CN103570911A - Waterborne polyurethaneacrylate, and waterborne polyurethane ultraviolet curing coating and preparation methods thereof - Google Patents
Waterborne polyurethaneacrylate, and waterborne polyurethane ultraviolet curing coating and preparation methods thereof Download PDFInfo
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Abstract
The invention discloses Waterborne polyurethaneacrylate and waterborne polyurethane ultraviolet curing coating and preparation methods thereof, belonging to the technical field of a ultraviolet curing coating, and solving the technical problems that the waterborne polyurethane coating in the prior art pollutes the environment and cannot be ultravioletly cured. The coating comprises the following components in parts by weight: 68-97 parts of waterbore polyurethaneacrylate, 0.1-0.5 part of waterborne leveling agent, 0.2-0.6 part of waterborne wetting agent, 0.2-0.5 part of waterborne defoaming agent, 3-7 parts of waterborne cosolvent, and 0.1-0.5 part of photoinitiator. The invention further provides a structure and a preparation method of the waterborne polyurethaneacrylate. The waterborne polyurethane ultraviolet curing coating has excellent water solubility, can be subjected to ultraviolet curing, does not contain pollutants of a diluent and the like, thus being green and environment-friendly.
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 ether-ether) dibasic alcohol of lower molecular weight is to take double metal cyanide as catalyzer, and carbonic acid gas and epoxy compounds are carried out to polyreaction under chain-transfer agent exists, and take respectively dibasic alcohol or di-carboxylic acid to be prepared from as chain-transfer agent.In the preparation process of such polymer diol, used carbonic acid gas as one of them important source material, thereby greatly reduced the pollution of carbonic acid gas to environment in environment, what is more important has reduced the dependence of petrochemical industry resource.And this poly-(carbonic ether-ether) dibasic alcohol combines the mechanical property of polyester polymer excellence and the hydrolytic resistance of polyether type polymer excellence, thereby, be a kind of soft section of component of important polyurethane polymer.
Chinese patent gathers (carbonic ether-ether) type polyurethane acrylate, ultraviolet photocurable anti-static paint and preparation method thereof (publication number CN103059256A) and has reported take and gather (carbonic ether-ether) dibasic alcohol as soft section of component, prepared solvent borne polyurethane acrylate, and take it as film-forming resin, prepared ultraviolet photocurable anti-static paint.Chinese patent gathers (carbonic ether-ether) type aqueous polyurethane, poly-(carbonic ether-ether) type aqueous polyurethane coating and preparation method thereof (CN103044650A) take and gather (carbonic ether-ether) dibasic alcohol as soft section of component, prepare aqueous polyurethane, and prepared aqueous polyurethane coating as matrix resin.But above-mentioned first patent need to be added reactive thinner and could be used, thereby reactive thinner still can bring certain harm to operator; Second above-mentioned patent, although prepared aqueous polyurethane, can not carry out ultraviolet light polymerization.
Summary of the invention
The object of the invention is to solve the technical problem that aqueous polyurethane coating in prior art endangers environment, can not carry out ultraviolet light polymerization, a kind of aqueous polyurethane acrylate, aqueous polyurethane ultraviolet-curing paint and preparation method thereof are provided.
Aqueous polyurethane acrylate of the present invention, is characterized 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 a kind of in following structure:
-R
1-be a kind of in following structure:
-R
3a kind of in following structure:
R
4a kind of in following structure:
Preparation method when the present invention also provides above-mentioned aqueous polyurethane acrylate to be formula (I) structural formula, comprises the following steps:
(1) under inert atmosphere, in reaction vessel, add 150-610 weight part to gather (carbonic ether-ether) dibasic alcohol, be warmed up to 110-130 ℃, decompression 1-1.5h, cool to again 70-80 ℃, add the acetone of 112-168 weight part and the catalyzer of 0.1-0.31 weight part, add the vulcabond of 53.8-78.5 weight part, reaction 2-4h, obtains the first intermediate;
(2) to the acetone that adds 96-120 weight part in the first intermediate, greenhouse cooling, to 30-45 ℃, drips the amine chain extender of 9.5-13.1 weight part, and after dropwising, reaction 0.5-2h, obtains the second intermediate;
(3) in the second intermediate, add the acetone of 88-208 weight part and the stopper of 0.28-0.44 weight part, add the hydroxy acrylate of 56.8-87.4 weight part, be warmed up to 85-90 ℃, reaction 2-3h; The deionized water that adds again 180-650 weight part, then, adds the protonic acid of 58-97 weight part, stirs 0.5-2h, and acetone is removed in decompression, the aqueous polyurethane acrylate of (I) structure that obtains having formula.
Preferably, the molecular weight of described poly-(carbonic ether-ether) dibasic alcohol is 1500-6000 dalton, described catalyzer is dibutyl tin laurate or stannous octoate, described vulcabond is 2, 4-tolylene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate, described amine hydrophilic chain extender is N methyldiethanol amine, diethanolamine or trolamine, described stopper is Resorcinol or MEHQ, described hydroxy acrylate is Hydroxyethyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate, described protonic acid neutralizing agent is sulfuric acid, oxyacetic acid or trifluoroacetic acid.
Preparation method when the present invention also provides above-mentioned aqueous polyurethane acrylate to be formula (II) structural formula, comprises the following steps:
(1) under inert atmosphere protection, in reaction vessel, add 130-540 weight part to gather (carbonic ether-ether) dibasic alcohol, be warmed up to 110-130 ℃, decompression 1-3h, cool to again 70-80 ℃, add the acetone of 96-128 weight part and the catalyzer of 0.1-0.4 weight part, add the vulcabond of 63.5-88.7 weight part, reaction 2-4h, obtains the first intermediate;
(2) to the acetone that adds 80-224 weight part in the first intermediate, add the dimethylol propionic acid of 13.1-16.8 weight part, be warmed up to 85-90 ℃, reaction 2-3h; The stopper that adds again 0.22-0.38 weight part, adds the hydroxy acrylate of 45.7-76.2 weight part, continues reaction 2-4h, obtains the second intermediate;
(3) cool to 30-45 ℃, in the second intermediate, add the amine neutralizing agent of 18.6-34.1 weight part to neutralize, then, the deionized water that adds 130-520 weight part, stir 15-45min, acetone is removed in decompression, the aqueous polyurethane acrylate of (II) structure that obtains having formula.
Preferably, the molecular weight of described poly-(carbonic ether-ether) dibasic alcohol is 1500-6000 dalton, described catalyzer is dibutyl tin laurate or stannous octoate, described vulcabond is 2, 4-tolylene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate, described stopper is Resorcinol or MEHQ, described hydroxy acrylate is Hydroxyethyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate, described amine neutralizing agent is N, N-dimethylethanolamine or triethylamine.
Preparation method when the present invention also provides above-mentioned aqueous polyurethane acrylate to be formula (III) structural formula, comprises the following steps:
(1) under inert atmosphere protection, in reaction vessel, add poly-(carbonic ether-ether) dibasic alcohol of 145-430 weight part and the polyoxyethylene glycol of 68-137 weight part, be warmed up to 110-130 ℃, decompression 1-3h, cool to again 70-80 ℃, add the acetone of 184-240 weight part and the catalyzer of 0.1-0.3 weight part, add the vulcabond of 102-156 weight part, reaction 2-4h, obtains the first intermediate;
(2) to the acetone that adds 96-104 weight part in the first intermediate, temperature is warmed up to 70-80 ℃, the stopper that adds 0.32-0.58 weight part, the hydroxy acrylate that adds 36.4-61.0 weight part, continues reaction 1-3h, then, the deionized water that adds 263-605 weight part, stir after 10-30min, acetone is removed in decompression, the aqueous polyurethane acrylate of (III) structure that obtains having formula.
Preferably, the molecular weight of described poly-(carbonic ether-ether) dibasic alcohol is 1500-6000 dalton, the molecular weight of described polyoxyethylene glycol is 200-2000 dalton, described catalyzer is dibutyl tin laurate or stannous octoate, described vulcabond is 2, 4-tolylene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate, described stopper is Resorcinol or MEHQ, described hydroxy acrylate is Hydroxyethyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate.
The present invention also provides the aqueous polyurethane that contains above-mentioned aqueous polyurethane acrylate ultraviolet-curing paint, the aqueous polyurethane acrylate that comprises 68-97 weight part, the water-based flow agent of 0.1-0.5 weight part, the aqueous wetting agent of 0.2-0.6 weight part, the water-based defoamer of 0.2-0.5 weight part, the water-based solubility promoter of 3-7 weight part and 0.1-0.5 weight part light trigger.
Preferably, described water-based flow 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 water-based defoamer is BYK-019, BYK-020, BYK-024, BYK-028 or BYK-1730, described water-based solubility promoter is Virahol, butyl glycol ether, alcohol ester-12 or dipropylene glycol butyl ether, and described light trigger is Irfacure184, Darocure1173, Irfacure2959 or Irfacure819.
The present invention also provides the preparation method of above-mentioned aqueous polyurethane ultraviolet-curing paint, comprises the following steps:
(1) the water-based defoamer of the aqueous wetting agent of the water-based flow agent of the aqueous polyurethane of 68-97 weight part, 0.1-0.5 weight part, 0.2-0.6 weight part and 0.2-0.5 weight part is stirred, obtain mixture;
(2) in said mixture, add the water-based solubility promoter of 3-7 weight part and the light trigger of 0.1-0.5 weight part, after stirring, obtain aqueous polyurethane ultraviolet-curing paint.
Beneficial effect of the present invention:
(1) compared to existing technology, aqueous polyurethane acrylate prepared by the present invention be take and gathered (carbonic ether-ether) dibasic alcohol as soft section, thereby reduced the dependence to petrochemical industry resource, and combined the mechanical property of polyester polymer excellence and the hydrolytic resistance of polyether type polymer excellence; In resin structure, introduced hydrophilic radical structure, guaranteed the water dispersible of resin, meanwhile, at end group, introduced unsaturated double-bond, made resin can carry out ultraviolet light polymerization;
(2) aqueous polyurethane ultraviolet-curing paint of the present invention does not contain any reactive thinner, not only fully combines environmental-friendly aqueous feature, and combines the energy-conservation feature of ultraviolet light polymerization, has wide application 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 preparations;
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 preparations.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these are described is just the restriction that further illustrates the features and advantages of the present invention rather than patent of the present invention is required.
The aqueous polyurethane ultraviolet-curing paint of aqueous polyurethane acrylate of the present invention, the aqueous polyurethane acrylate that comprises 68-97 weight part, the water-based flow agent of 0.1-0.5 weight part, the aqueous wetting agent of 0.2-0.6 weight part, the water-based defoamer of 0.2-0.5 weight part, the water-based solubility promoter of 3-7 weight part and 0.1-0.5 weight part light trigger.
In aqueous polyurethane ultraviolet-curing paint of the present invention, aqueous polyurethane acrylate is matrix resin, can 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 a kind of in following structure:
-R
1-be a kind of in following structure:
-R
3a kind of in following structure:
R
4a kind of in following structure:
The aqueous polyurethane acrylate with formula (I) structure, is prepared as follows:
(1), under inert atmosphere protection, poly-(carbonic ether-ether) dibasic alcohol to adding 150-610 weight part in reaction vessel, is warmed up to 110-130 ℃, decompression 1-1.5h; Cool to 70-80 ℃, add the acetone of 112-168 weight part and the catalyzer of 0.1-0.31 weight part, drip the vulcabond of 53.8-78.5 weight part with 5-12ml/min speed, after dropwising, reaction 2-4h, obtains the first intermediate;
(2) toward the acetone that adds 96-120 weight part in the first intermediate, greenhouse cooling, to 30-45 ℃, drips the amine chain extender of 9.5-13.1 weight part with 3-6ml/min speed, and after dropwising, reaction 0.5-2h, obtains the second intermediate;
(3) in the second intermediate, add the acetone of 88-208 weight part and the stopper of 0.28-0.44 weight part, add the hydroxy acrylate of 56.8-87.4 weight part, be warmed up to 85-90 ℃, reaction 2-3h; Then, add the deionized water of 180-650 weight part, then, add the protonic acid of 58-97 weight part, stir 0.5-2h, then, acetone is removed in decompression, the aqueous polyurethane acrylate of (I) structure that obtains having formula.
The aqueous polyurethane acrylate with formula (II) structure, is prepared as follows:
(1), under inert atmosphere protection, poly-(carbonic ether-ether) dibasic alcohol to adding 130-540 weight part in reaction vessel, is warmed up to 110-130 ℃, decompression 1-3h; Cool to 70-80 ℃, add the catalyzer of 96-128 weight part acetone and 0.1-0.4 weight part, drip the vulcabond of 63.5-88.7 weight part with 4-10ml/min speed, after dropwising, reaction 2-4h, obtains the first intermediate;
(2) toward the acetone that adds 80-224 weight part in the first intermediate, add the dimethylol propionic acid of 13.1-16.8 weight part, be warmed up to 85-90 ℃, reaction 2-3h; The stopper that adds 0.22-0.38 weight part, adds the hydroxy acrylate of 45.7-76.2 weight part, continues reaction 2-4h, obtains the second intermediate;
(3) cool to 30-45 ℃, add the amine neutralizing agent of 18.6-34.1 weight part to neutralize, then, the deionized water that adds 130-520 weight part, stirs 15-45min, then, acetone is removed in decompression, the aqueous polyurethane acrylate of (II) structure that obtains having formula.
The aqueous polyurethane acrylate with formula (III) structure, is prepared as follows:
(1) under inert atmosphere protection, in reaction vessel, add poly-(carbonic ether-ether) dibasic alcohol of lower molecular weight of 145-430 weight part and the polyoxyethylene glycol of 68-137 weight part, be warmed up to 110-130 ℃, decompression 1-3h; Cool to 70-80 ℃, add acetone and the 0.1-0.3 weight part catalyzer of 184-240 weight part, drip the vulcabond of 102-156 weight part with 6-13ml/min speed, after dropwising, reaction 2-4h, obtains the first intermediate;
(2) toward the acetone that adds 96-104 weight part in the first intermediate, temperature is warmed up to 70-80 ℃, the stopper that adds 0.32-0.58 weight part, the hydroxy acrylate that adds 36.4-61.0 weight part, continues reaction 1-3h, then, the deionized water that adds 263-605 weight part, stir after 10-30min, acetone is removed in decompression, the aqueous polyurethane acrylate of (III) structure that obtains having formula.
In three kinds of preparation methods of above-mentioned aqueous polyurethane acrylate, the molecular weight of poly-(carbonic ether-ether) dibasic alcohol is 1500-6000 dalton, according to CN102432857, prepares; The molecular weight of polyoxyethylene glycol is 200-2000 dalton; Catalyzer is dibutyl tin laurate or stannous octoate; Vulcabond is 2,4 toluene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or hexamethylene diisocyanate; Amine hydrophilic chain extender is N methyldiethanol amine, diethanolamine or trolamine; Stopper is Resorcinol or MEHQ; Hydroxy acrylate is Hydroxyethyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate; Amine neutralizing agent is N, N-dimethylethanolamine or triethylamine; Protonic acid neutralizing agent is sulfuric acid, oxyacetic acid or trifluoroacetic acid.
In aqueous polyurethane ultraviolet-curing paint of the present invention, the effect of water-based flow agent is to make coating in film process, at substrate surface, has good levelling effect, forms smooth, smooth, even, transparent paint film.Water-based flow agent is preferably the product B YK-380N of BYK company, BYK-381, BYK-307, BYK-341, BYK-345, BYK-346 or BYK-348.
In aqueous polyurethane ultraviolet-curing paint of the present invention, the effect of aqueous wetting agent is the dispersion of assisting material, improves the sticking power of coating.Aqueous wetting agent is preferably the product B YK-187 of BYK company, BYK-3400 or BYK-3410.
In aqueous polyurethane ultraviolet-curing paint of the present invention, the effect of water-based defoamer is in coating coating process, eliminate use or whipping process in the bubble that produces, thereby, reduced the defect that paint film that paint film causes due to the bubble producing produces.Water-based defoamer is preferably the product B YK-019 of BYK company, BYK-020, BYK-024, BYK-028 or BYK-1730.
In aqueous polyurethane ultraviolet-curing paint of the present invention, the effect of water-based solubility promoter is in coating coating process, reduce water-borne coatings in the surface tension of substrate surface, meanwhile, effectively control the film forming speed of coating, make the paint film obtaining have good appearance effect.Water-based solubility promoter is Virahol, butyl glycol ether, alcohol ester-12 or dipropylene glycol butyl ether.
In aqueous polyurethane ultraviolet-curing paint of the present invention, the effect of light trigger is to produce free radical under UV-irradiation, thereby cause aqueous polyurethane acrylate unsaturated double-bond, carries out radical polymerization.Light trigger is preferably Switzerland's vapour Bagong product I rfacure184 of department, Darocure1173, Irfacure2959 or Irfacure819.
The preparation method of aqueous polyurethane ultraviolet-curing paint of the present invention:
(1) the water-based defoamer of the aqueous wetting agent of the water-based flow agent of the aqueous polyurethane of 68-97 weight part, 0.1-0.5 weight part, 0.2-0.6 weight part and 0.2-0.5 weight part is added in homogenizer, rotating speed with 800-1200rpm stirs 1h-3h, obtains mixture;
(2) in described mixture, add the water-based solubility promoter of 3-7 weight part and the light trigger of 0.1-0.5 weight part, after the rotating speed stirring 10-30min with 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
There is the aqueous polyurethane acrylate preparation of formula (I) structure:
(1) under nitrogen protection, in there-necked flask, add 150g to gather (carbonic ether-ether) dibasic alcohol (molecular weight is 1500 dalton), be warmed up to 110 ℃, decompression 1h.Cool to 70 ℃, 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, reaction 2h, obtains the first intermediate.
(2) toward the acetone that adds 120ml in the first intermediate, greenhouse cooling to 30 ℃, drips the N methyldiethanol amine of 9.5g with 3ml/min speed, and after dropwising, reaction 0.5h, obtains the second intermediate.
(3) in the second intermediate, add the acetone of 110ml and the Resorcinol of 0.28g, add the pentaerythritol triacrylate of 56.8g, be warmed up to 85 ℃, reaction 2h.Then, add 180ml deionized water, then, add the oxyacetic acid of 58g, stir 0.5h, then, acetone is removed in decompression, the aqueous polyurethane acrylate of (I) structure that obtains having formula.
The aqueous polyurethane acrylate with formula (I) structure to embodiment 1 preparation carries out magnetic resonance detection, and result 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, confirm that its structure is really suc as formula shown in (I).
There is the aqueous polyurethane acrylate preparation of formula (I) structure:
(1) under nitrogen protection, in there-necked flask, add 610g to gather (carbonic ether-ether) dibasic alcohol (molecular weight is 6000 dalton), be warmed up to 130 ℃, decompression 1.5h.Cool to 80 ℃, add the acetone of 210ml and the stannous octoate of 0.31g, drip the diphenylmethanediisocyanate of 78.5g with 12ml/min speed, after dropwising, reaction 4h, obtains the first intermediate.
(2) toward the acetone that adds 200ml in the first intermediate, greenhouse cooling to 45 ℃, drips the diethanolamine of 13.1g with 6ml/min speed, and after dropwising, reaction 2h, obtains the second intermediate.
(3) toward the MEHQ that adds acetone and the 0.44g of 260ml in the second intermediate, add the double pentaerythritol C5 methacrylate of 87.4g, be warmed up to 90 ℃, reaction 3h.Then, add 650ml deionized water, then, add the trifluoroacetic acid of 97g, stir 2h, then, acetone is removed in decompression, the aqueous polyurethane acrylate of (I) structure that obtains having formula.
Embodiment 3
There is the aqueous polyurethane acrylate preparation of formula (I) structure:
(1) under nitrogen protection, in there-necked flask, add 300g to gather (carbonic ether-ether) dibasic alcohol (molecular weight is 3000 dalton), be warmed up to 120 ℃, decompression 1.5h.Cool to 75 ℃, 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, reaction 3h, obtains the first intermediate.
(2) toward the acetone that adds 190ml in the first intermediate, greenhouse cooling to 35 ℃, drips the trolamine of 11.6g with 5ml/min speed, and after dropwising, reaction 1h, obtains the second intermediate.
(3) toward the MEHQ that adds acetone and the 0.34g of 220ml in the second intermediate, add the trimethylolpropane diacrylate of 76.3g, be warmed up to 88 ℃, reaction 2.5h.Then, add 360ml deionized water, then, add the sulfuric acid of 76g, stir 1.5h, then, acetone is removed in decompression, the aqueous polyurethane acrylate of (I) structure that obtains having formula.
In conjunction with Fig. 2, embodiment 4 is described
There is the aqueous polyurethane acrylate preparation of formula (II) structure:
(1) under nitrogen protection, in there-necked flask, add 130g to gather (carbonic ether-ether) dibasic alcohol (molecular weight is 1500 dalton), be warmed up to 110 ℃, decompression 1h.Cool to 70 ℃, add the acetone of 120ml and the stannous octoate of 0.1g, drip the hexamethylene diisocyanate of 63.5g with 4ml/min speed, after dropwising, reaction 2h, obtains the first intermediate.
(2) toward the acetone that adds 100ml in the first intermediate, add the dimethylol propionic acid of 13.1g, be warmed up to 85 ℃, reaction 2h.The MEHQ that adds 0.22g, adds the Hydroxyethyl acrylate of 45.7g, continues reaction 2h, obtains the second intermediate.
(3) cool to 30 ℃, add the N of 18.6g, N-dimethylethanolamine neutralizes, and then, adds 130ml deionized water, stirs 15min, and then, acetone is removed in decompression, the aqueous polyurethane acrylate of (II) structure that obtains having formula.
The aqueous polyurethane acrylate with formula (II) structure to embodiment 4 preparations carries out magnetic resonance detection, and result 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 preparations: 1.23ppm, 1.65ppm, 2.10ppm, 2.20ppm, 2.29ppm, 4.09ppm, 4.38ppm, 5.88ppm, 6.15ppm, 6.39ppm, 7.08ppm, confirm that its structure is really suc as formula shown in (II).
Embodiment 5
There is the aqueous polyurethane acrylate preparation of formula (II) structure:
(1) under nitrogen protection, in there-necked flask, add 540g to gather (carbonic ether-ether) dibasic alcohol (molecular weight is 6000 dalton), be warmed up to 130 ℃, decompression 3h.Cool to 80 ℃, add the acetone of 160ml and the stannous octoate of 0.4g, drip the dicyclohexyl methane diisocyanate of 88.7g with 10ml/min speed, after dropwising, reaction 4h, obtains the first intermediate.
(2) toward the acetone that adds 280ml in the first intermediate, add the dimethylol propionic acid of 16.8g, be warmed up to 90 ℃, reaction 3h.The Resorcinol that adds 0.38g, adds the pentaerythritol triacrylate of 76.2g, continues reaction 4h, obtains the second intermediate.
(3) cool to 45 ℃, add the triethylamine of 34.1g to neutralize, then, add 520ml deionized water, stir 45min, then, acetone is removed in decompression, the aqueous polyurethane acrylate of (II) structure that obtains having formula.
There is the aqueous polyurethane acrylate preparation of formula (II) structure:
(1) under nitrogen protection, in there-necked flask, add 420g to gather (carbonic ether-ether) dibasic alcohol (molecular weight is 4500 dalton), be warmed up to 120 ℃, decompression 2h.Cool to 75 ℃, 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, reaction 3h, obtains the first intermediate.
(2) toward the acetone that adds 210ml in the first intermediate, add the dimethylol propionic acid of 14.7g, be warmed up to 88 ℃, reaction 2.5h.The Resorcinol that adds 0.28g, adds the double pentaerythritol C5 methacrylate of 67.4g, continues reaction 3h, obtains the second intermediate.
(3) cool to 35 ℃, add N, N-dimethylethanolamine neutralizes, and then, adds 410ml deionized water, stirs 30min, and then, acetone is removed in decompression, the aqueous polyurethane acrylate of (II) structure that obtains having formula.
Embodiment 7
In conjunction with Fig. 3, embodiment 7 is described
There is the aqueous polyurethane acrylate preparation of formula (III) structure:
(1) under nitrogen protection, in there-necked flask, add poly-(carbonic ether-ether) dibasic alcohol (molecular weight is 1500 dalton) of lower molecular weight of 145g and the polyoxyethylene glycol (molecular weight is 200 dalton) of 68g, be warmed up to 110 ℃, decompression 1h.Cool to 70 ℃, add acetone and the 0.1g dibutyl tin laurate of 230ml, drip the isophorone diisocyanate of 102g with 6ml/min speed, after dropwising, reaction 2h, obtains the first intermediate.
(2) toward the acetone that adds 80ml in the first intermediate, temperature is warmed up to 70 ℃, the MEHQ that adds 0.32g, the trimethylolpropane diacrylate that adds 36.4g, continues reaction 1h, then, the deionized water that adds 263g, stir after 10min, acetone is removed in decompression, the aqueous polyurethane acrylate of (III) structure that obtains having formula.
The aqueous polyurethane acrylate with formula (III) structure to embodiment 7 preparations carries out magnetic resonance detection, and result 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 preparations: 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, confirm that its structure is really suc as formula shown in (III).
There is the aqueous polyurethane acrylate preparation of formula (III) structure:
(1) under nitrogen protection, in there-necked flask, add poly-(carbonic ether-ether) dibasic alcohol (molecular weight is 6000 dalton) of lower molecular weight of 430g and the polyoxyethylene glycol (molecular weight is 2000 dalton) of 68-137g, be warmed up to 130 ℃, decompression 3h.Cool to 80 ℃, add acetone and the 0.3g stannous octoate of 300ml, drip the diphenylmethanediisocyanate of 156g with 13ml/min speed, after dropwising, reaction 4h, obtains the first intermediate.
(2) toward the acetone that adds 130ml in the first intermediate, temperature is warmed up to 80 ℃, the Resorcinol that adds 0.58g, the pentaerythritol triacrylate that adds 61.0g, continues reaction 3h, then, the deionized water that adds 605g, stir after 30min, acetone is removed in decompression, the aqueous polyurethane acrylate of (III) structure that obtains having formula.
Embodiment 9
There is the aqueous polyurethane acrylate preparation of formula (III) structure:
(1) under nitrogen protection, in there-necked flask, add poly-(carbonic ether-ether) dibasic alcohol (molecular weight is 3500 dalton) of lower molecular weight of 360g and the polyoxyethylene glycol (molecular weight is 1000 dalton) of 106g, be warmed up to 120 ℃, decompression 2h.Cool to 75 ℃, 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, reaction 3h, obtains the first intermediate.
(2) toward the acetone that adds 110ml in the first intermediate, temperature is warmed up to 75 ℃, the Resorcinol that adds 0.42g, the trimethylolpropane diacrylate that adds 52.3g, continues reaction 2h, then, the deionized water that adds 410g, stir after 20min, acetone is removed in decompression, the aqueous polyurethane acrylate of (III) structure that obtains having formula.
Aqueous polyurethane acrylate preparation method for coating:
According to the ratio of table 1 (unit is g), prepare in accordance with the following methods aqueous polyurethane acrylate coating:
(1) the water-based defoamer of the water-based flow agent of the aqueous polyurethane acrylate of 68-97g, 0.1-0.5g and 0.2-0.5g is added in homogenizer, the rotating speed stirring 1-3h with 800-1200rpm, obtains mixture;
(2) to the light trigger that adds 0.1-0.5g in described mixture, with the rotating speed of 600-800rpm, stir after 10-30min, obtain aqueous polyurethane acrylate coating.
Obtain aqueous polyurethane acrylate coating, be labeled as respectively WUP01, WUP02, WUP03, WUP04, WUP05, WUP06, WUP07, WUP08 and WUP09.
Table 1 is prepared aqueous polyurethane ultraviolet-curing paint WUP01-WUP09 material ratio
Respectively aqueous polyurethane ultraviolet-curing paint WUP01-WUP09 is coated on galvanized sheet iron, at 280~330mJ/cm
2under UV-light energy, solidify, the paint film after solidifying is tested.Test result is in Table 2.
The performance test results that table 2 aqueous polyurethane ultraviolet-curing paint WUP01-WUP09 obtains filming after solidifying
Obviously, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.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, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. aqueous polyurethane acrylate, is characterized 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 a kind of in following structure:
-R
1-be a kind of in following structure:
-R
3a kind of in following structure:
R
4a kind of in following structure:
2. the preparation method of aqueous polyurethane acrylate claimed in claim 1, is characterized in that, when the structural formula of aqueous polyurethane acrylate is formula (I), comprises the following steps:
(1) under inert atmosphere, to poly-(carbonic ether-ether) dibasic alcohol that adds 150-610 weight part in reaction vessel, be warmed up to 110-130 ℃, decompression 1-1.5h, cool to again 70-80 ℃, add the acetone of 112-168 weight part and the catalyzer of 0.1-0.31 weight part, add the vulcabond of 53.8-78.5 weight part, reaction 2-4h, obtains the first intermediate;
(2) to the acetone that adds 96-120 weight part in the first intermediate, cool to 30-45 ℃, drip the amine chain extender of 9.5-13.1 weight part, after dropwising, reaction 0.5-2h, obtains the second intermediate;
(3) in the second intermediate, add the acetone of 88-208 weight part and the stopper of 0.28-0.44 weight part, add the hydroxy acrylate of 56.8-87.4 weight part, be warmed up to 85-90 ℃, reaction 2-3h; The deionized water that adds again 180-650 weight part, then, adds the protonic acid of 58-97 weight part, stirs 0.5-2h, and acetone is removed in decompression, the aqueous polyurethane acrylate of (I) structure that obtains having formula.
3. the preparation method of aqueous polyurethane acrylate according to claim 2, it is characterized in that, the molecular weight of described poly-(carbonic ether-ether) dibasic alcohol is 1500-6000 dalton, described catalyzer is dibutyl tin laurate or stannous octoate, described vulcabond is 2, 4-tolylene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate, described amine hydrophilic chain extender is N methyldiethanol amine, diethanolamine or trolamine, described stopper is Resorcinol or MEHQ, described hydroxy acrylate is Hydroxyethyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate, described protonic acid neutralizing agent is sulfuric acid, oxyacetic acid or trifluoroacetic acid.
4. the preparation method of aqueous polyurethane acrylate claimed in claim 1, is characterized in that, when the structural formula of aqueous polyurethane acrylate is formula (II), comprises the following steps:
(1) under inert atmosphere protection, to poly-(carbonic ether-ether) dibasic alcohol that adds 130-540 weight part in reaction vessel, be warmed up to 110-130 ℃, decompression 1-3h, cool to again 70-80 ℃, add the acetone of 96-128 weight part and the catalyzer of 0.1-0.4 weight part, add the vulcabond of 63.5-88.7 weight part, reaction 2-4h, obtains the first intermediate;
(2) to the acetone that adds 80-224 weight part in the first intermediate, add the dimethylol propionic acid of 13.1-16.8 weight part, be warmed up to 85-90 ℃, reaction 2-3h; The stopper that adds again 0.22-0.38 weight part, adds the hydroxy acrylate of 45.7-76.2 weight part, continues reaction 2-4h, obtains the second intermediate;
(3) cool to 30-45 ℃, in the second intermediate, add the amine neutralizing agent of 18.6-34.1 weight part to neutralize, then, the deionized water that adds 130-520 weight part, stir 15-45min, acetone is removed in decompression, the aqueous polyurethane acrylate of (II) structure that obtains having formula.
5. the preparation method of aqueous polyurethane acrylate according to claim 4, it is characterized in that, the molecular weight of described poly-(carbonic ether-ether) dibasic alcohol is 1500-6000 dalton, described catalyzer is dibutyl tin laurate or stannous octoate, described vulcabond is 2, 4-tolylene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate, described stopper is Resorcinol or MEHQ, described hydroxy acrylate is Hydroxyethyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate, described amine neutralizing agent is N, N-dimethylethanolamine or triethylamine.
6. the preparation method of aqueous polyurethane acrylate claimed in claim 1, is characterized in that, when the structural formula of aqueous polyurethane acrylate is formula (III), comprises the following steps:
(1) under inert atmosphere protection, in reaction vessel, add poly-(carbonic ether-ether) dibasic alcohol of 145-430 weight part and the polyoxyethylene glycol of 68-137 weight part, be warmed up to 110-130 ℃, decompression 1-3h, cool to again 70-80 ℃, add the acetone of 184-240 weight part and the catalyzer of 0.1-0.3 weight part, add the vulcabond of 102-156 weight part, reaction 2-4h, obtains the first intermediate;
(2) to the acetone that adds 96-104 weight part in the first intermediate, temperature is warmed up to 70-80 ℃, the stopper that adds 0.32-0.58 weight part, the hydroxy acrylate that adds 36.4-61.0 weight part, continues reaction 1-3h, then, the deionized water that adds 263-605 weight part, stir after 10-30min, acetone is removed in decompression, the aqueous polyurethane acrylate of (III) structure that obtains having formula.
7. the preparation method of aqueous polyurethane acrylate according to claim 6, it is characterized in that, the molecular weight of described poly-(carbonic ether-ether) dibasic alcohol is 1500-6000 dalton, the molecular weight of described polyoxyethylene glycol is 200-2000 dalton, described catalyzer is dibutyl tin laurate or stannous octoate, described vulcabond is 2, 4-tolylene diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate, described stopper is Resorcinol or MEHQ, described hydroxy acrylate is Hydroxyethyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate.
8. the aqueous polyurethane ultraviolet-curing paint that contains aqueous polyurethane acrylate claimed in claim 1, is characterized in that, comprising:
The aqueous polyurethane acrylate of 68-97 weight part;
The water-based flow agent of 0.1-0.5 weight part;
The aqueous wetting agent of 0.2-0.6 weight part;
The water-based defoamer of 0.2-0.5 weight part;
The water-based solubility promoter of 3-7 weight part;
0.1-0.5 weight part light trigger.
9. aqueous polyurethane ultraviolet-curing paint according to claim 8, it is characterized in that, described water-based flow 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 water-based defoamer is BYK-019, BYK-020, BYK-024, BYK-028 or BYK-1730, described water-based solubility promoter is Virahol, butyl glycol ether, alcohol ester-12 or dipropylene glycol butyl ether, described light trigger is Irfacure 184, Darocure 1173, Irfacure 2959 or Irfacure 819.
10. the preparation method of aqueous polyurethane ultraviolet-curing paint claimed in claim 8, is characterized in that, comprises the following steps:
(1) the water-based defoamer of the aqueous wetting agent of the water-based flow agent of the aqueous polyurethane of 68-97 weight part, 0.1-0.5 weight part, 0.2-0.6 weight part and 0.2-0.5 weight part is uniformly mixed, obtains mixture;
(2) in said mixture, add the water-based solubility promoter of 3-7 weight part and the light trigger of 0.1-0.5 weight part, be uniformly mixed, obtain aqueous polyurethane ultraviolet-curing paint.
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