CN112480368A - Light-cured waterborne polyurethane acrylate resin and preparation method thereof - Google Patents
Light-cured waterborne polyurethane acrylate resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of chemical industry, in particular to a light-cured waterborne polyurethane acrylate resin and a preparation method thereof; the invention prepares a carboxylated hyperbranched polyester, then reacts with prepared acrylic acid grafted isocyanate, and uses triethylamine to salify to obtain aqueous hyperbranched polyurethane acrylic emulsion, and the aqueous hyperbranched polyurethane acrylic emulsion can be cured into a film after ultraviolet light curing; the aqueous hyperbranched polyurethane acrylic emulsion has excellent stability and ultrahigh solid content (about 65 percent), can save energy consumption to the maximum extent in the curing process and shorten the construction period; the hyperbranched polyurethane acrylic emulsion has higher double bond content, a film formed by ultraviolet curing has higher crosslinking density and excellent mechanical property, and compared with a linear polymer, the hyperbranched polyurethane acrylic emulsion has more excellent comprehensive property and wider application due to the unique tree-shaped multi-branch three-dimensional spherical structure.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a photocuring waterborne polyurethane acrylate resin and a preparation method thereof.
Background
In the coating industry, polyurethane is widely applied and is one of the coating varieties with the highest growth speed. It is even thought that the proportion and growth rate of the paint in the industry represent the development level of the coating industry in a country. However, most of the traditional solvent-based PU coatings contain a large amount of organic solvents and a certain amount of free isocyanate, and a large amount of the organic solvents and the free isocyanate volatilize in the using process, so that the health of people is damaged, and the environment is also seriously polluted.
CN109280473A discloses a waterborne polyurethane coating, which consists of waterborne polyurethane resin, silver nano colloidal particles and an auxiliary agent. Specifically, SMA is adopted as a polymer matrix, AgNO3 is added, nano silver is reduced by means of ultraviolet light, the nano silver with antibacterial performance is stably loaded on SMA colloidal particles through the complexation between carbonyl groups on an SMA anhydride ring and the silver, and the obtained silver nano colloidal particles are further added into an aqueous polyurethane coating system to replace conventionally used bactericides such as isothiazolinone and the like in the aqueous polyurethane coating.
CN107841875A relates to a waterborne polyurethane slurry, which comprises the following components in parts by mass: 12-20 parts of waterborne polyurethane, 30-40 parts of starch and 40-60 parts of water, wherein the waterborne polyurethane is a mixture consisting of toluene diisocyanate, polypropylene glycol and dimethylolpropionic acid, and the mass ratio of the toluene diisocyanate to the polypropylene glycol to the dimethylolpropionic acid is 10: 3: 3. the aqueous polyurethane slurry is easy to desize, high in biodegradation speed and free of environmental pollution.
CN103613921A discloses waterborne polyurethane, the raw materials of which are composed of polyether polyurethane prepolymer, dibutyl phthalate, calcium carbonate, calcium magnesium carbonate, 1, 4-butanediol and 1-hydroxy-cyclohexyl-phenyl ketone. The waterborne polyurethane disclosed by the invention is reasonable in formula, has good water resistance and weather resistance, can be used in an external environment for a long time without generating bonding performance, and is low in cost and wide in application range.
The waterborne polyurethane acrylic resin is most applied to a UV curing waterborne system due to the excellent comprehensive performance. For aqueous polyurethane acrylic resin systems, high solids contents and low system viscosities have long been the goals sought by researchers, particularly when applied to UV-curable systems. High solids content means a reduction in the amount of water used in the system, i.e. a reduction in energy consumption; however, most of the water-based polyurethane systems on the market at present contain less than 40 percent of solid content, so that great waste exists on energy sources, and the performance is not slightly lost. In addition, the common problems of low double bond content, insufficient film crosslinking degree, poor mechanical property and heat resistance and the like of the UV curing system also become difficult problems for researchers.
Disclosure of Invention
In order to solve the problems, the invention provides a light-cured water-based polyurethane acrylate resin and a preparation method thereof.
A light-cured water-based polyurethane acrylate resin and a preparation method thereof, the specific scheme is as follows:
adding 10.2-18.4 parts of ferrocene modified polyisocyanate and 0.1-0.4 part of organic tin catalyst into a reaction kettle according to the mass parts, controlling the temperature to be 20-35 ℃, stirring and mixing uniformly, slowly adding 5.3-6.8 parts of ethylene glycol acrylate into the reaction kettle within 10-60min, heating to 30-50 ℃, stirring and reacting for 120-180min to obtain acrylic acid grafted isocyanate; and slowly adding the obtained acrylic acid grafted isocyanate into 58-82 parts of carboxylated modified hyperbranched polyester, finishing the addition within 10-20min, then adding 0.05-0.15 part of organic tin catalyst, controlling the temperature to 65-85 ℃, stirring for reaction for 3-8h, cooling to 40-55 ℃ after the completion, adding 2.4-3.5 parts of triethylamine, continuing to stir for reaction for 30-60min, adding 40-60 parts of deionized water under vigorous stirring, and continuing to stir for 60-180min to obtain the photocuring waterborne polyurethane acrylate resin.
The preparation method of the carboxylated modified hyperbranched polyester comprises the following steps:
adding 27.2-35.6 parts of pentaerythritol and 80-160 parts of N, N-dimethylformamide into a reaction kettle according to the mass parts, stirring and mixing uniformly, adding 0.05-0.14 part of double metal cyanide, heating to 150 ℃ and dissolving 60.4-72.6 parts of succinic acid into 150 parts of N, N-dimethylformamide, separating 40-70% of the mixture, slowly adding the mixture into the reaction kettle, controlling the mixture to be added within 20-50min, carrying out heat preservation and reflux reaction for 1-5h, slowly adding the rest succinic acid solution into the reaction kettle after the reaction is finished, controlling the mixture to be added within 10-30min, and then carrying out heat preservation and reflux reaction for 3-6 h; obtaining hyperbranched polyester after completion; then reducing the reaction temperature to 40-70 ℃, adding 0.08-0.16 part of catalyst 4-dimethylaminopyridine, stirring and mixing uniformly, adding 34.8-52.6 parts of maleic anhydride into a reaction kettle, carrying out heat preservation reaction for 1-5h, and then evaporating the solvent to obtain the carboxylated modified hyperbranched polyester.
The double metal cyanide is iron-zinc double metal cyanide or cobalt-zinc double metal cyanide or nickel-zinc double metal cyanide.
The preparation method of the ferrocene modified polyisocyanate comprises the following steps:
according to the parts by weight,
1) adding 30-50 parts of acetone, 10-20 parts of diisocyanate and 20-40 parts of allyl alcohol into a closed reaction kettle, heating 1-5 parts of hydroxyethyl acrylate to 30-50 ℃ for reaction for 4-8h, and then carrying out rotary evaporation at 60 ℃ for 1-3h to obtain an intermediate mixture.
2) Adding 40-60 parts of n-butyl ketone into a closed high-pressure reaction kettle, adding 10-20 parts of tetramethyl tetravinylcyclotetrasiloxane, 15-25 parts of the intermediate mixture described in 1), 0.05-0.2 part of vinyl ferrocene, 0.01-0.05 part of 4-vinylpyridine-nickel, heating and stirring to 50-70 ℃, adding 0.01-1 part of benzoyl peroxide, reacting for 3-6h, and carrying out rotary evaporation at 80-150 ℃ for 1-3h to obtain the ferrocene modified polyisocyanate.
The diisocyanate is isophorone diisocyanate or methylene diphenyl diisocyanate or toluene diisocyanate.
Part of the preparation of the ferrocene-modified polyisocyanate is shown in the following formula:
firstly, primary alcohol with double bonds is combined with isocyanic acid radical of diisocyanate, and then a product containing the double bonds and other components containing the double bonds react with double bonds of tetramethylvinylcyclotetrasiloxane by free radical addition to generate branched polyisocyanate, namely the ferrocene modified polyisocyanate.
The equation of part of the reaction mechanism is shown as follows:
the organic tin catalyst is dibutyltin dilaurate or dibutyltin bis (dodecyl sulfur) or dibutyltin diacetate.
The curing method of the light-cured water-based polyurethane acrylate resin comprises the following steps: adding 1-5% ultraviolet benzoyl peroxide into resin, stirring and mixing uniformly, spreading a film, drying, and curing under ultraviolet irradiation.
The ultraviolet benzoyl peroxide is 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone or 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone or 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone.
The invention relates to a light-cured water-based polyurethane acrylate resin and a preparation method thereof, wherein the invention uses pentaerythritol and succinic acid to prepare hyperbranched polyester under the action of a catalyst, then hydroxyl on the polyester and maleic anhydride are subjected to ring opening to prepare carboxylated hyperbranched polyester, the carboxylated hyperbranched polyester is reacted with prepared acrylic acid grafted isocyanate, and triethylamine is used for salifying to obtain water-based hyperbranched polyurethane acrylic emulsion which is subjected to ultraviolet light curing to obtain a cured film; the aqueous hyperbranched polyurethane acrylic emulsion has excellent stability and ultrahigh solid content (about 65 percent), can save energy consumption to the maximum extent in the curing process and shorten the construction period; the hyperbranched polyurethane acrylic emulsion has higher double bond content, the ferrocene and the pyridine-nickel functional group enable a film formed by ultraviolet curing to have higher crosslinking density and excellent mechanical property, and the unique tree-shaped multi-branch three-dimensional spherical structure enables the hyperbranched polyurethane acrylic emulsion to have more excellent comprehensive property and wider application than a linear polymer.
Drawings
FIG. 1 is a Fourier infrared spectrum of a photocurable aqueous urethane acrylate resin prepared in example 2:
at 1735cm-1NearbyThere is a stretching absorption peak of ester carbonyl at 1175cm-1An antisymmetric telescopic absorption peak of ester carbon-oxygen single bond exists nearby, and is 2931cm-1The expansion absorption peak of carbon-hydrogen bond is present nearby and is 1451/927cm-1In-plane bending/out-of-plane bending absorption peaks of carboxyl hydroxyl exist nearby, which indicates that the carboxylated modified hyperbranched polyester participates in the reaction; at 3385cm-1The expansion absorption peak of nitrogen hydrogen bond is present nearby and is 1276cm-1A stretching absorption peak of a carbon-nitrogen single bond exists nearby, so that diisocyanate participates in the reaction; at 1634cm-1An absorption peak of carbon-carbon double bonds exists nearby, which indicates that the ethylene glycol acrylate participates in the reaction.
Detailed Description
The invention is further illustrated by the following specific examples:
the solid content determination method comprises the following steps: uniformly coating 10g of sample in a mold, drying in an oven at 80 ℃ to obtain constant weight, and measuring the solid content;
dilution stability of the emulsion: and (3) measuring by a standing method, taking 5ml of polymer emulsion, diluting by 100 times with deionized water, standing for seven days at room temperature, and observing whether the polymer emulsion is layered or precipitated.
Heat and cold resistance of the emulsion: 10ml of the polymer emulsion was placed in a jar at-5 ℃ for 7 days and the change was observed. Adding 10ml of emulsion sample into a test tube with a ground stopper, covering the stopper tightly, placing the test tube into a thermostat, adjusting the temperature to 80 ℃, keeping the temperature for 48 hours, and measuring the heat resistance stability of the emulsion by observing the stability of the emulsion.
Example 1
A light-cured water-based polyurethane acrylate resin and a preparation method thereof, the specific scheme is as follows:
adding 10.2g of ferrocene modified polyisocyanate and 0.1g of organic tin catalyst into a reaction kettle, controlling the temperature to be 20 ℃, stirring and mixing uniformly, then slowly adding 5.3g of ethylene glycol acrylate into the reaction kettle within 10min, heating to 30 ℃, and stirring for reaction for 120min to obtain acrylic acid grafted isocyanate; and slowly adding the obtained acrylic acid grafted isocyanate into 58g of carboxylated modified hyperbranched polyester, finishing the addition within 10min, then adding 0.05g of organic tin catalyst, controlling the temperature to 65 ℃, stirring for reaction for 3h, cooling to 40 ℃ after the completion, adding 2.4g of triethylamine, continuing to stir for reaction for 30min, adding 40g of deionized water under vigorous stirring, and continuing to stir for 60min to obtain the photocuring waterborne polyurethane acrylate resin.
The preparation method of the carboxylated modified hyperbranched polyester comprises the following steps:
adding 27.2g of pentaerythritol and 80g of N, N-dimethylformamide into a reaction kettle, stirring and mixing uniformly, adding 0.05g of double metal cyanide, heating to 130 ℃, dissolving 60.4g of succinic acid into 150g of N, N-dimethylformamide, slowly adding 40% of succinic acid into the reaction kettle, controlling the addition to be finished within 20min, carrying out heat preservation and reflux reaction for 1h, slowly adding the rest succinic acid solution into the reaction kettle after the completion, controlling the addition to be finished within 10min, and carrying out heat preservation and reflux reaction for 3 h; obtaining hyperbranched polyester after completion; then reducing the reaction temperature to 40 ℃, adding 0.08g of catalyst 4-dimethylaminopyridine, stirring and mixing uniformly, adding 34.8g of maleic anhydride into a reaction kettle, carrying out heat preservation reaction for 1 hour, and then evaporating the solvent to obtain the carboxylated modified hyperbranched polyester.
The double metal cyanide is iron-zinc double metal cyanide.
The preparation method of the ferrocene modified polyisocyanate comprises the following steps:
1) 50g of acetone, 10g of diisocyanate, 20g of allyl alcohol and 5g of hydroxyethyl acrylate are added into a closed reaction kettle, the temperature is increased to 50 ℃ for reaction for 8 hours, and then rotary evaporation is carried out at 60 ℃ for 1 hour to obtain an intermediate mixture.
2) Adding 40g of n-butyl ketone into a closed high-pressure reaction kettle, adding 20g of tetramethyl tetravinylcyclotetrasiloxane, 15g of the intermediate mixture described in 1), 0.2g of vinyl ferrocene and 0.01g of 4-vinylpyridine-nickel, heating and stirring to 70 ℃, adding 1g of benzoyl peroxide, reacting for 3h, and carrying out rotary evaporation for 3h at 80 ℃ to obtain the ferrocene modified polyisocyanate.
The diisocyanate is isophorone diisocyanate.
The organic tin catalyst is dibutyltin dilaurate.
Example 2
A light-cured water-based polyurethane acrylate resin and a preparation method thereof, the specific scheme is as follows:
adding 15.2g of ferrocene modified polyisocyanate and 0.3g of organic tin catalyst into a reaction kettle, controlling the temperature to be 25 ℃, stirring and mixing uniformly, then slowly adding 5.8g of ethylene glycol acrylate into the reaction kettle within 30min, heating to 40 ℃, and stirring for reaction for 150min to obtain acrylic acid grafted isocyanate; and slowly adding the obtained acrylic acid grafted isocyanate into 64g of carboxylated modified hyperbranched polyester, finishing the addition within 15min, then adding 0.1g of organic tin catalyst, controlling the temperature to be 75 ℃, stirring for reaction for 5h, cooling to 45 ℃ after the completion, adding 3.1g of triethylamine, continuing to stir for reaction for 40min, adding 48g of deionized water under vigorous stirring, and continuing to stir for 120min to obtain the photocuring waterborne polyurethane acrylate resin.
The preparation method of the carboxylated modified hyperbranched polyester comprises the following steps:
adding 32.4g of pentaerythritol and 120g of N, N-dimethylformamide into a reaction kettle, stirring and mixing uniformly, adding 0.08g of double metal cyanide, heating to 140 ℃, dissolving 66.4g of succinic acid into 155g of N, N-dimethylformamide, slowly adding 60% of succinic acid into the reaction kettle, controlling the addition to be finished within 30min, carrying out heat preservation reflux reaction for 3h, slowly adding the rest succinic acid solution into the reaction kettle after the completion, controlling the addition to be finished within 20min, and carrying out heat preservation reflux reaction for 4.5 h; obtaining hyperbranched polyester after completion; then reducing the reaction temperature to 60 ℃, adding 0.12g of catalyst 4-dimethylaminopyridine, stirring and mixing uniformly, adding 44.2g of maleic anhydride into a reaction kettle, carrying out heat preservation reaction for 3 hours, and then evaporating the solvent to obtain the carboxylated modified hyperbranched polyester.
The double metal cyanide is cobalt-zinc double metal cyanide.
The preparation method of the ferrocene modified polyisocyanate comprises the following steps:
1) adding 30g of acetone, 20g of diisocyanate, 40g of allyl alcohol and 1g of hydroxyethyl acrylate into a closed reaction kettle, heating to 30 ℃, reacting for 4 hours, and then carrying out rotary evaporation for 3 hours at 60 ℃ to obtain an intermediate mixture.
2) Adding 60g of n-butyl ketone into a closed high-pressure reaction kettle, adding 10g of tetramethyl tetravinylcyclotetrasiloxane, 25g of the intermediate mixture described in 1), 0.05g of vinyl ferrocene and 0.05g of 4-vinylpyridine-nickel, heating and stirring to 50 ℃, adding 0.01g of benzoyl peroxide, reacting for 6h, and carrying out rotary evaporation at 150 ℃ for 1h to obtain the ferrocene modified polyisocyanate.
The diisocyanate is methylene diphenyl diisocyanate.
The organic tin catalyst is dibutyltin didodecyl sulfide.
Example 3
A light-cured water-based polyurethane acrylate resin and a preparation method thereof, the specific scheme is as follows:
adding 18.4g of ferrocene modified polyisocyanate and 0.4g of organic tin catalyst into a reaction kettle, controlling the temperature to be 35 ℃, stirring and mixing uniformly, then slowly adding 6.8g of ethylene glycol acrylate into the reaction kettle within 60min, heating to 50 ℃, and stirring for reacting for 180min to obtain acrylic acid grafted isocyanate; and slowly adding the obtained acrylic acid grafted isocyanate into 82g of carboxylated modified hyperbranched polyester, finishing the addition within 20min, then adding 0.15g of organic tin catalyst, controlling the temperature to be 85 ℃, stirring and reacting for 8h, cooling to 55 ℃ after the completion, adding 3.5g of triethylamine, continuing to stir and react for 60min, adding 60g of deionized water under vigorous stirring, and continuing to stir for 180min to obtain the photocuring waterborne polyurethane acrylate resin.
The preparation method of the carboxylated modified hyperbranched polyester comprises the following steps:
adding 35.6g of pentaerythritol and 160g of N, N-dimethylformamide into a reaction kettle, stirring and mixing uniformly, adding 0.14g of double metal cyanide, heating to 150 ℃, dissolving 72.6g of succinic acid into 160g of N, N-dimethylformamide, then slowly adding 70% of succinic acid into the reaction kettle, controlling the addition to be finished within 50min, carrying out heat preservation reflux reaction for 5h, slowly adding the rest succinic acid solution into the reaction kettle after the completion, controlling the addition to be finished within 30min, and then carrying out heat preservation reflux reaction for 6 h; obtaining hyperbranched polyester after completion; then reducing the reaction temperature to 70 ℃, adding 0.16g of catalyst 4-dimethylaminopyridine, stirring and mixing uniformly, adding 52.6g of maleic anhydride into a reaction kettle, carrying out heat preservation reaction for 5 hours, and then evaporating the solvent to obtain the carboxylated modified hyperbranched polyester.
The double metal cyanide is nickel-zinc double metal cyanide.
The preparation method of the ferrocene modified polyisocyanate comprises the following steps:
1) adding 40g of acetone, 16g of diisocyanate, 28g of allyl alcohol and 3g of hydroxyethyl acrylate into a closed reaction kettle, heating to 40 ℃, reacting for 6 hours, and then carrying out rotary evaporation for 2 hours at 60 ℃ to obtain an intermediate mixture.
2) Adding 50g of n-butanone into a closed high-pressure reaction kettle, adding 14g of tetramethyltetravinylcyclotetrasiloxane, 20g of the intermediate mixture described in 1), 1.0g of vinylferrocene and 0.07g of 4-vinylpyridine-nickel, heating and stirring to 60 ℃, adding 0.6g of benzoyl peroxide, reacting for 4.5h, and carrying out rotary evaporation for 2h at 120 ℃ to obtain the ferrocene modified polyisocyanate.
The diisocyanate is toluene diisocyanate.
The organic tin catalyst is dibutyltin diacetate.
The results of the solid content and stability tests on the aqueous polyurethane emulsion prepared in the above examples are shown in the following table:
| solid content (%) | Stable dilutionCharacterization of nature | Stability against cold | Stability against Heat | |
| Example 1 | 65.49 | No precipitation | No precipitation | No precipitation |
| Example 2 | 64.73 | No precipitation | No precipitation | No precipitation |
| Example 3 | 64.85 | No precipitation | No precipitation | No precipitation |
Comparative example 1
A light-cured water-based polyurethane acrylate resin and a preparation method thereof, the specific scheme is as follows:
adding 10.2g of ferrocene modified polyisocyanate and 0.1g of organic tin catalyst into a reaction kettle, controlling the temperature to be 20 ℃, stirring and mixing uniformly, then slowly adding 5.3g of ethylene glycol acrylate into the reaction kettle within 10min, heating to 30 ℃, and stirring for reaction for 120min to obtain acrylic acid grafted isocyanate; and then slowly adding the obtained acrylic acid grafted isocyanate into 50g of polyester diol and 8g of dihydroxy malonic acid, adding the mixture within 10min, then adding 0.05g of organic tin catalyst, controlling the temperature to 65 ℃, stirring and reacting for 3h, cooling to 40 ℃, adding 2.4g of triethylamine, continuously stirring and reacting for 30min, adding 40g of deionized water under vigorous stirring, and continuously stirring for 60min to obtain the photocuring waterborne polyurethane acrylate resin.
The double metal cyanide is iron-zinc double metal cyanide.
The preparation method of the ferrocene modified polyisocyanate comprises the following steps:
1) 50g of acetone, 10g of diisocyanate, 20g of allyl alcohol and 5g of hydroxyethyl acrylate are added into a closed reaction kettle, the temperature is increased to 50 ℃ for reaction for 8 hours, and then rotary evaporation is carried out at 60 ℃ for 1 hour to obtain an intermediate mixture.
2) Adding 40g of n-butyl ketone into a closed high-pressure reaction kettle, adding 20g of tetramethyl tetravinylcyclotetrasiloxane, 15g of the intermediate mixture described in 1), 0.2g of vinyl ferrocene and 0.01g of 4-vinylpyridine-nickel, heating and stirring to 70 ℃, adding 1g of benzoyl peroxide, reacting for 3h, and carrying out rotary evaporation for 3h at 80 ℃ to obtain the ferrocene modified polyisocyanate.
The diisocyanate is isophorone diisocyanate.
The organic tin catalyst is dibutyltin dilaurate.
Comparative example 2
A light-cured water-based polyurethane acrylate resin and a preparation method thereof, the specific scheme is as follows:
adding 10.2g of ferrocene modified polyisocyanate and 0.1g of organic tin catalyst into a reaction kettle, controlling the temperature to be 20 ℃, stirring and mixing uniformly, then slowly adding 5.3g of ethylene glycol acrylate into the reaction kettle within 10min, heating to 30 ℃, and stirring for reaction for 120min to obtain acrylic acid grafted isocyanate; and slowly adding the obtained acrylic acid grafted isocyanate into 58g of carboxylated modified hyperbranched polyester, finishing the addition within 10min, then adding 0.05g of organic tin catalyst, controlling the temperature to 65 ℃, stirring for reaction for 3h, cooling to 40 ℃ after the completion, adding 2.4g of triethylamine, continuing to stir for reaction for 30min, adding 40g of deionized water under vigorous stirring, and continuing to stir for 60min to obtain the photocuring waterborne polyurethane acrylate resin.
The preparation method of the carboxylated modified hyperbranched polyester comprises the following steps:
adding 27.2g of pentaerythritol and 80g of N, N-dimethylformamide into a reaction kettle, heating to 130 ℃, dissolving 60.4g of succinic acid into 150g of N, N-dimethylformamide, separating 40% of succinic acid, slowly adding into the reaction kettle, controlling the addition to be finished within 20min, carrying out heat preservation reflux reaction for 1h, slowly adding the rest succinic acid solution into the reaction kettle after the completion, controlling the addition to be finished within 10min, and carrying out heat preservation reflux reaction for 3 h; obtaining hyperbranched polyester after completion; then reducing the reaction temperature to 40 ℃, adding 0.08g of catalyst 4-dimethylaminopyridine, stirring and mixing uniformly, adding 34.8g of maleic anhydride into a reaction kettle, carrying out heat preservation reaction for 1 hour, and then evaporating the solvent to obtain the carboxylated modified hyperbranched polyester.
The preparation method of the ferrocene modified polyisocyanate comprises the following steps:
1) 50g of acetone, 10g of diisocyanate, 20g of allyl alcohol and 5g of hydroxyethyl acrylate are added into a closed reaction kettle, the temperature is increased to 50 ℃ for reaction for 8 hours, and then rotary evaporation is carried out at 60 ℃ for 1 hour to obtain an intermediate mixture.
2) Adding 40g of n-butyl ketone into a closed high-pressure reaction kettle, adding 20g of tetramethyl tetravinylcyclotetrasiloxane, 15g of the intermediate mixture described in 1), 0.2g of vinyl ferrocene and 0.01g of 4-vinylpyridine-nickel, heating and stirring to 70 ℃, adding 1g of benzoyl peroxide, reacting for 3h, and carrying out rotary evaporation for 3h at 80 ℃ to obtain the ferrocene modified polyisocyanate.
The diisocyanate is isophorone diisocyanate.
The organic tin catalyst is dibutyltin dilaurate.
Comparative example 3
A light-cured water-based polyurethane acrylate resin and a preparation method thereof, the specific scheme is as follows:
adding 10.2g of ferrocene modified polyisocyanate and 0.1g of organic tin catalyst into a reaction kettle, controlling the temperature to be 20 ℃, stirring and mixing uniformly, then slowly adding 5.3g of ethylene glycol acrylate into the reaction kettle within 10min, heating to 30 ℃, and stirring for reaction for 120min to obtain acrylic acid grafted isocyanate; and slowly adding the obtained acrylic acid grafted isocyanate into 58g of carboxylated modified hyperbranched polyester, finishing the addition within 10min, then adding 0.05g of organic tin catalyst, controlling the temperature to 65 ℃, stirring for reaction for 3h, cooling to 40 ℃ after the completion, adding 2.4g of triethylamine, continuing to stir for reaction for 30min, adding 40g of deionized water under vigorous stirring, and continuing to stir for 60min to obtain the photocuring waterborne polyurethane acrylate resin.
The preparation method of the carboxylated modified hyperbranched polyester comprises the following steps:
adding 27.2g of pentaerythritol and 80g of N, N-dimethylformamide into a reaction kettle, stirring and mixing uniformly, adding 0.05g of double metal cyanide, heating to 130 ℃, dissolving 60.4g of succinic acid into 150g of N, N-dimethylformamide, slowly adding 40% of succinic acid into the reaction kettle, controlling the addition to be finished within 20min, carrying out heat preservation and reflux reaction for 1h, slowly adding the rest succinic acid solution into the reaction kettle after the completion, controlling the addition to be finished within 10min, and carrying out heat preservation and reflux reaction for 3 h; obtaining hyperbranched polyester after completion; then reducing the reaction temperature to 40 ℃, preserving the heat for reaction for 1h, and then evaporating the solvent to obtain the carboxylated modified hyperbranched polyester.
The double metal cyanide is iron-zinc double metal cyanide.
The preparation method of the ferrocene modified polyisocyanate comprises the following steps:
1) 50g of acetone, 10g of diisocyanate, 20g of allyl alcohol and 5g of hydroxyethyl acrylate are added into a closed reaction kettle, the temperature is increased to 50 ℃ for reaction for 8 hours, and then rotary evaporation is carried out at 60 ℃ for 1 hour to obtain an intermediate mixture.
2) Adding 40g of n-butyl ketone into a closed high-pressure reaction kettle, adding 20g of tetramethyl tetravinylcyclotetrasiloxane, 15g of the intermediate mixture described in 1), 0.2g of vinyl ferrocene and 0.01g of 4-vinylpyridine-nickel, heating and stirring to 70 ℃, adding 1g of benzoyl peroxide, reacting for 3h, and carrying out rotary evaporation for 3h at 80 ℃ to obtain the ferrocene modified polyisocyanate.
The diisocyanate is isophorone diisocyanate.
The organic tin catalyst is dibutyltin dilaurate.
Comparative example 4
A light-cured water-based polyurethane acrylate resin and a preparation method thereof, the specific scheme is as follows:
adding 10.2g of diisocyanate and 0.1g of organic tin catalyst into a reaction kettle, controlling the temperature to be 20 ℃, stirring and mixing uniformly, slowly adding 5.3g of ethylene glycol acrylate into the reaction kettle within 10min, heating to 30 ℃, and stirring for reaction for 120min to obtain acrylic acid grafted isocyanate; and slowly adding the obtained acrylic acid grafted isocyanate into 58g of carboxylated modified hyperbranched polyester, finishing the addition within 10min, then adding 0.05g of organic tin catalyst, controlling the temperature to 65 ℃, stirring for reaction for 3h, cooling to 40 ℃ after the completion, adding 2.4g of triethylamine, continuing to stir for reaction for 30min, adding 40g of deionized water under vigorous stirring, and continuing to stir for 60min to obtain the photocuring waterborne polyurethane acrylate resin.
The preparation method of the carboxylated modified hyperbranched polyester comprises the following steps:
adding 27.2g of pentaerythritol and 80g of N, N-dimethylformamide into a reaction kettle, stirring and mixing uniformly, adding 0.05g of double metal cyanide, heating to 130 ℃, dissolving 60.4g of succinic acid into 150g of N, N-dimethylformamide, slowly adding 40% of succinic acid into the reaction kettle, controlling the addition to be finished within 20min, carrying out heat preservation and reflux reaction for 1h, slowly adding the rest succinic acid solution into the reaction kettle after the completion, controlling the addition to be finished within 10min, and carrying out heat preservation and reflux reaction for 3 h; obtaining hyperbranched polyester after completion; then reducing the reaction temperature to 40 ℃, adding 0.08g of catalyst 4-dimethylaminopyridine, stirring and mixing uniformly, adding 34.8g of maleic anhydride into a reaction kettle, carrying out heat preservation reaction for 1 hour, and then evaporating the solvent to obtain the carboxylated modified hyperbranched polyester.
The double metal cyanide is iron-zinc double metal cyanide.
The diisocyanate is isophorone diisocyanate.
The organic tin catalyst is dibutyltin dilaurate.
Comparative example 5
The preparation method of the ferrocene modified polyisocyanate comprises the following steps:
1) 50g of acetone, 10g of diisocyanate, 20g of allyl alcohol and 5g of hydroxyethyl acrylate are added into a closed reaction kettle, the temperature is increased to 50 ℃ for reaction for 8 hours, and then rotary evaporation is carried out at 60 ℃ for 1 hour to obtain an intermediate mixture.
2) Adding 40g of n-butyl ketone into a closed high-pressure reaction kettle, adding 20g of tetramethyl tetravinylcyclotetrasiloxane, 15g of the intermediate mixture in the step 1) and 0.01g of 4-vinylpyridine-nickel, heating and stirring to 70 ℃, adding 1g of benzoyl peroxide, reacting for 3h, and carrying out rotary evaporation at 80 ℃ for 3h to obtain the ferrocene modified polyisocyanate.
Otherwise, the same procedure as in example 1 was repeated.
Comparative examples 1 and 3 in the above practical examples failed to form stable emulsions, and the results of the solid content and stability tests of the aqueous polyurethane emulsion prepared in comparative example 2 are shown in the following table:
| solid content (%) | Stability in dilution | Stability against cold | Stability against Heat | |
| Comparative example 1 | -- | -- | -- | -- |
| Comparative example 2 | 60.86 | With a small amount of precipitation | No precipitation | Complete phase separation |
| Comparative example 3 | -- | -- | -- | -- |
| Comparative example 4 | 52.32 | With a small amount of precipitation | No precipitation | No precipitation |
| Comparative example 5 | 62.21 | With a small amount of precipitation | No precipitation | No precipitation |
Claims (8)
1. A light-cured water-based polyurethane acrylate resin and a preparation method thereof, the specific scheme is as follows:
adding 10.2-18.4 parts of ferrocene modified polyisocyanate and 0.1-0.4 part of organic tin catalyst into a reaction kettle according to the mass parts, controlling the temperature to be 20-35 ℃, stirring and mixing uniformly, slowly adding 5.3-6.8 parts of ethylene glycol acrylate into the reaction kettle within 10-60min, heating to 30-50 ℃, stirring and reacting for 120-180min to obtain acrylic acid grafted isocyanate; and slowly adding the obtained acrylic acid grafted isocyanate into 58-82 parts of carboxylated modified hyperbranched polyester, finishing the addition within 10-20min, then adding 0.05-0.15 part of organic tin catalyst, controlling the temperature to 65-85 ℃, stirring for reaction for 3-8h, cooling to 40-55 ℃ after the completion, adding 2.4-3.5 parts of triethylamine, continuing to stir for reaction for 30-60min, adding 40-60 parts of deionized water under vigorous stirring, and continuing to stir for 60-180min to obtain the photocuring waterborne polyurethane acrylate resin.
2. The photo-curable aqueous urethane acrylate resin and the preparation method thereof according to claim 1, wherein: the preparation method of the carboxylated modified hyperbranched polyester comprises the following steps:
adding 27.2-35.6 parts of pentaerythritol and 80-160 parts of N, N-dimethylformamide into a reaction kettle according to the mass parts, stirring and mixing uniformly, adding 0.05-0.14 part of double metal cyanide, heating to 150 ℃ and dissolving 60.4-72.6 parts of succinic acid into 150 parts of N, N-dimethylformamide, separating 40-70% of the mixture, slowly adding the mixture into the reaction kettle, controlling the mixture to be added within 20-50min, carrying out heat preservation and reflux reaction for 1-5h, slowly adding the rest succinic acid solution into the reaction kettle after the reaction is finished, controlling the mixture to be added within 10-30min, and then carrying out heat preservation and reflux reaction for 3-6 h; obtaining hyperbranched polyester after completion; then reducing the reaction temperature to 40-70 ℃, adding 0.08-0.16 part of catalyst 4-dimethylaminopyridine, stirring and mixing uniformly, adding 34.8-52.6 parts of maleic anhydride into a reaction kettle, carrying out heat preservation reaction for 1-5h, and then evaporating the solvent to obtain the carboxylated modified hyperbranched polyester.
3. The photo-curable aqueous urethane acrylate resin and the preparation method thereof according to claim 2, wherein: the double metal cyanide is iron-zinc double metal cyanide or cobalt-zinc double metal cyanide or nickel-zinc double metal cyanide.
4. The photo-curable aqueous urethane acrylate resin and the preparation method thereof according to claim 1, wherein: the preparation method of the ferrocene modified polyisocyanate comprises the following steps: according to the parts by weight,
1) adding 30-50 parts of acetone, 10-20 parts of diisocyanate and 20-40 parts of allyl alcohol into a closed reaction kettle, heating 1-5 parts of hydroxyethyl acrylate to 30-50 ℃ for reaction for 4-8h, and then carrying out rotary evaporation at 60 ℃ for 1-3h to obtain an intermediate mixture.
2) Adding 40-60 parts of n-butyl ketone into a closed high-pressure reaction kettle, adding 10-20 parts of tetramethyl tetravinylcyclotetrasiloxane, 15-25 parts of the intermediate mixture described in 1), 0.05-0.2 part of vinyl ferrocene, 0.01-0.05 part of 4-vinylpyridine-nickel, heating and stirring to 50-70 ℃, adding 0.01-1 part of benzoyl peroxide, reacting for 3-6h, and carrying out rotary evaporation at 80-150 ℃ for 1-3h to obtain the ferrocene modified polyisocyanate.
5. The photo-curable aqueous urethane acrylate resin and the preparation method thereof according to claim 4, wherein: the diisocyanate is isophorone diisocyanate or methylene diphenyl diisocyanate or toluene diisocyanate.
6. The photo-curable aqueous urethane acrylate resin and the preparation method thereof according to claim 1, wherein: the organic tin catalyst is dibutyltin dilaurate or dibutyltin bis (dodecyl sulfur) or dibutyltin diacetate.
7. The photo-curable aqueous urethane acrylate resin and the preparation method thereof according to claim 1, wherein: the curing method of the light-cured water-based polyurethane acrylate resin comprises the following steps: adding 1-5% ultraviolet benzoyl peroxide into resin, stirring and mixing uniformly, spreading a film, drying, and curing under ultraviolet irradiation.
8. The photo-curable aqueous urethane acrylate resin and the preparation method thereof according to claim 7, wherein: the ultraviolet benzoyl peroxide is 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone or 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone or 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113072872A (en) * | 2021-03-31 | 2021-07-06 | 安徽鸿之浩电子科技有限公司 | Anti-ultraviolet bright plastic paint coating and preparation method thereof |
| CN114249874A (en) * | 2021-12-22 | 2022-03-29 | 上海工程技术大学 | Dendritic polyurethane, preparation method thereof and application of dendritic polyurethane in chlorinated butyl damping rubber |
| CN114958271A (en) * | 2022-06-09 | 2022-08-30 | 南宁市匠心鸣居建筑材料有限公司 | Heat-resistant high-performance polyurethane adhesive and preparation method thereof |
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2020
- 2020-11-26 CN CN202011347801.7A patent/CN112480368A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113072872A (en) * | 2021-03-31 | 2021-07-06 | 安徽鸿之浩电子科技有限公司 | Anti-ultraviolet bright plastic paint coating and preparation method thereof |
| CN114249874A (en) * | 2021-12-22 | 2022-03-29 | 上海工程技术大学 | Dendritic polyurethane, preparation method thereof and application of dendritic polyurethane in chlorinated butyl damping rubber |
| CN114958271A (en) * | 2022-06-09 | 2022-08-30 | 南宁市匠心鸣居建筑材料有限公司 | Heat-resistant high-performance polyurethane adhesive and preparation method thereof |
| CN116574237A (en) * | 2023-07-13 | 2023-08-11 | 广州亚伊汽车零部件有限公司 | Foaming material for automotive interior and production process thereof |
| CN116574237B (en) * | 2023-07-13 | 2023-09-22 | 广州亚伊汽车零部件有限公司 | Foaming material for automotive interior and production process thereof |
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