CN103570911B - Aqueous polyurethane acrylate, aqueous polyurethane ultraviolet-curing paint and preparation method thereof - Google Patents
Aqueous polyurethane acrylate, aqueous polyurethane ultraviolet-curing paint and preparation method thereof Download PDFInfo
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- 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
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a kind of aqueous polyurethane acrylate, aqueous polyurethane ultraviolet-curing paint and preparation method thereof, belong to ultraviolet-curing paint technical field.Solve aqueous polyurethane coating harm environment in prior art, the technical problem of ultraviolet light polymerization can not be carried out.The coating of the present invention includes the aqueous polyurethane acrylate of 68-97 weight portion, the aqueous levelling agent of 0.1-0.5 weight portion, the aqueous wetting agent of 0.2-0.6 weight portion, the aqueous defoamer of 0.2-0.5 weight portion, the aqueous cosolvent of 3-7 weight portion and 0.1-0.5 weight portion light trigger.Present invention also offers the structure of aqueous polyurethane acrylate and preparation method.The aqueous polyurethane ultraviolet-curing paint of the present invention has good water solublity, and can carry out ultraviolet light polymerization, does not contain the pollutant such as diluent, environmental protection.
Description
Technical field
The present invention relates to a kind of aqueous polyurethane acrylate, aqueous polyurethane ultraviolet-curing paint and preparation method thereof, belong to ultraviolet-curing paint technical field.
Technical background
Poly-(carbonic ester-ether) dihydroxylic alcohols of low-molecular-weight is with double metal cyanide for catalyst, under chain-transferring agent exists, carbon dioxide and epoxide is carried out polyreaction, is prepared from for chain-transferring agent with dihydroxylic alcohols or dicarboxylic acids respectively.Employing carbon dioxide in the preparation process of such polymer diol as one of them important source material, thus greatly reduce the carbon dioxide pollution to environment in environment, what is more important reduces the dependence of fossil resources.And, this poly-(carbonic ester-ether) dihydroxylic alcohols combines the excellent mechanical performance of polyester polymer and the hydrolytic resistance of polyether type polymer excellence, thus, it is soft section of component of a kind of important polyurethane polymer.
Chinese patent poly-(carbonic ester-ether) type polyurethane acrylate, ultraviolet photocurable anti-static paint and preparation method thereof (publication number CN103059256A) report with poly-(carbonic ester-ether) dihydroxylic alcohols for soft section of component, it is prepared for solvent borne polyurethane acrylate, and with it for film-forming resin, it is prepared for ultraviolet photocurable anti-static paint.Chinese patent gathers (carbonic ester-ether) type aqueous polyurethane, poly-(carbonic ester-ether) type aqueous polyurethane coating and preparation method thereof (CN103044650A) with poly-(carbonic ester-ether) dihydroxylic alcohols for soft section of component, it is prepared for aqueous polyurethane, and is prepared for aqueous polyurethane coating as matrix resin.But, above-mentioned Section 1 patent needs to add reactive diluent and could use, thus, reactive diluent still can bring certain harm to operator；Above-mentioned Section 2 patent, although be prepared for aqueous polyurethane, but ultraviolet light polymerization can not be carried out.
Summary of the invention
Present invention aim to address aqueous polyurethane coating harm environment in prior art, the technical problem of ultraviolet light polymerization can not be carried out, it is provided that a kind of aqueous polyurethane acrylate, aqueous polyurethane ultraviolet-curing paint and preparation method thereof.
The aqueous polyurethane acrylate of the present invention, it is characterised in that structural formula is formula (I), formula (II) or formula (III):
In formula, m, n, x are integer, 10≤m≤70,10≤n≤70,10≤x≤50；
R-is the one in following structure:
-R1-for the one in following structure:
-R2One in following structure:
-R3One in following structure:
R4One in following structure:
It is preparation method during formula (I) structural formula that the present invention also provides for above-mentioned aqueous polyurethane acrylate, comprises the following steps:
(1) under inert atmosphere, poly-(carbonic ester-ether) dihydroxylic alcohols of 150-610 weight portion is added in reaction vessel, it is warmed up to 110-130 DEG C, decompression 1-1.5h, cool to 70-80 DEG C again, add the acetone of 112-168 weight portion and the catalyst of 0.1-0.31 weight portion, add the diisocyanate of 53.8-78.5 weight portion, reaction 2-4h, obtains the first intermediate；
(2) in the first intermediate, add the acetone of 96-120 weight portion, greenhouse cooling to 30-45 DEG C, the amine chain extender of dropping 9.5-13.1 weight portion, after dropwising, react 0.5-2h, obtain the second intermediate；
(3) in the second intermediate, add the acetone of 88-208 weight portion and the polymerization inhibitor of 0.28-0.44 weight portion, add the hydroxy acrylate of 56.8-87.4 weight portion, be warmed up to 85-90 DEG C, react 2-3h；Adding the deionized water of 180-650 weight portion, then, add the Bronsted acid of 58-97 weight portion, stir 0.5-2h, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (I) structure.
Preferably, the molecular weight of described poly-(carbonic ester-ether) dihydroxylic alcohols is 1500-6000 dalton, described catalyst is dibutyl tin laurate or stannous octoate, described diisocyanate is 2, 4-toluene di-isocyanate(TDI), dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate, described amine hydrophilic chain extender is N methyldiethanol amine, diethanolamine or triethanolamine, described polymerization inhibitor is hydroquinone or MEHQ, described hydroxy acrylate is 2-(Acryloyloxy)ethanol, trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate, described Bronsted acid nertralizer is sulphuric acid, hydroxyacetic acid or trifluoroacetic acid.
It is preparation method during formula (II) structural formula that the present invention also provides for above-mentioned aqueous polyurethane acrylate, comprises the following steps:
(1) under inert atmosphere protection; poly-(carbonic ester-ether) dihydroxylic alcohols of 130-540 weight portion is added in reaction vessel; it is warmed up to 110-130 DEG C; decompression 1-3h; cool to 70-80 DEG C again, add the acetone of 96-128 weight portion and the catalyst of 0.1-0.4 weight portion, add the diisocyanate of 63.5-88.7 weight portion; reaction 2-4h, obtains the first intermediate；
(2) in the first intermediate, add the acetone of 80-224 weight portion, add the dihydromethyl propionic acid of 13.1-16.8 weight portion, be warmed up to 85-90 DEG C, react 2-3h；Add the polymerization inhibitor of 0.22-0.38 weight portion, add the hydroxy acrylate of 45.7-76.2 weight portion, continue reaction 2-4h, obtain the second intermediate；
(3) 30-45 DEG C is cooled to, the amine nertralizer adding 18.6-34.1 weight portion in the second intermediate is neutralized, then, add the deionized water of 130-520 weight portion, stirring 15-45min, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (II) structure.
Preferably, the molecular weight of described poly-(carbonic ester-ether) dihydroxylic alcohols is 1500-6000 dalton, described catalyst is dibutyl tin laurate or stannous octoate, described diisocyanate is 2, 4-toluene di-isocyanate(TDI), dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate, described polymerization inhibitor is hydroquinone or MEHQ, described hydroxy acrylate is 2-(Acryloyloxy)ethanol, trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate, described amine nertralizer is N, N-dimethylethanolamine or triethylamine.
It is preparation method during formula (III) structural formula that the present invention also provides for above-mentioned aqueous polyurethane acrylate, comprises the following steps:
(1) under inert atmosphere protection; poly-(carbonic ester-ether) dihydroxylic alcohols of 145-430 weight portion and the Polyethylene Glycol of 68-137 weight portion is added in reaction vessel; it is warmed up to 110-130 DEG C; decompression 1-3h; cool to 70-80 DEG C again, add the acetone of 184-240 weight portion and the catalyst of 0.1-0.3 weight portion, add the diisocyanate of 102-156 weight portion; reaction 2-4h, obtains the first intermediate；
(2) in the first intermediate, add the acetone of 96-104 weight portion, temperature to 70-80 DEG C, add the polymerization inhibitor of 0.32-0.58 weight portion, add the hydroxy acrylate of 36.4-61.0 weight portion, continue reaction 1-3h, then, add the deionized water of 263-605 weight portion, after stirring 10-30min, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (III) structure.
Preferably, the molecular weight of described poly-(carbonic ester-ether) dihydroxylic alcohols is 1500-6000 dalton, the molecular weight of described Polyethylene Glycol is 200-2000 dalton, described catalyst is dibutyl tin laurate or stannous octoate, described diisocyanate is 2, 4-toluene di-isocyanate(TDI), dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate, described polymerization inhibitor is hydroquinone or MEHQ, described hydroxy acrylate is 2-(Acryloyloxy)ethanol, trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate.
The present invention also provides for the aqueous polyurethane ultraviolet-curing paint containing above-mentioned aqueous polyurethane acrylate, aqueous polyurethane acrylate including 68-97 weight portion, the aqueous levelling agent of 0.1-0.5 weight portion, the aqueous wetting agent of 0.2-0.6 weight portion, the aqueous defoamer of 0.2-0.5 weight portion, the aqueous cosolvent of 3-7 weight portion and 0.1-0.5 weight portion light trigger.
Preferably, described aqueous levelling agent is BYK-380N, BYK-381, BYK-307, BYK-341, BYK-345, BYK-346 or BYK-348, described aqueous wetting agent is BYK-187, BYK-3400 or BYK-3410, described aqueous defoamer is BYK-019, BYK-020, BYK-024, BYK-028 or BYK-1730, described aqueous cosolvent is isopropanol, butyl glycol ether, alcohol ester-12 or dipropylene, and described light trigger is Irfacure184, Darocure1173, Irfacure2959 or Irfacure819.
The preparation method that the present invention also provides for above-mentioned aqueous polyurethane ultraviolet-curing paint, comprises the following steps:
(1) aqueous polyurethane of 68-97 weight portion, the aqueous levelling agent of 0.1-0.5 weight portion, the aqueous wetting agent of 0.2-0.6 weight portion and the aqueous defoamer of 0.2-0.5 weight portion are stirred, obtain mixture；
(2) in said mixture, add the aqueous cosolvent of 3-7 weight portion and the light trigger of 0.1-0.5 weight portion, after stirring, obtain aqueous polyurethane ultraviolet-curing paint.
Beneficial effects of the present invention:
(1) compared to existing technology, aqueous polyurethane acrylate prepared by the present invention is with poly-(carbonic ester-ether) dihydroxylic alcohols for soft section, thus decreasing the dependence to fossil resources, and combine the excellent mechanical performance of polyester polymer and the hydrolytic resistance of polyether type polymer excellence；Resin structure introduces hydrophilic radical structure, it is ensured that the water dispersible of resin, meanwhile, introduce unsaturated double-bond at end group, make resin can carry out ultraviolet light polymerization；
(2) aqueous polyurethane ultraviolet-curing paint of the present invention does not contain any reactive diluent, not only fully combines environmental-friendly aqueous feature, and combines the feature that ultraviolet light polymerization is energy-conservation, is widely applied prospect.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the aqueous polyurethane acrylate with formula (I) structure of the embodiment of the present invention 1 preparation；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of the aqueous polyurethane acrylate with formula (II) structure of the embodiment of the present invention 4 preparation；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of the aqueous polyurethane acrylate with formula (III) structure of the embodiment of the present invention 7 preparation.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with detailed description of the invention, the preferred embodiments of the invention are described, but it is to be understood that these describe simply as to further illustrate the features and advantages of the present invention rather than the restriction to patent requirements of the present invention.
The aqueous polyurethane ultraviolet-curing paint of the aqueous polyurethane acrylate of the present invention, aqueous polyurethane acrylate including 68-97 weight portion, the aqueous levelling agent of 0.1-0.5 weight portion, the aqueous wetting agent of 0.2-0.6 weight portion, the aqueous defoamer of 0.2-0.5 weight portion, the aqueous cosolvent of 3-7 weight portion and 0.1-0.5 weight portion light trigger.
In aqueous polyurethane ultraviolet-curing paint of the present invention, aqueous polyurethane acrylate is matrix resin, it is possible to have formula (I), formula (II) and three kinds of structures of formula (II):
In formula, m, n, x are integer, 10≤m≤70,10≤n≤70,10≤x≤50；
R-is the one in following structure:
-R1-for the one in following structure:
-R2One in following structure:
-R3One in following structure:
R4One in following structure:
There is the aqueous polyurethane acrylate of formula (I) structure, be prepared as follows:
(1) under inert atmosphere protection, adding poly-(carbonic ester-ether) dihydroxylic alcohols of 150-610 weight portion, be warmed up to 110-130 DEG C in reaction vessel, reduce pressure 1-1.5h；Cool to 70-80 DEG C, add the acetone of 112-168 weight portion and the catalyst of 0.1-0.31 weight portion, drip the diisocyanate of 53.8-78.5 weight portion with 5-12ml/min speed, after dropwising, react 2-4h, obtain the first intermediate；
(2) in the first intermediate, add the acetone of 96-120 weight portion, greenhouse cooling to 30-45 DEG C, drip the amine chain extender of 9.5-13.1 weight portion with 3-6ml/min speed, after dropwising, react 0.5-2h, obtain the second intermediate；
(3) in the second intermediate, add the acetone of 88-208 weight portion and the polymerization inhibitor of 0.28-0.44 weight portion, add the hydroxy acrylate of 56.8-87.4 weight portion, be warmed up to 85-90 DEG C, react 2-3h；Then, adding the deionized water of 180-650 weight portion, then, add the Bronsted acid of 58-97 weight portion, stir 0.5-2h, then, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (I) structure.
There is the aqueous polyurethane acrylate of formula (II) structure, be prepared as follows:
(1) under inert atmosphere protection, adding poly-(carbonic ester-ether) dihydroxylic alcohols of 130-540 weight portion, be warmed up to 110-130 DEG C in reaction vessel, reduce pressure 1-3h；Cool to 70-80 DEG C, add the catalyst of 96-128 pbw acetone and 0.1-0.4 weight portion, drip the diisocyanate of 63.5-88.7 weight portion with 4-10ml/min speed, after dropwising, react 2-4h, obtain the first intermediate；
(2) in the first intermediate, add the acetone of 80-224 weight portion, add the dihydromethyl propionic acid of 13.1-16.8 weight portion, be warmed up to 85-90 DEG C, react 2-3h；Add the polymerization inhibitor of 0.22-0.38 weight portion, add the hydroxy acrylate of 45.7-76.2 weight portion, continue reaction 2-4h, obtain the second intermediate；
(3) cooling to 30-45 DEG C, the amine nertralizer adding 18.6-34.1 weight portion is neutralized, then, add the deionized water of 130-520 weight portion, stir 15-45min, then, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (II) structure.
There is the aqueous polyurethane acrylate of formula (III) structure, be prepared as follows:
(1) under inert atmosphere protection, adding poly-(carbonic ester-ether) dihydroxylic alcohols of low-molecular-weight of 145-430 weight portion and the Polyethylene Glycol of 68-137 weight portion, be warmed up to 110-130 DEG C in reaction vessel, reduce pressure 1-3h；Cool to 70-80 DEG C, add acetone and the 0.1-0.3 part by weight of catalyst of 184-240 weight portion, drip the diisocyanate of 102-156 weight portion with 6-13ml/min speed, after dropwising, react 2-4h, obtain the first intermediate；
(2) in the first intermediate, add the acetone of 96-104 weight portion, temperature to 70-80 DEG C, add the polymerization inhibitor of 0.32-0.58 weight portion, add the hydroxy acrylate of 36.4-61.0 weight portion, continue reaction 1-3h, then, add the deionized water of 263-605 weight portion, after stirring 10-30min, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (III) structure.
In three kinds of preparation methoies of above-mentioned aqueous polyurethane acrylate, the molecular weight of poly-(carbonic ester-ether) dihydroxylic alcohols is 1500-6000 dalton, prepares according to CN102432857；The molecular weight of Polyethylene Glycol is 200-2000 dalton；Catalyst is dibutyl tin laurate or stannous octoate；Diisocyanate is 2,4 toluene diisocyanate, dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate；Amine hydrophilic chain extender is N methyldiethanol amine, diethanolamine or triethanolamine；Polymerization inhibitor is hydroquinone or MEHQ；Hydroxy acrylate is 2-(Acryloyloxy)ethanol, trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate；Amine nertralizer is N, N-dimethylethanolamine or triethylamine；Bronsted acid nertralizer is sulphuric acid, hydroxyacetic acid or trifluoroacetic acid.
In aqueous polyurethane ultraviolet-curing paint of the present invention, the effect of aqueous levelling agent is so that coating is in film forming procedure, has good levelling effect at substrate surface, forms smooth, smooth, uniform, transparent paint film.Aqueous levelling agent is preferably BYK Products BYK-380N, BYK-381, BYK-307, BYK-341, BYK-345, BYK-346 or BYK-348.
In the aqueous polyurethane ultraviolet-curing paint of the present invention, the effect of aqueous wetting agent is the dispersion assisting material, improves the adhesive force of coating.Aqueous wetting agent is preferably BYK Products BYK-187, BYK-3400 or BYK-3410.
In aqueous polyurethane ultraviolet-curing paint of the present invention, the effect of aqueous defoamer is in coatings process, eliminates at the bubble used or produce in whipping process, thus, decrease the defect of the paint film generation that paint film causes due to the bubble of generation.Aqueous defoamer is preferably BYK Products BYK-019, BYK-020, BYK-024, BYK-028 or BYK-1730.
In aqueous polyurethane ultraviolet-curing paint of the present invention, the effect of aqueous cosolvent is in coatings process, reduce water paint in the surface tension of substrate surface, meanwhile, efficiently control the film forming speed of coating to paint film have good appearance.Aqueous cosolvent is isopropanol, butyl glycol ether, alcohol ester-12 or dipropylene.
In aqueous polyurethane ultraviolet-curing paint of the present invention, the effect of light trigger is generation free radical under irradiation under ultraviolet ray, thus causing aqueous polyurethane acrylate unsaturated double-bond to carry out radical polymerization.Light trigger is preferably Switzerland's vapour Bagong department product I rfacure184, Darocure1173, Irfacure2959 or Irfacure819.
The preparation method of the aqueous polyurethane ultraviolet-curing paint of the present invention:
(1) aqueous polyurethane of 68-97 weight portion, the aqueous levelling agent of 0.1-0.5 weight portion, the aqueous wetting agent of 0.2-0.6 weight portion and the aqueous defoamer of 0.2-0.5 weight portion are added in homogenizer, stir 1h-3h with the rotating speed of 800-1200rpm, obtain mixture；
(2) in described mixture, add the aqueous cosolvent of 3-7 weight portion and the light trigger of 0.1-0.5 weight portion, after stirring 10-30min with the rotating speed of 600-800rpm, obtain aqueous polyurethane ultraviolet-curing paint.
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described.
Embodiment 1
In conjunction with Fig. 1, embodiment 1 is described
Prepared by the aqueous polyurethane acrylate with formula (I) structure:
(1) under nitrogen protection, adding poly-(carbonic ester-ether) dihydroxylic alcohols (molecular weight is 1500 dalton) of 150g, be warmed up to 110 DEG C in there-necked flask, reduce pressure 1h.Cool to 70 DEG C, add the acetone of 140ml and the dibutyl tin laurate of 0.1g, drip the 2,4 toluene diisocyanate of 53.8g with 5ml/min speed, after dropwising, react 2h, obtain the first intermediate.
(2) in the first intermediate, add the acetone of 120ml, greenhouse cooling to 30 DEG C, drip the N methyldiethanol amine of 9.5g with 3ml/min speed, after dropwising, react 0.5h, obtain the second intermediate.
(3) in the second intermediate, add the acetone of 110ml and the hydroquinone of 0.28g, add the pentaerythritol triacrylate of 56.8g, be warmed up to 85 DEG C, react 2h.Then, adding 180ml deionized water, then, add the hydroxyacetic acid of 58g, stir 0.5h, then, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (I) structure.
The aqueous polyurethane acrylate with formula (I) structure of embodiment 1 preparation is carried out magnetic resonance detection, and result is as shown in Figure 1.As can be seen from Figure 1, the nucleus magnetic hydrogen spectrum data (deuterochloroform is deuterated reagent) of the aqueous polyurethane acrylate of embodiment 1 preparation: 1.25ppm, 1.65ppm, 2.14ppm, 2.30ppm, 4.06ppm, 4.38ppm, 5.86ppm, 6.15ppm, 6.41ppm, 7.06ppm, 7.77ppm, it was demonstrated that its structure is really as shown in formula (I).
Embodiment 2
Prepared by the aqueous polyurethane acrylate with formula (I) structure:
(1) under nitrogen protection, adding poly-(carbonic ester-ether) dihydroxylic alcohols (molecular weight is 6000 dalton) of 610g, be warmed up to 130 DEG C in there-necked flask, reduce pressure 1.5h.Cool to 80 DEG C, add the acetone of 210ml and the stannous octoate of 0.31g, drip the methyl diphenylene diisocyanate of 78.5g with 12ml/min speed, after dropwising, react 4h, obtain the first intermediate.
(2) in the first intermediate, add the acetone of 200ml, greenhouse cooling to 45 DEG C, drip the diethanolamine of 13.1g with 6ml/min speed, after dropwising, react 2h, obtain the second intermediate.
(3) in the second intermediate, add the acetone of 260ml and the MEHQ of 0.44g, add the double pentaerythritol C5 methacrylate of 87.4g, be warmed up to 90 DEG C, react 3h.Then, adding 650ml deionized water, then, add the trifluoroacetic acid of 97g, stir 2h, then, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (I) structure.
Embodiment 3
Prepared by the aqueous polyurethane acrylate with formula (I) structure:
(1) under nitrogen protection, adding poly-(carbonic ester-ether) dihydroxylic alcohols (molecular weight is 3000 dalton) of 300g, be warmed up to 120 DEG C in there-necked flask, reduce pressure 1.5h.Cool to 75 DEG C, add the acetone of 180ml and the dibutyl tin laurate of 0.2g, drip the isophorone diisocyanate of 64.5g with 8ml/min speed, after dropwising, react 3h, obtain the first intermediate.
(2) in the first intermediate, add the acetone of 190ml, greenhouse cooling to 35 DEG C, drip the triethanolamine of 11.6g with 5ml/min speed, after dropwising, react 1h, obtain the second intermediate.
(3) in the second intermediate, add the acetone of 220ml and the MEHQ of 0.34g, add the trimethylolpropane diacrylate of 76.3g, be warmed up to 88 DEG C, react 2.5h.Then, adding 360ml deionized water, then, add the sulphuric acid of 76g, stir 1.5h, then, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (I) structure.
Embodiment 4
In conjunction with Fig. 2, embodiment 4 is described
Prepared by the aqueous polyurethane acrylate with formula (II) structure:
(1) under nitrogen protection, adding poly-(carbonic ester-ether) dihydroxylic alcohols (molecular weight is 1500 dalton) of 130g, be warmed up to 110 DEG C in there-necked flask, reduce pressure 1h.Cool to 70 DEG C, add the acetone of 120ml and the stannous octoate of 0.1g, drip the 1 of 63.5g with 4ml/min speed, hexamethylene-diisocyanate, after dropwising, reacts 2h, obtains the first intermediate.
(2) in the first intermediate, add the acetone of 100ml, add the dihydromethyl propionic acid of 13.1g, be warmed up to 85 DEG C, react 2h.Add the MEHQ of 0.22g, add the 2-(Acryloyloxy)ethanol of 45.7g, continue reaction 2h, obtain the second intermediate.
(3) cooling to 30 DEG C, N, the N-dimethylethanolamine adding 18.6g is neutralized, and then, adds 130ml deionized water, stirs 15min, and then, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (II) structure.
The aqueous polyurethane acrylate with formula (II) structure of embodiment 4 preparation is carried out magnetic resonance detection, and result is as shown in Figure 2.As can be seen from Figure 2, the nucleus magnetic hydrogen spectrum data (deuterochloroform is deuterated reagent) of the aqueous polyurethane acrylate of embodiment 4 preparation: 1.23ppm, 1.65ppm, 2.10ppm, 2.20ppm, 2.29ppm, 4.09ppm, 4.38ppm, 5.88ppm, 6.15ppm, 6.39ppm, 7.08ppm, it was demonstrated that its structure is really as shown in formula (II).
Embodiment 5
Prepared by the aqueous polyurethane acrylate with formula (II) structure:
(1) under nitrogen protection, adding poly-(carbonic ester-ether) dihydroxylic alcohols (molecular weight is 6000 dalton) of 540g, be warmed up to 130 DEG C in there-necked flask, reduce pressure 3h.Cool to 80 DEG C, add the acetone of 160ml and the stannous octoate of 0.4g, drip the dicyclohexyl methyl hydride diisocyanate of 88.7g with 10ml/min speed, after dropwising, react 4h, obtain the first intermediate.
(2) in the first intermediate, add the acetone of 280ml, add the dihydromethyl propionic acid of 16.8g, be warmed up to 90 DEG C, react 3h.Add the hydroquinone of 0.38g, add the pentaerythritol triacrylate of 76.2g, continue reaction 4h, obtain the second intermediate.
(3) cooling to 45 DEG C, the triethylamine adding 34.1g is neutralized, and then, adds 520ml deionized water, stirs 45min, and then, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (II) structure.
Embodiment 6
Prepared by the aqueous polyurethane acrylate with formula (II) structure:
(1) under nitrogen protection, adding poly-(carbonic ester-ether) dihydroxylic alcohols (molecular weight is 4500 dalton) of 420g, be warmed up to 120 DEG C in there-necked flask, reduce pressure 2h.Cool to 75 DEG C, add the acetone of 140ml and the dibutyl tin laurate of 0.3g, drip the isophorone diisocyanate of 71.3g with 8ml/min speed, after dropwising, react 3h, obtain the first intermediate.
(2) in the first intermediate, add the acetone of 210ml, add the dihydromethyl propionic acid of 14.7g, be warmed up to 88 DEG C, react 2.5h.Add the hydroquinone of 0.28g, add the double pentaerythritol C5 methacrylate of 67.4g, continue reaction 3h, obtain the second intermediate.
(3) cooling to 35 DEG C, add N, N-dimethylethanolamine and be neutralized, then, add 410ml deionized water, stir 30min, then, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (II) structure.
Embodiment 7
In conjunction with Fig. 3, embodiment 7 is described
Prepared by the aqueous polyurethane acrylate with formula (III) structure:
(1) under nitrogen protection; there-necked flask adds poly-(carbonic ester-ether) dihydroxylic alcohols (molecular weight is 1500 dalton) of low-molecular-weight of 145g and the Polyethylene Glycol (molecular weight is 200 dalton) of 68g; being warmed up to 110 DEG C, reduce pressure 1h.Cool to 70 DEG C, add acetone and the 0.1g dibutyl tin laurate of 230ml, drip the isophorone diisocyanate of 102g with 6ml/min speed, after dropwising, react 2h, obtain the first intermediate.
(2) in the first intermediate, add the acetone of 80ml, temperature to 70 DEG C, add the MEHQ of 0.32g, add the trimethylolpropane diacrylate of 36.4g, continue reaction 1h, then, add the deionized water of 263g, after stirring 10min, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (III) structure.
The aqueous polyurethane acrylate with formula (III) structure of embodiment 7 preparation is carried out magnetic resonance detection, and result is as shown in Figure 3.As can be seen from Figure 3, the nucleus magnetic hydrogen spectrum data (deuterochloroform is deuterated reagent) of the aqueous polyurethane acrylate of embodiment 7 preparation: 1.12ppm, 1.25ppm, 1.43ppm, 2.10ppm, 2.20ppm, 3.40ppm, 3.51ppm, 4.31ppm, 5.02ppm, 5.86ppm, 6.15ppm, 6.39ppm, 6.46ppm, 7.06ppm, 7.30ppm, it was demonstrated that its structure is really as shown in formula (III).
Embodiment 8
Prepared by the aqueous polyurethane acrylate with formula (III) structure:
(1) under nitrogen protection; there-necked flask adds poly-(carbonic ester-ether) dihydroxylic alcohols (molecular weight is 6000 dalton) of low-molecular-weight of 430g and the Polyethylene Glycol (molecular weight is 2000 dalton) of 68-137g; being warmed up to 130 DEG C, reduce pressure 3h.Cool to 80 DEG C, add acetone and the 0.3g stannous octoate of 300ml, drip the methyl diphenylene diisocyanate of 156g with 13ml/min speed, after dropwising, react 4h, obtain the first intermediate.
(2) in the first intermediate, add the acetone of 130ml, temperature to 80 DEG C, add the hydroquinone of 0.58g, add the pentaerythritol triacrylate of 61.0g, continue reaction 3h, then, add the deionized water of 605g, after stirring 30min, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (III) structure.
Embodiment 9
Prepared by the aqueous polyurethane acrylate with formula (III) structure:
(1) under nitrogen protection; there-necked flask adds poly-(carbonic ester-ether) dihydroxylic alcohols (molecular weight is 3500 dalton) of low-molecular-weight of 360g and the Polyethylene Glycol (molecular weight is 1000 dalton) of 106g; being warmed up to 120 DEG C, reduce pressure 2h.Cool to 75 DEG C, add acetone and the 0.2g dibutyl tin laurate of 280ml, drip the 2,4 toluene diisocyanate of 132g with 10ml/min speed, after dropwising, react 3h, obtain the first intermediate.
(2) in the first intermediate, add the acetone of 110ml, temperature to 75 DEG C, add the hydroquinone of 0.42g, add the trimethylolpropane diacrylate of 52.3g, continue reaction 2h, then, add the deionized water of 410g, after stirring 20min, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (III) structure.
Embodiment 10
Aqueous polyurethane acrylate preparation method for coating:
According to the ratio (unit is g) of table 1, prepare aqueous polyurethane acrylate coating in accordance with the following methods:
(1) aqueous polyurethane acrylate of 68-97g, the aqueous levelling agent of 0.1-0.5g and the aqueous defoamer of 0.2-0.5g are added in homogenizer, stir 1-3h with the rotating speed of 800-1200rpm, obtain mixture；
(2) in described mixture, add the light trigger of 0.1-0.5g, after stirring 10-30min with the rotating speed of 600-800rpm, obtain aqueous polyurethane acrylate coating.
Obtain aqueous polyurethane acrylate coating, be respectively labeled as WUP01, WUP02, WUP03, WUP04, WUP05, WUP06, WUP07, WUP08 and WUP09.
Aqueous polyurethane ultraviolet-curing paint WUP01-WUP09 material ratio prepared by table 1
Respectively aqueous polyurethane ultraviolet-curing paint WUP01-WUP09 is coated on galvanized sheet iron, at 280～330mJ/cm2Solidify under UV energy, the paint film after solidifying is tested.Test result is in Table 2.
Table 2 aqueous polyurethane ultraviolet-curing paint WUP01-WUP09 obtains the performance test results of film after solidifying
Obviously, the explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It should be pointed out that, the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (8)
1. aqueous polyurethane acrylate, it is characterised in that structural formula is formula (I) or formula (III):
In formula, m, n, x are integer, 10≤m≤70,10≤n≤70,10≤x≤50；
R-is the one in following structure:
-R1-for the one in following structure:
-R2One in following structure:
-R3One in following structure:
2. the preparation method of the aqueous polyurethane acrylate described in claim 1, it is characterised in that when the structural formula of aqueous polyurethane acrylate is formula (I), comprise the following steps:
(1) under inert atmosphere, poly-(carbonic ester-ether) dihydroxylic alcohols of 150-610 weight portion is added in reaction vessel, it is warmed up to 110-130 DEG C, decompression 1-1.5h, cool to 70-80 DEG C again, add the acetone of 112-168 weight portion and the catalyst of 0.1-0.31 weight portion, add the diisocyanate of 53.8-78.5 weight portion, reaction 2-4h, obtains the first intermediate；
(2) in the first intermediate, add the acetone of 96-120 weight portion, cool to 30-45 DEG C, the amine chain extender of dropping 9.5-13.1 weight portion, after dropwising, react 0.5-2h, obtain the second intermediate；
(3) in the second intermediate, add the acetone of 88-208 weight portion and the polymerization inhibitor of 0.28-0.44 weight portion, add the hydroxy acrylate of 56.8-87.4 weight portion, be warmed up to 85-90 DEG C, react 2-3h；Adding the deionized water of 180-650 weight portion, then, add the Bronsted acid of 58-97 weight portion, stir 0.5-2h, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (I) structure.
3. the preparation method of aqueous polyurethane acrylate according to claim 2, it is characterized in that, the molecular weight of described poly-(carbonic ester-ether) dihydroxylic alcohols is 1500-6000 dalton, described catalyst is dibutyl tin laurate or stannous octoate, described diisocyanate is 2, 4-toluene di-isocyanate(TDI), dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate, described amine hydrophilic chain extender is N methyldiethanol amine, diethanolamine or triethanolamine, described polymerization inhibitor is hydroquinone or MEHQ, described hydroxy acrylate is 2-(Acryloyloxy)ethanol, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate, described Bronsted acid nertralizer is sulphuric acid, hydroxyacetic acid or trifluoroacetic acid.
4. the preparation method of the aqueous polyurethane acrylate described in claim 1, it is characterised in that when the structural formula of aqueous polyurethane acrylate is formula (III), comprise the following steps:
(1) under inert atmosphere protection; poly-(carbonic ester-ether) dihydroxylic alcohols of 145-430 weight portion and the Polyethylene Glycol of 68-137 weight portion is added in reaction vessel; it is warmed up to 110-130 DEG C; decompression 1-3h; cool to 70-80 DEG C again, add the acetone of 184-240 weight portion and the catalyst of 0.1-0.3 weight portion, add the diisocyanate of 102-156 weight portion; reaction 2-4h, obtains the first intermediate；
(2) in the first intermediate, add the acetone of 96-104 weight portion, temperature to 70-80 DEG C, add the polymerization inhibitor of 0.32-0.58 weight portion, add the hydroxy acrylate of 36.4-61.0 weight portion, continue reaction 1-3h, then, add the deionized water of 263-605 weight portion, after stirring 10-30min, decompression removes acetone, obtains the aqueous polyurethane acrylate with formula (III) structure.
5. the preparation method of aqueous polyurethane acrylate according to claim 4, it is characterized in that, the molecular weight of described poly-(carbonic ester-ether) dihydroxylic alcohols is 1500-6000 dalton, the molecular weight of described Polyethylene Glycol is 200-2000 dalton, described catalyst is dibutyl tin laurate or stannous octoate, described diisocyanate is 2, 4-toluene di-isocyanate(TDI), dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate, described polymerization inhibitor is hydroquinone or MEHQ, described hydroxy acrylate is 2-(Acryloyloxy)ethanol, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate.
6. contain the aqueous polyurethane ultraviolet-curing paint of aqueous polyurethane acrylate described in claim 1, it is characterised in that including:
The aqueous polyurethane acrylate of 68-97 weight portion；
The aqueous levelling agent of 0.1-0.5 weight portion；
The aqueous wetting agent of 0.2-0.6 weight portion；
The aqueous defoamer of 0.2-0.5 weight portion；
The aqueous cosolvent of 3-7 weight portion；
0.1-0.5 weight portion light trigger.
7. aqueous polyurethane ultraviolet-curing paint according to claim 6, it is characterized in that, described aqueous levelling agent is BYK-380N, BYK-381, BYK-307, BYK-341, BYK-345, BYK-346 or BYK-348, described aqueous wetting agent is BYK-187, BYK-3400 or BYK-3410, described aqueous defoamer is BYK-019, BYK-020, BYK-024, BYK-028 or BYK-1730, described aqueous cosolvent is isopropanol, butyl glycol ether, alcohol ester-12 or dipropylene, described light trigger is Irgacure184, Darocur1173, Irgacure2959 or Irgacure819.
8. the preparation method of the aqueous polyurethane ultraviolet-curing paint described in claim 6, it is characterised in that comprise the following steps:
(1) aqueous polyurethane of 68-97 weight portion, the aqueous levelling agent of 0.1-0.5 weight portion, the aqueous wetting agent of 0.2-0.6 weight portion and the aqueous defoamer stirring of 0.2-0.5 weight portion are mixed, obtain mixture；
(2) in said mixture, the aqueous cosolvent of 3-7 weight portion and the light trigger of 0.1-0.5 weight portion are added, stirring mixing, obtain aqueous polyurethane ultraviolet-curing paint.
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| CN104312422A (en) * | 2014-10-28 | 2015-01-28 | 成都纳硕科技有限公司 | Ultraviolet-curable water-based paint for plastic surface |
| CN105404095A (en) * | 2015-12-23 | 2016-03-16 | 河南工程学院 | Washable ultraviolet laser curing and rapid prototyping photosensitive resin and preparation method thereof |
| CN105542651B (en) * | 2015-12-30 | 2018-03-23 | 砺剑防务技术集团有限公司 | Urethane acrylate dispersoid and preparation method thereof and ultraviolet light solidification electrically-conducting paint and preparation method thereof |
| CN106752880A (en) * | 2017-03-15 | 2017-05-31 | 建德市顺发化工助剂有限公司 | A kind of glossy leather finishing agent of ultraviolet light solidfication water polyurethane acrylate |
| CN109851720A (en) * | 2019-02-15 | 2019-06-07 | 临沂市鲁源浸渍纸业有限公司 | A kind of no aldehyde dipping glue and its synthesis technology |
| CN111072910A (en) * | 2019-12-31 | 2020-04-28 | 湖南松井新材料股份有限公司 | Nonionic polyurethane acrylate and preparation method and application thereof |
| CN111334183A (en) * | 2020-04-29 | 2020-06-26 | 温州好惠报企业管理有限公司 | Water-based ultraviolet-curable coating and preparation method thereof |
| CN115505328B (en) * | 2022-10-20 | 2023-12-08 | 江南大学 | Waterborne photo-curing strippable coating and application thereof |
| CN117801664B (en) * | 2023-12-28 | 2024-05-28 | 广东金冠科技股份有限公司 | Scratch-resistant composition, preparation method and application thereof |
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