CN109054623A - A kind of curable urethane acrylate aqueous dispersion and preparation method thereof - Google Patents
A kind of curable urethane acrylate aqueous dispersion and preparation method thereof Download PDFInfo
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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
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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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
- C08G18/67—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
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Abstract
The present invention discloses a kind of curable urethane acrylate aqueous dispersion and preparation method thereof, wherein, the method includes the steps: under the conditions of 60-95 DEG C, diisocyanate, dihydromethyl propionic acid and organic silicon-fluorine polyalcohol are mixed, reaction obtains the base polyurethane prepolymer for use as of grafted-organosilicon fluorine under the effect of the catalyst；Under the conditions of 70-90 DEG C, polymerization inhibitor, antioxidant and hydroxy acryl acid ester are added in the base polyurethane prepolymer for use as of the grafted-organosilicon fluorine, the urethane acrylate that hybrid reaction is blocked；Under the conditions of 10-40 DEG C, organic amine and deionized water are added in the urethane acrylate of the sealing end, hybrid reaction obtains curable urethane acrylate aqueous dispersion.The advantages of curable urethane acrylate aqueous dispersion prepared by the present invention combines water paint and photocureable coating, its solid content is up to 50%, without organic solvent, and there is extreme hardness and extremely strong adhesive force, the anti-graffiti performance of resistant after forming paint film is stronger, more longlasting.
Description
Technical field
The present invention relates to paint field more particularly to a kind of curable urethane acrylate aqueous dispersion and its preparation sides
Method.
Background technique
Ultraviolet solidified aqueous coating is increasingly concerned because of its environmental protection, energy conservation and clean manufacturing theory.It is ultraviolet
UV curable waterborne coatings combine the advantages of both water paint and photocureable coating, and it is hard to solve traditional photocureable coating film
Contradiction between degree and flexibility.
However, the photocuring resistant resin reported at present, most of is solvent type, or needs to add activity dilution
Agent carries out viscosity reduction.And the anti-graffiti performance of its resistant is realized by outer addition organic silicon-fluorine component, practical organic silicon-fluorine
Group is not connected in backbone structure, so the anti-graffiti performance of resistant is poor and not lasting.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of curable urethane acrylate water
Dispersion and preparation method thereof, it is intended to solve that existing light-cured resin solid content is low and the anti-graffiti performance of resistant is poor and not
Lasting problem.
Technical scheme is as follows:
A kind of preparation method of curable urethane acrylate aqueous dispersion, wherein comprising steps of
Under the conditions of 60-95 DEG C, diisocyanate, dihydromethyl propionic acid and organic silicon-fluorine polyalcohol are mixed, in catalyst
Under the action of reaction obtain the base polyurethane prepolymer for use as of grafted-organosilicon fluorine；
Under the conditions of 70-90 DEG C, the grafted-organosilicon fluorine is added in polymerization inhibitor, antioxidant and hydroxy acryl acid ester
In base polyurethane prepolymer for use as, urethane acrylate that hybrid reaction is blocked；
Under the conditions of 10-40 DEG C, organic amine and deionized water are added in the urethane acrylate of the sealing end, mixing is anti-
It should obtain curable urethane acrylate aqueous dispersion.
The preparation method of the curable urethane acrylate aqueous dispersion, wherein the diisocyanate, dihydroxy first
The molar ratio of base propionic acid and organic silicon-fluorine polyalcohol are as follows: (3-7): (1-5): 1.
The preparation method of the curable urethane acrylate aqueous dispersion, wherein the organic silicon-fluorine polyalcohol is
One of organosilicon polyalcohol and perfluoropolyether are a variety of.
The preparation method of the curable urethane acrylate aqueous dispersion, wherein the diisocyanate is toluene
Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, methyl diphenylene diisocyanate and oneself is two different
One of cyanate is a variety of.
The preparation method of the curable urethane acrylate aqueous dispersion, wherein the catalyst is tin dilaurate
Dibutyl tin, and the additional amount of the catalyst is diisocyanate, dihydromethyl propionic acid, organic silicon-fluorine polyalcohol and contains hydroxyl
The 0.1-1% of base acrylate gross mass.
The preparation method of the curable urethane acrylate aqueous dispersion, wherein the hydroxy acryl acid ester is
One of two trimethylolpropane trimethacrylates, pentaerythritol triacrylate and double pentaerythritol C5 methacrylate are more
Kind.
The preparation method of the curable urethane acrylate aqueous dispersion, wherein the polymerization inhibitor is para hydroxybenzene
Methyl ether, the additional amount of the polymerization inhibitor are diisocyanate and dihydromethyl propionic acid, organic silicon-fluorine polyalcohol and hydroxyl third
The 0.1-0.5% of olefin(e) acid ester gross mass；
And/or the antioxidant is BHT, the additional amount of the antioxidant be diisocyanate with dihydromethyl propionic acid, have
The 0.1-0.5% of machine fluosilicic polyalcohol and hydroxy acryl acid ester gross mass.
The preparation method of the curable urethane acrylate aqueous dispersion, wherein the step is in 10-40 DEG C of condition
Under, organic amine and deionized water are added in the urethane acrylate of the sealing end, hybrid reaction obtains light-solidifying poly ammonia
Ester acrylate aqueous dispersion, later further include:
At room temperature, polyamine is added in the curable urethane acrylate aqueous dispersion, mixing is expanded
Chain reaction obtains polyurethane acrylate resin.
The preparation method of the curable urethane acrylate aqueous dispersion, wherein the polyamine be ethylenediamine, oneself
Diamines and isophorone diamine it is one or more.
A kind of curable urethane acrylate aqueous dispersion, wherein be prepared using the preparation method.
The utility model has the advantages that the present invention provides a kind of preparation method of curable urethane acrylate aqueous dispersion, by setting
Organic silicon-fluorine group is grafted in the molecular backbone of the urethane acrylate by meter, to effectively promote light-cured polyurethane
The anti-graffiti performance of resistant and holding after acrylate aqueous dispersion formation paint film is permanent.Further, by the method for the invention
The advantages of curable urethane acrylate aqueous dispersion of preparation combines water paint and photocureable coating, solid content are high
Up to 50%, organic solvent is free of, and there is extreme hardness and extremely strong adhesive force.
Detailed description of the invention
Fig. 1 is a kind of process of the preparation method preferred embodiment of curable urethane acrylate aqueous dispersion of the present invention
Figure.
Specific embodiment
It is of the invention to make the present invention provides a kind of curable urethane acrylate aqueous dispersion and preparation method thereof
Purpose, technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that this place is retouched
It states that specific examples are only used to explain the present invention, is not intended to limit the present invention.
Referring to Fig. 1, Fig. 1 is that a kind of preparation method of curable urethane acrylate aqueous dispersion of the present invention is preferably real
Apply the flow chart of example, wherein as shown, including the following steps:
S100, under the conditions of 60-95 DEG C, by diisocyanate, dihydromethyl propionic acid and organic silicon-fluorine polyalcohol mix, urging
Reaction obtains the base polyurethane prepolymer for use as of grafted-organosilicon fluorine under the action of agent；
S200, under the conditions of 70-90 DEG C, by polymerization inhibitor, antioxidant and hydroxy acryl acid ester be added it is described grafting it is organic
In the base polyurethane prepolymer for use as of fluosilicic, urethane acrylate that hybrid reaction is blocked；
S300, under the conditions of 10-40 DEG C, organic amine and deionized water are added in the urethane acrylate of the sealing end,
Hybrid reaction obtains curable urethane acrylate aqueous dispersion.
Organic silicon-fluorine group is grafted to the molecule of the urethane acrylate by chemical reaction design by the present embodiment
In main chain, i.e., organic silicon-fluorine group and urethane acrylate are bonded by chemical bond；In compared with the existing technology directly
Organic silicon-fluorine auxiliary agent, curable urethane acrylate manufactured in the present embodiment are adulterated in the urethane acrylate prepared
For aqueous dispersion after forming paint film, the anti-graffiti performance of resistant is stronger, more longlasting.
Further, in this embodiment preparation curable urethane acrylate aqueous dispersion combine water paint and
The advantages of photocureable coating, solid content is up to 50%, without organic solvent, and has extreme hardness and extremely strong adhesive force.
In a preferred embodiment, under the conditions of 60-95 DEG C, by diisocyanate, dihydromethyl propionic acid and
Organic silicon-fluorine polyalcohol is (3-7): (1-5) according to molar ratio: 1 ratio mixes, and reacts 2-3h under the effect of the catalyst and obtains
The base polyurethane prepolymer for use as being grafted to organic silicon-fluorine.
In this embodiment, the hydroxyl in the dihydromethyl propionic acid and organic silicon-fluorine polyalcohol and the diisocyanate
In-NCO group reacts generate polyurethanes under the effect of the catalyst, isocyanates (- NCO) is anti-with hydroxyl
It should be second order reaction, reaction rate constant changes with hydroxy radical content.If the content mistake of organic silicon-fluorine polyalcohol in reactant
Height, then under 60-95 DEG C of hot conditions, reaction rate is too fast to be easy to cause product that coking occurs, to influence product production
Efficiency；If the content of organic silicon-fluorine polyalcohol is too low in reactant, the organic silicon-fluorine being grafted in the base polyurethane prepolymer for use as generated
It is less, cause the anti-graffiti performance of the resistant of product that cannot reach best.
In a preferred embodiment, the organic silicon-fluorine polyalcohol is in organosilicon polyalcohol and perfluoropolyether
It is one or more, but not limited to this.Preferably, the organosilicon polyalcohol is hydroxyalkyl polysiloxanes.
In a preferred embodiment, the diisocyanate is toluene di-isocyanate(TDI), two isocyanide of isophorone
One of acid esters, hexamethylene diisocyanate, methyl diphenylene diisocyanate and hexamethylene diisocyanate are a variety of, but not
It is limited to this.
In a preferred embodiment, the catalyst be dibutyl tin dilaurate, and the catalyst plus
Enter the 0.1- that amount is diisocyanate, dihydromethyl propionic acid, organic silicon-fluorine polyalcohol and hydroxy acryl acid ester gross mass
1%.
In a preferred embodiment, under the conditions of 70-90 DEG C, by polymerization inhibitor, antioxidant and hydroxyl third
Olefin(e) acid ester is added in the base polyurethane prepolymer for use as of the grafted-organosilicon fluorine, and hybrid reaction 3-4h is obtained partially end-blocked or blocked entirely
Urethane acrylate.
In this embodiment, the partially end-blocked urethane acrylate during subsequent production can according to demand into
Row chain extending reaction obtains the higher urethane acrylate of solid content to increase the relative molecular weight of urethane acrylate
Resin.And the urethane acrylate blocked entirely can not carry out chain extending reaction then since-NCO group content is few, generate
The relative molecular weight of urethane acrylate is fixed value.
In a preferred embodiment, the hydroxy acryl acid ester be two trimethylolpropane trimethacrylates,
One of pentaerythritol triacrylate and double pentaerythritol C5 methacrylate are a variety of, but not limited to this.
In a preferred embodiment, the polymerization inhibitor is p-hydroxyanisole, and the additional amount of the polymerization inhibitor is
The 0.1-0.5% of diisocyanate and dihydromethyl propionic acid, organic silicon-fluorine polyalcohol and hydroxy acryl acid ester gross mass.
In a preferred embodiment, the antioxidant is BHT, and the additional amount of the antioxidant is two isocyanides
The 0.1-0.5% of acid esters and dihydromethyl propionic acid, organic silicon-fluorine polyalcohol and hydroxy acryl acid ester gross mass.
In a preferred embodiment, temperature is controlled at 10-40 DEG C, is added into the urethane acrylate of sealing end
Enter organic amine neutralize 15-30 minutes, is slowly added to deionized water, is quickly stirred dispersion, obtains light-cured polyurethane
Acrylate aqueous dispersion.The organic amine is mainly used for neutralizing the carboxylic acid group in urethane acrylate, so that final
To urethane acrylate can form aqueous dispersion in deionized water.
Preferably, the organic amine for neutralization is triethylamine, contained in the triethylamine and urethane acrylate
The molar ratio of carboxyl is (0.8-1): 1.
In a preferred embodiment, at room temperature, polyamine the partially end-blocked light is added to consolidate
Change in urethane acrylate aqueous dispersion, mixing carries out chain extending reaction and obtains the polyurethane acrylate resin of 50% solid content.
Preferably, the polyamine is the one or more of ethylenediamine, hexamethylene diamine and isophorone diamine, but is not limited to
This.
Based on the above method, the present invention also provides a kind of curable urethane acrylate aqueous dispersions, wherein uses institute
The preparation method stated is prepared.
Below by specific embodiment to a kind of preparation method of curable urethane acrylate aqueous dispersion of the present invention
And its paint film property is further explained explanation:
Embodiment 1
1), the base polyurethane prepolymer for use as synthesis of organosilicon grafting:
88.8g isophorone diisocyanate is added in the drying four-hole boiling flask that blender, thermometer, condenser are housed
(IPDI) it reacts with 100g organosilicon polyalcohol (Mw=1000), dropwise addition 1.25g catalyst dibutyltin dilaurylate in band
Have in temperature controlled electric jacket and carry out, be warming up to 90 DEG C, keep this thermotonus about 2h, surveys NCO's with di-n-butylamine method
Content when NCO content is less than or equal to theoretical value, then 13.4g dihydromethyl propionic acid (DMPA) is added in four-hole boiling flask, protects
This thermotonus 3h is held, di-n-butylamine method surveys the content of NCO, when NCO content is less than or equal to theoretical value, obtains organosilicon grafting
Base polyurethane prepolymer for use as；
2), the synthesis of partially end-blocked urethane acrylate:
65 DEG C are cooled to, can not have to that catalyst is added, weigh 0.5g polymerization inhibitor p-hydroxyanisole, 0.5g antioxidant BHT adds
Enter in four-hole boiling flask, 49.6g pentaerythritol triacrylate is added dropwise in four-hole boiling flask, is warming up to 90 DEG C of holding reaction 3h, uses
Di-n-butylamine method surveys the content of NCO, when NCO content is less than or equal to theoretical value, obtains partially end-blocked urethane acrylate；
3) it, neutralizes and disperses:
30 DEG C are cooled to hereinafter, 10.1g triethylamine neutralization reaction 15min is added into polyurethane acrylate prepolymer, by setting
Deionized water is added in fixed 50% solid content, and mechanical stirring 30min obtains curable urethane acrylate aqueous dispersion；
4), amine chain extension:
Temperature is controlled in room temperature, is slowly added into 3.0g ethylenediamine to the curable urethane acrylate water dispersion being dispersed
In body, carries out chain extending reaction and obtain 50% solid content curable urethane acrylate resin.
Embodiment 2
1), the synthesis of the base polyurethane prepolymer for use as of perfluoropolyether grafting:
Equipped with blender, thermometer, condenser drying four-hole boiling flask in be added 87g toluene di-isocyanate(TDI) (TDI) and
300g perfluoropolyether (Mw=1000), is added dropwise 2g catalyst dibutyltin dilaurylate, and reaction is having temperature controlled electricity
It is carried out in hot jacket, is warming up to 90 DEG C, keep this thermotonus about 2h, the content of NCO is surveyed with di-n-butylamine method, works as NCO content
When less than or equal to theoretical value, then by 13.4g dihydromethyl propionic acid (DMPA), it is added in four-hole boiling flask, keeps this thermotonus
3h, di-n-butylamine method survey the content of NCO, when NCO content is less than or equal to theoretical value, obtain the polyurethane prepolymer of perfluoropolyether grafting
Body；
2), the synthesis of partially end-blocked urethane acrylate:
65 DEG C are cooled to, can not have to that catalyst is added, weigh 0.8g polymerization inhibitor p-hydroxyanisole, 0.8g antioxidant BHT adds
Enter in four-hole boiling flask, 49.6g pentaerythritol triacrylate is added dropwise in four-hole boiling flask, is warming up to 90 DEG C of holding reaction 3h, uses
Di-n-butylamine method surveys the content of NCO, when NCO content is less than or equal to theoretical value, obtains partially end-blocked urethane acrylate；
3) it, neutralizes and disperses:
30 DEG C are cooled to hereinafter, 10.1g triethylamine neutralization reaction 15min is added into polyurethane acrylate prepolymer, by setting
Deionized water is added in fixed 50% solid content, and mechanical stirring 30min obtains curable urethane acrylate aqueous dispersion；
4), amine chain extension:
Temperature is controlled in room temperature, is slowly added into 3.0g ethylenediamine to the curable urethane acrylate water dispersion being dispersed
In body, carries out chain extending reaction and obtain 50% solid content photocuring aqueous polyurethane acrylate resin.
Embodiment 3
1), the synthesis of organosilicon and the base polyurethane prepolymer for use as of perfluoropolyether grafting:
117.6 hexamethylene diisocyanates are added in the drying four-hole boiling flask that blender, thermometer, condenser are housed
(HDI) and 500g organosilicon polyalcohol and perfluoropolyether (Mw=1000) 2.5g catalyst dibutyltin cinnamic acid dibutyl, is added dropwise
Tin, reaction carry out in having temperature controlled electric jacket, are warming up to 90 DEG C, keep this thermotonus about 2h, with two positive fourths
Amine method surveys the content of NCO, when NCO content is less than or equal to theoretical value, then by 13.4g dihydromethyl propionic acid (DMPA), is added four
In mouth flask, this thermotonus 3h is kept, di-n-butylamine method surveys the content of NCO, when NCO content is less than or equal to theoretical value, obtains
The base polyurethane prepolymer for use as of organosilicon and perfluoropolyether grafting；
2), the synthesis of partially end-blocked urethane acrylate:
65 DEG C are cooled to, can not have to that catalyst is added, weigh 1g polymerization inhibitor p-hydroxyanisole, 1g antioxidant BHT is added four
In mouth flask, 49.6g pentaerythritol triacrylate is added dropwise in four-hole boiling flask, is warming up to 90 DEG C of holdings reaction 3h, just with two
Butylamine method surveys the content of NCO, when NCO content is less than or equal to theoretical value, obtains partially end-blocked urethane acrylate；
3) it, neutralizes and disperses:
30 DEG C are cooled to hereinafter, 10.1g triethylamine neutralization reaction 15min is added into polyurethane acrylate prepolymer, by setting
Deionized water is added in fixed 50% solid content, and mechanical stirring 30min obtains curable urethane acrylate aqueous dispersion；
4), amine chain extension:
Temperature is controlled in room temperature, is slowly added into 3.0g ethylenediamine to the curable urethane acrylate water dispersion being dispersed
In body, carries out chain extending reaction and obtain 50% solid content photocuring aqueous polyurethane acrylate resin.
Comparative example 1
1), the synthesis of base polyurethane prepolymer for use as:
66.6g isophorone diisocyanate is added in the drying four-hole boiling flask that blender, thermometer, condenser are housed
(IPDI) and 100g adipic acid type polyester diol (Mw=1000) 1.25g catalyst dibutyltin dilaurylate, is added dropwise,
Reaction carries out in having temperature controlled electric jacket, is warming up to 90 DEG C, keeps this thermotonus about 2h, with di-n-butylamine method
The content for surveying NCO, when NCO content is less than or equal to theoretical value, then by 13.4g dihydromethyl propionic acid (DMPA), the acetone of 20g
The viscosity in four-hole boiling flask for reducing performed polymer is added, keeps this thermotonus 3h, di-n-butylamine method surveys the content of NCO, when
When NCO content is less than or equal to theoretical value, base polyurethane prepolymer for use as is obtained；
2), the synthesis of partially end-blocked urethane acrylate:
65 DEG C are cooled to, weighs 0.5g polymerization inhibitor to hydroxyl Neo-thyl, 0.5g antioxidant BHT is added in four-hole boiling flask, is added dropwise
49.6g pentaerythritol triacrylate is warming up to 90 DEG C of holding reaction 3h, surveys NCO's with di-n-butylamine method in four-hole boiling flask
Content obtains partially end-blocked urethane acrylate when NCO content is less than or equal to theoretical value；
3) it, neutralizes and disperses:
30 DEG C are cooled to hereinafter, 10.1g triethylamine neutralization reaction 15min is added into polyurethane acrylate prepolymer, by setting
Deionized water is added in fixed 40% solid content, and mechanical stirring 30min obtains curable urethane acrylate aqueous dispersion；
4), amine chain extension:
Temperature is controlled in room temperature, is slowly added into 3.0g ethylenediamine to the curable urethane acrylate water dispersion being dispersed
In body, carries out chain extending reaction and obtain 40% solid content ultraviolet light solidfication water polyurethane acrylate resin；
5), outer addition organic silicon-fluorine auxiliary agent:
Organic silicon-fluorine auxiliary agent will be added in the curable urethane acrylate aqueous dispersion prepared, stirs 30 minutes.
Further, the polyurethane acrylate resin prepared by above-described embodiment 1-3 and comparative example 1, according to such as the following table 1
Component prepares paint film with paint:
1 paint film component of table
| Urethane acrylate aqueous dispersion | 65-75% |
| Water | 20-25% |
| Cosolvent | 2-4% |
| Photoinitiator | 3-4% |
| Defoaming agent | 0.1-1% |
| Levelling agent | 0.1-1% |
| PH regulator | 1-2% |
Cosolvent is dipropylene glycol methyl ether in the table 1, photoinitiator 1173, defoaming agent are Tego 810, levelling agent is
Tego 450, PH regulator are AMP-95.The performance of paint film is tried, the results are shown in Table 2.Wherein solid content is pressed
GB1725-89 measurement；The viscosity of resin is measured by GB/T1723-1993；Hardness of film is measured by GB/T6739-2006；Attachment
Power is measured by GB/T9286-1998；Flexibility measurement: preparing paint film on tinplate, and bending certain angle sees cracking degree；Water
Boiling property: boiling 30min in 80 DEG C of water, sees paint film situation of change；Oil resistivity wiping: oiliness is carried out in coating the same area
Pen wiping measures coating anti-pollution characteristic with the erasable number of scratch.
The paint film property that table 2 is embodiment 1-3 and the curable urethane acrylate aqueous dispersion of comparative example 1 obtains is surveyed
Examination comparison
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Appearance | Milky translucent liquid | Milky translucent liquid | Milky translucent liquid | Milky translucent liquid |
| Gu containing/% | 50 | 50 | 50 | 40 |
| Viscosity (25 DEG C)/CPS | 50 | 60 | 100 | 200 |
| Hardness | 2H | 2H | H | HB |
| Adhesive force | 5B | 5B | 5B | 4B |
| Flexibility | It is excellent | It is excellent | It is excellent | It is good |
| Boiling (80 DEG C/30min) | It is unchanged | It is unchanged | It is unchanged | There is slight bubble |
| Anti-pollution characteristic (secondary) | 500 | 550 | 580 | 200 |
As seen from Table 2, example 1-3 can prepare high solids content, extreme hardness, adhesive force well can resistant be anti-graffiti has excellent performance
The cured curable urethane acrylate aqueous dispersion of ultraviolet light, admittedly contain up to 50%, Diamond Search, prepared paint film stream
Flat richness is high, adhesive force is good, hardness is up to 2H, extremely low surface tension, can effectively resistant it is anti-graffiti.If using being added with outside
Machine fluosilicic auxiliary agent, anti-pollution characteristic is general, and not persistently.
In conclusion the present invention provides a kind of preparation method of curable urethane acrylate aqueous dispersion, by setting
Organic silicon-fluorine group is grafted in the molecular backbone of the urethane acrylate by meter, to effectively promote light-cured polyurethane
The anti-graffiti performance of resistant and holding after acrylate aqueous dispersion formation paint film is permanent.Further, by the method for the invention
The advantages of curable urethane acrylate aqueous dispersion of preparation combines water paint and photocureable coating, solid content are high
Up to 50%, organic solvent is free of, and there is extreme hardness and extremely strong adhesive force.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of preparation method of curable urethane acrylate aqueous dispersion, which is characterized in that comprising steps of
Under the conditions of 60-95 DEG C, diisocyanate, dihydromethyl propionic acid and organic silicon-fluorine polyalcohol are mixed, in catalyst
Under the action of reaction obtain the base polyurethane prepolymer for use as of grafted-organosilicon fluorine；
Under the conditions of 70-90 DEG C, the grafted-organosilicon fluorine is added in polymerization inhibitor, antioxidant and hydroxy acryl acid ester
In base polyurethane prepolymer for use as, urethane acrylate that hybrid reaction is blocked；
Under the conditions of 10-40 DEG C, organic amine and deionized water are added in the urethane acrylate of the sealing end, mixing is anti-
It should obtain curable urethane acrylate aqueous dispersion.
2. the preparation method of curable urethane acrylate aqueous dispersion according to claim 1, which is characterized in that described
The molar ratio of diisocyanate, dihydromethyl propionic acid and organic silicon-fluorine polyalcohol are as follows: (3-7): (1-5): 1.
3. the preparation method of curable urethane acrylate aqueous dispersion according to claim 1, which is characterized in that described
Organic silicon-fluorine polyalcohol is one of organosilicon polyalcohol and perfluoropolyether or a variety of.
4. the preparation method of curable urethane acrylate aqueous dispersion according to claim 1, which is characterized in that described
Diisocyanate is toluene di-isocyanate(TDI), isophorone diisocyanate, hexamethylene diisocyanate, diphenyl methane two
One of isocyanates and hexamethylene diisocyanate are a variety of.
5. the preparation method of curable urethane acrylate aqueous dispersion according to claim 1, which is characterized in that described
Catalyst is dibutyl tin dilaurate, and the additional amount of the catalyst is diisocyanate, dihydromethyl propionic acid, organosilicon
The 0.1-1% of fluorine polyalcohol and hydroxy acryl acid ester gross mass.
6. the preparation method of curable urethane acrylate aqueous dispersion according to claim 1, which is characterized in that described
Hydroxy acryl acid ester is five propylene of two trimethylolpropane trimethacrylates, pentaerythritol triacrylate and dipentaerythritol
One of acid esters is a variety of.
7. the preparation method of curable urethane acrylate aqueous dispersion according to claim 1, which is characterized in that described
Polymerization inhibitor is p-hydroxyanisole, and the additional amount of the polymerization inhibitor is that diisocyanate and dihydromethyl propionic acid, organic silicon-fluorine are more
The 0.1-0.5% of first alcohol and hydroxy acryl acid ester gross mass；
And/or the antioxidant is BHT, the additional amount of the antioxidant be diisocyanate with dihydromethyl propionic acid, have
The 0.1-0.5% of machine fluosilicic polyalcohol and hydroxy acryl acid ester gross mass.
8. the preparation method of curable urethane acrylate aqueous dispersion according to claim 1, which is characterized in that described
Step organic amine and deionized water is added in the urethane acrylate of the sealing end under the conditions of 10-40 DEG C, and mixing is anti-
Curable urethane acrylate aqueous dispersion should be obtained, later further include:
At room temperature, polyamine is added in the curable urethane acrylate aqueous dispersion, mixing is expanded
Chain reaction obtains polyurethane acrylate resin.
9. the preparation method of curable urethane acrylate aqueous dispersion according to claim 8, which is characterized in that described
Polyamine is the one or more of ethylenediamine, hexamethylene diamine and isophorone diamine.
10. a kind of curable urethane acrylate aqueous dispersion, which is characterized in that any described using claim 1-9
Preparation method is prepared.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080008838A1 (en) * | 2004-02-23 | 2008-01-10 | Leibniz-Institut Fuer Neue Materialien Gemeinnuetz | Abrasion-Resistant and Alkali-Resistant Coatings or Moulded Bodies Having a Low-Energy Surface |
| CN102746782A (en) * | 2011-04-18 | 2012-10-24 | 中国科学院化学研究所 | Anti-icing and anti-frosting polyurethane coating and preparation method thereof |
| EP2690117A1 (en) * | 2012-07-24 | 2014-01-29 | ALLNEX AUSTRIA GmbH | Aqueously Dispersible Polyurethane |
| CN105001396A (en) * | 2015-07-08 | 2015-10-28 | 华南理工大学 | 80-95% solid content waterborne UV-curable urethane acrylate and preparation method |
| CN106866912A (en) * | 2017-03-09 | 2017-06-20 | 广东昊辉新材料有限公司 | A kind of ultraviolet light solidfication water polyurethane acrylate and preparation method thereof |
-
2018
- 2018-08-22 CN CN201810961502.9A patent/CN109054623A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080008838A1 (en) * | 2004-02-23 | 2008-01-10 | Leibniz-Institut Fuer Neue Materialien Gemeinnuetz | Abrasion-Resistant and Alkali-Resistant Coatings or Moulded Bodies Having a Low-Energy Surface |
| CN102746782A (en) * | 2011-04-18 | 2012-10-24 | 中国科学院化学研究所 | Anti-icing and anti-frosting polyurethane coating and preparation method thereof |
| EP2690117A1 (en) * | 2012-07-24 | 2014-01-29 | ALLNEX AUSTRIA GmbH | Aqueously Dispersible Polyurethane |
| CN105001396A (en) * | 2015-07-08 | 2015-10-28 | 华南理工大学 | 80-95% solid content waterborne UV-curable urethane acrylate and preparation method |
| CN106866912A (en) * | 2017-03-09 | 2017-06-20 | 广东昊辉新材料有限公司 | A kind of ultraviolet light solidfication water polyurethane acrylate and preparation method thereof |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021074113A1 (en) * | 2019-10-15 | 2021-04-22 | Akzo Nobel Coatings International B.V. | Waterborne, uv curable coating composition for easy-clean coatings |
| CN114599748B (en) * | 2019-10-15 | 2023-09-15 | 阿克佐诺贝尔国际涂料股份有限公司 | Water-based UV curable coating composition for easy-to-clean coatings |
| CN114599748A (en) * | 2019-10-15 | 2022-06-07 | 阿克佐诺贝尔国际涂料股份有限公司 | Water-based UV curable coating compositions for easy-clean coatings |
| CN110606932A (en) * | 2019-10-28 | 2019-12-24 | 广东昊辉新材料有限公司 | Photo-curing polyurethane acrylate aqueous dispersion and preparation method thereof |
| CN115087681A (en) * | 2020-02-18 | 2022-09-20 | 阿克佐诺贝尔国际涂料股份有限公司 | Aqueous UV curable coating composition for anti-fouling and anti-scratch coatings |
| WO2021165223A1 (en) | 2020-02-18 | 2021-08-26 | Akzo Nobel Coatings International B.V. | Waterborne uv curable coating composition for anti-stain and anti-scratch coatings |
| CN112300357A (en) * | 2020-11-06 | 2021-02-02 | 广州市嵩达新材料科技有限公司 | Photo-curing hydrophobic polyurea nano particle and preparation method and application thereof |
| CN112538156A (en) * | 2020-12-11 | 2021-03-23 | 南雄市沃太化工有限公司 | Smoke head scalding resistant stain resistant flame retardant photocureable resin and photocureable coating |
| CN112538156B (en) * | 2020-12-11 | 2023-06-16 | 南雄市沃太化工有限公司 | Cigarette end scalding-resistant stain-resistant flame-retardant photo-cured resin and photo-cured coating |
| CN113354791A (en) * | 2021-06-24 | 2021-09-07 | 哈尔滨工业大学无锡新材料研究院 | UV-curable hyperbranched fluorine-silicon modified polyurethane, preparation method thereof and coating prepared from polyurethane |
| CN113831459A (en) * | 2021-09-28 | 2021-12-24 | 泉州师范学院 | Low-temperature-resistant flexible photosensitive resin composition for photocuring 3D printing and preparation method thereof |
| CN113831459B (en) * | 2021-09-28 | 2023-10-10 | 泉州师范学院 | Low-temperature-resistant photo-curing flexible photosensitive resin composition for 3D printing and preparation method thereof |
| CN113999367A (en) * | 2021-12-06 | 2022-02-01 | 南雄西顿化工有限公司 | Stain-resistant UV-curable aqueous polyurethane acrylate dispersion and preparation method thereof |
| CN115029059A (en) * | 2022-07-04 | 2022-09-09 | 广东省蜂巢纳米材料有限公司 | Ultraviolet-curing water-based anti-graffiti coating and preparation method thereof |
| CN117683183A (en) * | 2023-12-18 | 2024-03-12 | 无锡八禾新材料科技有限公司 | Photo-curing flexible conductive polyurethane and preparation method and application thereof |
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