind of novel UV-cured polyurethane acrylate is also provided.
A preparation method for UV-cured polyurethane acrylate, comprises the steps:
Under the environment of protective gas, mixed by vulcabond with properties-correcting agent, in 60 ~ 85 DEG C of reactions 1 ~ 3 hour, obtain the vulcabond of modification, wherein, the mol ratio of described properties-correcting agent 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, in described second reaction solution, add 2-ethyl-1,3-hexylene glycol, chain extending reaction 2 ~ 3 hours, obtains the 3rd reaction solution, wherein, the mol ratio of the vulcabond of described 2-ethyl-1,3-hexylene glycol 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; And
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 UV-cured polyurethane acrylate, wherein, the mass ratio of described polyurethane acrylate prepolymer and described deionized water is 30 ~ 50:40 ~ 60.
Wherein in an embodiment, described vulcabond is selected from least one in 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 quality of described catalyzer is 0.1% ~ 1% of the summation of the quality of described multi-hydroxy carboxy acid and described first reaction solution.
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.
Wherein in an embodiment, described stopper is p methoxy phenol, and the mass ratio of described stopper and described hydroxy acrylate is 0.1 ~ 0.5:20 ~ 60.
Wherein in an embodiment, described properties-correcting agent is selected from least one in dihydroxyphenyl propane, 1,3-diamantane glycol, 1,3-bis-(4-hydroxybenzene) diamantane and Isosorbide-5-Nitrae-cyclohexane dimethanol.
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 quality of described acetone is 5 ~ 10% of the total mass of described 3rd reaction solution, described hydroxy acrylate and described stopper.
A kind of UV-cured polyurethane acrylate prepared by the preparation method of above-mentioned UV-cured polyurethane acrylate.
The preparation method of above-mentioned UV-cured polyurethane acrylate is simple to operate, is easy to suitability for industrialized production.Above-mentioned UV-cured polyurethane acrylate by introduce properties-correcting agent to vulcabond modification, continue with dibasic alcohol, multi-hydroxy carboxy acid, and functional glycol chain extender, acrylate monomers reaction, synthesized a kind of novel urethane acrylate.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the UV-cured polyurethane acrylate of an embodiment.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments UV-cured polyurethane acrylate and preparation method thereof is described in further detail below.
As shown in Figure 1, the preparation method of the UV-cured polyurethane acrylate of an embodiment, comprises the steps:
Step S110: under the environment of protective gas, mixed by vulcabond with properties-correcting agent, in 60 ~ 85 DEG C of reactions 1 ~ 3 hour, obtains the vulcabond of modification.
Wherein, the mol ratio of properties-correcting agent 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 and isophorone diisocyanate.
Wherein, properties-correcting agent is selected from least one in dihydroxyphenyl propane, 1,3-diamantane glycol, 1,3-bis-(4-hydroxybenzene) diamantane and Isosorbide-5-Nitrae-cyclohexane dimethanol.
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 described dibasic alcohol and described 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 described multi-hydroxy carboxy acid and described 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 quality of catalyzer is 0.1% ~ 1% of the summation of the quality of multi-hydroxy carboxy acid and the first reaction solution.
Step S140: under the condition of 50 ~ 60 DEG C, adds 2-ethyl-1,3-hexylene glycol in the second reaction solution, and chain extending reaction 2 ~ 3 hours obtains the 3rd reaction solution.
Wherein, the mol ratio of the vulcabond of described 2-ethyl-1,3-hexylene glycol and described 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, wherein, the mol ratio of the vulcabond of described hydroxy acrylate and described modification is 0.2 ~ 0.6:1,
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 quality of acetone is 5 ~ 10% 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 0.5 ~ 1.0 hour, obtains polyurethane acrylate prepolymer.
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 UV-cured polyurethane acrylate.
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.
The preparation method of above-mentioned UV-cured polyurethane acrylate is simple to operate, is easy to suitability for industrialized production.Above-mentioned UV-cured polyurethane acrylate by properties-correcting agent to vulcabond modification, continue with dibasic alcohol, multi-hydroxy carboxy acid, and functional glycol chain extender, acrylate monomers reaction, synthesized a kind of novel urethane acrylate.
A kind of UV-cured polyurethane acrylate prepared by the preparation method of above-mentioned UV-cured polyurethane acrylate, this UV-cured polyurethane acrylate is a kind of novel urethane acrylate, can be used in UV-light coating, to make the coating containing this UV-cured polyurethane acrylate, there is good performance.
Be below specific embodiment part:
Embodiment 1
The preparation process of the UV-cured polyurethane acrylate of the present embodiment is as follows:
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; constant pressure funnel is utilized to be added drop-wise to by properties-correcting agent in four mouthfuls of reaction flasks; insulation reaction 3 hours, obtains the vulcabond of modification.Wherein, the mol ratio of properties-correcting agent and vulcabond is 1:2.Vulcabond be selected from dicyclohexyl methane diisocyanate.Properties-correcting agent is selected from dihydroxyphenyl propane.
2, in the vulcabond of modification, add dibasic alcohol, in 60 DEG C of stirring reactions 4 hours, obtain the first reaction solution.Wherein, the mol ratio of the vulcabond of dibasic alcohol and modification is 1:2.Dibasic alcohol is selected from polyether Glycols.
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 0.1:1, and multi-hydroxy carboxy acid is dimethylol propionic acid, and catalyzer is dibutyl tin laurate, and the quality of catalyzer is 0.1% of the summation of the quality of multi-hydroxy carboxy acid and the first reaction solution.
4, be cooled to 50 DEG C, adopt constant pressure funnel to add in the second reaction solution by 2-ethyl-1,3-hexylene glycol, chain extending reaction 2 hours, obtains the 3rd reaction solution.Wherein, the mol ratio of the vulcabond of 2-ethyl-1,3-hexylene glycol and modification is 0.1:1.
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 vulcabond of hydroxy acrylate and modification is 0.2:1.Hydroxy acrylate is selected from Hydroxyethyl acrylate.Stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 0.1:20.The 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 1.0 hours, 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, will join in polyurethane acrylate prepolymer, and continue to disperse 30 minutes with the speed stirring and emulsifying of 400 revs/min, through cooling, obtain UV-cured polyurethane acrylate.
Embodiment 2
The preparation process of the UV-cured polyurethane acrylate of the present embodiment is as follows:
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 85 DEG C; constant pressure funnel is utilized to be added drop-wise to by properties-correcting agent in four mouthfuls of reaction flasks; insulation reaction 1 hour, obtains the vulcabond of modification.Wherein, the mol ratio of properties-correcting agent and vulcabond is 1:2.Vulcabond is selected from '-diphenylmethane diisocyanate.Properties-correcting agent is selected from 1,3-diamantane glycol.
2, in the vulcabond of modification, add dibasic alcohol, in 80 DEG C of stirring reactions 2 hours, obtain the first reaction solution.Wherein, the mol ratio of the vulcabond of dibasic alcohol and modification is 1:6.Dibasic alcohol is selected from polyether Glycols.
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 quality of catalyzer is 1% of the summation of the quality of multi-hydroxy carboxy acid and the first reaction solution.
4, be cooled to 60 DEG C, adopt constant pressure funnel to add in the second reaction solution by 2-ethyl-1,3-hexylene glycol, chain extending reaction 2 hours, obtains the 3rd reaction solution.Wherein, the mol ratio of the vulcabond of 2-ethyl-1,3-hexylene glycol 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 vulcabond of hydroxy acrylate and modification 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 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 0.5 hour, 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 350 revs/min, deionized water is joined in polyurethane acrylate prepolymer, continue to disperse 30 minutes with the speed stirring and emulsifying of 600 revs/min, through cooling, obtain UV-cured polyurethane acrylate.
Embodiment 3
The preparation process of the UV-cured polyurethane acrylate of the present embodiment is as follows:
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; constant pressure funnel is utilized to be added drop-wise to by properties-correcting agent in four mouthfuls of reaction flasks; insulation reaction 2 hours, obtains the vulcabond of modification.Wherein, the mol ratio of properties-correcting agent and vulcabond is 1:2.Vulcabond is selected oneself vulcabond.Properties-correcting agent is selected from 1,3-bis-(4-hydroxybenzene) diamantane.
2, in the vulcabond of modification, add dibasic alcohol, in 70 DEG C of stirring reactions 3 hours, obtain the first reaction solution.Wherein, the mol ratio of the vulcabond of dibasic alcohol and modification is 1:4.Dibasic alcohol is selected from PCDL.
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 0.2:1, and multi-hydroxy carboxy acid is dimethylol propionic acid, and catalyzer is dibutyl tin laurate, and the quality of catalyzer is 0.5% of the summation of the quality of multi-hydroxy carboxy acid and the first reaction solution.
4, be cooled to 55 DEG C, adopt constant pressure funnel to add in the second reaction solution by 2-ethyl-1,3-hexylene glycol, chain extending reaction 2.5 hours, obtains the 3rd reaction solution.Wherein, the mol ratio of the vulcabond of 2-ethyl-1,3-hexylene glycol and modification is 0.2:1.
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 vulcabond of hydroxy acrylate and modification is 0.4:1.Hydroxy acrylate is selected from pentaerythritol triacrylate.Stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 0.3:40.The 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 0.7 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, will join in polyurethane acrylate prepolymer, and continue to disperse 35 minutes with the speed stirring and emulsifying of 500 revs/min, through cooling, obtain UV-cured polyurethane acrylate.
The identical testing method of embodiment 1 is adopted to obtain the performance of the UV-cured polyurethane acrylate of the present embodiment in table 1.
Embodiment 4
The preparation process of the UV-cured polyurethane acrylate of the present embodiment is as follows:
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; constant pressure funnel is utilized to be added drop-wise to by properties-correcting agent in four mouthfuls of reaction flasks; insulation reaction 3 hours, obtains the vulcabond of modification.Wherein, the mol ratio of properties-correcting agent and vulcabond is 1:2.Vulcabond is selected from isophorone diisocyanate.Properties-correcting agent is selected from 1,3-bis-(4-hydroxybenzene) diamantane.
2, in the vulcabond of modification, add dibasic alcohol, in 70 DEG C of stirring reactions 3 hours, obtain the first reaction solution.Wherein, the mol ratio of the vulcabond of dibasic alcohol and modification is 1:5.Dibasic alcohol is selected from PCDL.
3, in the first reaction solution, add multi-hydroxy carboxy acid and catalyzer, in 75 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 0.2:1, and multi-hydroxy carboxy acid is dimethylol propionic acid, and catalyzer is dibutyl tin laurate, and the quality of catalyzer is 1% of the summation of the quality of multi-hydroxy carboxy acid and the first reaction solution.
4, be cooled to 60 DEG C, adopt constant pressure funnel to add in the second reaction solution by 2-ethyl-1,3-hexylene glycol, chain extending reaction 3 hours, obtains the 3rd reaction solution.Wherein, the mol ratio of the vulcabond of 2-ethyl-1,3-hexylene glycol 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 85 DEG C, then add acetone, continue reaction 2 hours, obtain the 4th reaction solution.Wherein, the mol ratio of the vulcabond 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 0.3:40.The 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, 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 is joined in polyurethane acrylate prepolymer, continue to disperse 40 minutes with the speed stirring and emulsifying of 600 revs/min, through cooling, obtain UV-cured polyurethane acrylate.
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 UV-cured polyurethane acrylate, is characterized in that, comprises the steps:
Under the environment of protective gas, mixed by vulcabond with properties-correcting agent, in 60 ~ 85 DEG C of reactions 1 ~ 3 hour, obtain the vulcabond of modification, wherein, the mol ratio of described properties-correcting agent 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, in described second reaction solution, add 2-ethyl-1,3-hexylene glycol, chain extending reaction 2 ~ 3 hours, obtains the 3rd reaction solution, wherein, the mol ratio of the vulcabond of described 2-ethyl-1,3-hexylene glycol 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; 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 Keep agitation, deionized water is joined in described polyurethane acrylate prepolymer, continue stirring and emulsifying dispersion 30 ~ 40 minutes, through cooling, obtain UV-cured polyurethane acrylate, wherein, the mass ratio of described polyurethane acrylate prepolymer and described deionized water is 30 ~ 50: 40 ~ 60.
2. the preparation method of UV-cured polyurethane acrylate according to claim 1, it is characterized in that, described vulcabond is selected from least one in dicyclohexyl methane diisocyanate, '-diphenylmethane diisocyanate, terephthalylidene vulcabond, hexamethylene diisocyanate and isophorone diisocyanate.
3. the preparation method of UV-cured polyurethane acrylate 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 UV-cured polyurethane acrylate 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 UV-cured polyurethane acrylate according to claim 1 or 4, is characterized in that, described catalyzer is dibutyl tin laurate; Wherein, the quality of described catalyzer is 0.1% ~ 1% of the summation of the quality of described multi-hydroxy carboxy acid and described first reaction solution.
6. the preparation method of UV-cured polyurethane acrylate 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.
7. the preparation method of the UV-cured polyurethane acrylate according to claim 1 or 6, is characterized in that, described stopper is p methoxy phenol, and the mass ratio of described stopper and described hydroxy acrylate is 0.1 ~ 0.5: 20 ~ 60.
8. the preparation method of UV-cured polyurethane acrylate according to claim 1, it is characterized in that, described properties-correcting agent is selected from dihydroxyphenyl propane, 1,3-diamantane glycol, 1, at least one in 3-bis-(4-hydroxybenzene) diamantane and Isosorbide-5-Nitrae-cyclohexane dimethanol.
9. the preparation method of UV-cured polyurethane acrylate 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 quality of described acetone is 5 ~ 10% of the total mass of described 3rd reaction solution, described hydroxy acrylate and described stopper.
10. the UV-cured polyurethane acrylate for preparing of the preparation method of a UV-cured polyurethane acrylate as claimed in any one of claims 1 to 9 wherein.
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CN105778042A (en) * 2016-05-06 2016-07-20 南昌航空大学 Preparation method for curing fingerprint-resistant urethane acrylate with electron beam
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CN105778040A (en) * 2016-05-06 2016-07-20 南昌航空大学 Method for preparing environment-friendly anti-fingerprint resin
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