CN111116862B - Hyperbranched castor oil-based aqueous UV curing prepolymer and preparation method and application thereof - Google Patents
Hyperbranched castor oil-based aqueous UV curing prepolymer and preparation method and application thereof Download PDFInfo
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- CN111116862B CN111116862B CN201911390371.4A CN201911390371A CN111116862B CN 111116862 B CN111116862 B CN 111116862B CN 201911390371 A CN201911390371 A CN 201911390371A CN 111116862 B CN111116862 B CN 111116862B
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Abstract
The invention belongs to the field of aqueous UV curing high polymer materials, and particularly relates to a hyperbranched castor oil based aqueous UV curing prepolymer and a preparation method and application thereof. The method comprises the following steps: adding dimethylolpropionic acid, castor oil and an esterification catalyst into a reaction kettle, heating, vacuumizing, dehydrating, cooling, adding a solvent for dissolving, adding a separating agent to crystallize, precipitate and separate out a product, and vacuum drying to obtain the hyperbranched hydroxyl resin; dripping the mixture of diisocyanate and catalyst into hyperbranched hydroxyl resin, and heating and stirring for reaction to obtain an intermediate product; and dissolving the intermediate product with a solvent, dropwise adding polyethylene glycol acrylate and a polymerization inhibitor, and reacting to obtain the hyperbranched castor oil-based aqueous UV curing prepolymer. The hyperbranched castor oil-based aqueous UV curing prepolymer prepared by the invention has high crosslinking density, so that a coating prepared by using the hyperbranched castor oil-based aqueous UV curing prepolymer has excellent mechanical and water-resistant properties and the like, and can be used as a film forming base material in the fields of paint and ink.
Description
Technical Field
The invention belongs to the field of aqueous UV curing materials, and particularly relates to a hyperbranched castor oil based aqueous UV curing prepolymer and a preparation method and application thereof.
Background
The consumption of global fossil resources and the environmental pollution caused by the consumption of global fossil resources lead people to deeply realize that the resource problem not only influences the ecological environment of people, but also hinders the development of organic polymer chemical industry based on fossil raw materials, and biomass resources are the only raw materials and chemical resources which can be continuously utilized at present. Therefore, the important point is to comprehensively utilize biomass resources to manufacture high-performance bio-based chemicals and bio-based materials, and the important theoretical and practical significance is achieved in enhancing the research on the core key technologies such as biological conversion, chemical conversion, composite forming and the like in the manufacturing process of the bio-based materials and the chemicals. The UV curing coating has high energy utilization rate; no solvent is discharged, and the method is safe and pollution-free; the curing speed is high, and the production efficiency is high; can coat the base material sensitive to heat; high coating quality, excellent coating performance and the like, and is an environment-friendly coating. However, the main raw material acrylic monomer depended by the UV curing coating is mainly from fossil raw materials, and the defects of high volatility, large smell, non-regeneration and the like greatly limit the raw material source of the UV curing coating. A large number of natural products can be extracted from agricultural and forestry resources, and many of the natural products contain double bonds or hydroxyl and other active reaction groups, so that a UV curing system is easily constructed, the agricultural and forestry natural resources are converted into UV curing raw materials, and the raw material source of the UV curing material is greatly developed. The oil-based UV curable coatings can achieve an excellent balance of properties, but their environmental advantages are diminished by irritation and toxicity problems due to the use of reactive diluents for viscosity adjustment. Although the existing water-based paint is excellent in the aspect of environmental protection, the service performance is poor, and particularly, improvement on the aspects of appearance, hardness and the like is needed. Therefore, the research of the water-based UV coating combining the advantages of the two becomes a popular research field of the coating industry at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a hyperbranched castor oil based water-based UV curing prepolymer.
According to the invention, castor oil is taken as the center for preparing the hyperbranched resin, and dimethylolpropionic acid is used for grafting the castor oil to prepare a hydroxyl-terminated second-generation hyperbranched prepolymer. And (2) carrying out graft end capping on the hyperbranched prepolymer by using a diisocyanate crosslinking agent and polyethylene glycol acrylate with hydrophilicity and UV curing activity to obtain the hyperbranched castor oil based waterborne UV curing prepolymer. The prepared hyperbranched castor oil based waterborne UV curing prepolymer contains twelve hydrophilic polyethylene glycol acrylate long chains, so that the prepolymer can be ensured to have good hydrophilicity, and can be stably dispersed in water.
Another object of the present invention is to provide the above hyperbranched castor oil-based aqueous UV-curable prepolymer.
The invention further aims to provide application of the hyperbranched castor oil-based aqueous UV curing prepolymer in the fields of aqueous UV curing coatings, aqueous UV curing inks, aqueous UV curing adhesives and the like.
A preparation method of hyperbranched castor oil based water-based UV curing prepolymer comprises the following steps:
(1) adding dimethylolpropionic acid, castor oil and an esterification catalyst into a reaction kettle, stirring, heating to 120-150 ℃, performing vacuum dehydration reaction for 2-3 hours, then cooling to 65-75 ℃, adding a solvent for dissolution, then adding a separating agent into the reaction kettle at 5-15 ℃ to crystallize, precipitate and separate a product, and performing vacuum drying to obtain the hyperbranched hydroxyl resin;
(2) dripping a mixture of diisocyanate and a catalyst into the hyperbranched hydroxyl resin prepared in the step (1) at 15-25 ℃, adjusting the dripping speed to be controlled within 1-2 h, heating to 50-80 ℃, stirring and reacting for 2-3 h to obtain an intermediate product;
(3) dissolving all the intermediate products obtained in the step (2) by using a solvent, dropwise adding polyethylene glycol acrylate and a polymerization inhibitor, controlling the temperature to be 60-78 ℃, reacting for 1.5-2.5 h, and performing rotary evaporation to remove the solvent to obtain the hyperbranched castor oil-based aqueous UV curing prepolymer.
Preferably, the molar ratio of the castor oil to the dimethylolpropionic acid in the step (1) is 1: 9; the esterification catalyst is at least one of N, N' -diisopropylcarbodiimide, dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, p-toluenesulfonic acid and tetrabutyl titanate, and the using amount of the esterification catalyst is 1-3% of the molar amount of dimethylolpropionic acid.
Preferably, the solvent in the step (1) is at least one of acetone, methyl ethyl ketone, methyl isopropyl ketone and cyclohexanone, and the dosage of the solvent is 10-15 times of the total mass of the dimethylolpropionic acid and the castor oil; the precipitating agent is at least one of cyclohexane, n-hexane, heptane, 2-methylhexane and octane, and the dosage of the precipitating agent is 10-15 times of the total mass of the dimethylolpropionic acid and the castor oil.
Preferably, the diisocyanate in the step (2) is aromatic and/or aliphatic isocyanate, preferably diisocyanate, more preferably at least one of isophorone diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate and dicyclohexyl hexane diisocyanate; the diisocyanate was present in a 12 molar amount based on moles of the initial castor oil (i.e., a 1: 12 molar ratio of initial castor oil to diisocyanate).
Preferably, the catalyst in the step (2) is dibutyltin dilaurate, and the weight of the catalyst is 0.1-0.15 parts by weight based on 100 parts by weight of the hyperbranched hydroxyl resin.
Preferably, the solvent in the step (3) is at least one of acetone, butanone and tetrahydrofuran; and (3) the solvent accounts for 10-50 parts by weight based on 100 parts by weight of the intermediate product prepared in the step (2).
Preferably, the polyethylene glycol acrylate in the step (3) is liquid, and the number average molecular weight of the polyethylene glycol acrylate is 600-1000; the usage amount of the castor oil is 12-13 times of the molar amount of the castor oil used in the step (1) in terms of molar parts.
Preferably, the polymerization inhibitor in the step (3) is p-hydroxyanisole or/and hydroquinone; the polymerization inhibitor is 0.1-0.5 part by weight based on 100 parts by weight of polyethylene glycol acrylate.
Preferably, the speed of dripping the solution in the steps (2) and (3) is 1-15 mL/min.
The hyperbranched castor oil-based aqueous UV curing prepolymer is prepared by a three-step method, and has the advantages of regular molecular structure, strong reaction controllability and good reproducibility. Renewable castor oil is used as a main raw material to synthesize the aqueous UV curing prepolymer, so that the conversion of low-grade biomass to high value-added chemicals is realized.
The hyperbranched castor oil-based aqueous UV curing prepolymer prepared by the invention has high crosslinking density, so that a coating prepared by using the hyperbranched castor oil-based aqueous UV curing prepolymer has excellent mechanical and water-resistant properties and the like, and can be used as a film forming base material in the fields of paint and ink.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, the castor oil is used as a raw material for preparing the aqueous UV curing prepolymer, so that the application range and value of the renewable biomass product are improved, and the method has great popularization significance. And introducing castor oil as a polyhydroxy hyperbranched resin core, dehydrating and condensing side end hydroxyl groups of the castor oil and carboxyl groups of dimethylolpropionic acid, then carrying out self-condensation reaction on the dimethylolpropionic acid to form a dendritic polyhydroxy compound, and grafting polyethylene glycol acrylate with water solubility and UV curing activity to obtain the hyperbranched castor oil-based waterborne UV curing prepolymer surrounded by a hydrophilic chain segment.
(2) The prepolymer has the advantages of good hydrophilicity and high functionality, and the good hydrophilicity can ensure the excellent dispersion performance of the prepolymer in water, thereby ensuring that the prepared water-based UV curing material has excellent stability. The core of the prepolymer is castor oil with excellent hydrophobicity, and the hydrophilic chain segment of the prepolymer contains twelve double bonds, so that a three-dimensional network structure with extremely high crosslinking degree can be formed when the prepolymer is solidified into a film, and the solidified film has excellent water resistance. Therefore, the hyperbranched castor oil based water-based UV curing prepolymer prepared by the invention effectively solves the problem of contradiction between the hydrophilicity of the prepolymer of the water-based UV curing coating and the water resistance of a curing film.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Sequentially adding metered dimethylolpropionic acid, castor oil (the molar ratio of the castor oil to the dimethylolpropionic acid is 1:9) and N, N' -diisopropylcarbodiimide (the dosage is 1% of the molar quantity of the dimethylolpropionic acid), stirring, heating to 120 ℃, performing vacuum dehydration reaction for 3 hours, cooling to 65 ℃, adding a certain amount of acetone (the dosage is 10 times of the total mass of the dimethylolpropionic acid and the castor oil) for dissolving, then placing at 5 ℃, adding a certain amount of cyclohexane (the dosage is 15 times of the total mass of the dimethylolpropionic acid and the castor oil) to crystallize, precipitate and separate out a product, and performing vacuum drying to obtain the hyperbranched hydroxyl resin;
(2) dripping a mixture of isophorone diisocyanate (the dosage is 12 times of the molar weight of castor oil) and dibutyltin dilaurate (the dosage is 0.1 percent of the weight of the hyperbranched hydroxyl resin) into the hyperbranched hydroxyl resin prepared in the step (1) in a 15-DEG C constant-temperature water bath, controlling the dripping speed within 1h, heating to 80 ℃, stirring and reacting for 2h to obtain an intermediate product;
(3) dissolving all the intermediate products obtained in the step (2) by using acetone (the dosage is 10% of the weight of the intermediate product prepared in the step (2)), dropwise adding polyethylene glycol acrylate with the molecular weight of 600 (the dosage is 12 times of the molar quantity of castor oil, and the dropwise adding speed is 10mL/min) and p-hydroxyanisole (the dosage is 0.5% of the weight of the polyethylene glycol acrylate), controlling the temperature to be 78 ℃, reacting for 2.5h, and rotationally evaporating to remove the solvent to obtain the hyperbranched castor oil based waterborne UV curing prepolymer.
Example 2
(1) Sequentially adding metered dimethylolpropionic acid, castor oil (the molar ratio of the castor oil to the dimethylolpropionic acid is 1:9) and dicyclohexylcarbodiimide (the dosage of the dimethylolpropionic acid is 3% of the molar quantity of the dimethylolpropionic acid), stirring, heating to 150 ℃, performing vacuum dehydration reaction for 2 hours, cooling to 75 ℃, adding a certain amount of cyclohexanone (the dosage of the cyclohexanone is 15 times of the total mass of the dimethylolpropionic acid and the castor oil) for dissolving, placing the mixture at 15 ℃, adding a certain amount of octane (the dosage of the octane is 10 times of the total mass of the dimethylolpropionic acid and the castor oil) to crystallize and precipitate a product, and performing vacuum drying to obtain the hyperbranched hydroxyl resin;
(2) dripping a mixture of toluene diisocyanate (the dosage is 12 times of the molar weight of castor oil) and dibutyltin dilaurate (the dosage is 0.15 percent of the weight of the hyperbranched hydroxyl resin) into the hyperbranched hydroxyl resin prepared in the step (1) in a thermostatic water bath at 25 ℃, adjusting the dripping speed to be controlled to be 2 hours, heating to 50 ℃, stirring and reacting for 3 hours to obtain an intermediate product;
(3) dissolving all the intermediate products obtained in the step (2) with butanone (the dosage is 50% of the weight of the intermediate products prepared in the step (2)), dropwise adding polyethylene glycol acrylate with the molecular weight of 1000 (the dosage is 13 times of the molar quantity of castor oil, and the dropwise adding speed is 15mL/min) and hydroquinone (the dosage is 0.4% of the weight of the polyethylene glycol acrylate), controlling the temperature to be 60 ℃, reacting for 1.5h, and rotationally evaporating to remove the solvent to obtain the hyperbranched castor oil based waterborne UV curing prepolymer.
Example 3
(1) Sequentially adding metered dimethylolpropionic acid, castor oil (the molar ratio of the castor oil to the dimethylolpropionic acid is 1:9) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (the dosage is 2 percent of the molar weight of the dimethylolpropionic acid) into a reaction kettle, stirring, heating to 130 ℃, performing vacuum dehydration reaction for 2.5 hours, cooling to 68 ℃, adding a certain amount of methyl ethyl ketone (the dosage is 12 times of the total weight of the dimethylolpropionic acid and the castor oil) for dissolving, adding a certain amount of n-hexane (the dosage is 13 times of the total weight of the dimethylolpropionic acid and the castor oil) into the reaction kettle, placing the reaction kettle at 10 ℃ to crystallize and precipitate a product, and performing vacuum drying to obtain the hyperbranched hydroxyl resin;
(2) dripping a mixture of p-phenylene diisocyanate (the dosage is 12 times of the molar weight of castor oil) and dibutyltin dilaurate (the dosage is 0.12 percent of the weight of the hyperbranched hydroxyl resin) into the hyperbranched hydroxyl resin prepared in the step (1) in a constant-temperature water bath at the temperature of 20 ℃, adjusting the dripping speed to be controlled to be 1.5h, heating to 65 ℃, stirring and reacting for 2.8h to obtain an intermediate product;
(3) dissolving all the intermediate products obtained in the step (2) by using acetone (the dosage is 25% of the weight of the intermediate product prepared in the step (2)), dropwise adding polyethylene glycol acrylate with the molecular weight of 800 (the dosage is 12.5 times of the molar weight of castor oil, and the dropwise adding speed is 12mL/min) and hydroquinone (the dosage is 0.3% of the weight of the polyethylene glycol acrylate), controlling the temperature to be 75 ℃, reacting for 2.3h, and performing rotary evaporation to remove the solvent to obtain the hyperbranched castor oil based aqueous UV curing prepolymer.
Example 4
(1) Sequentially adding metered dimethylolpropionic acid, castor oil (the molar ratio of the castor oil to the dimethylolpropionic acid is 1:9) and p-toluenesulfonic acid (the dosage is 2.5 percent of the molar quantity of the dimethylolpropionic acid), stirring, heating to 140 ℃, performing vacuum dehydration reaction for 2.0h, then cooling to 73 ℃, adding a certain amount of methylisopropyl ketone (the dosage is 15 times of the total mass of the dimethylolpropionic acid and the castor oil) for dissolving, then placing the mixture at 12 ℃, adding a certain amount of heptane (the dosage is 12 times of the total mass of the dimethylolpropionic acid and the castor oil) to crystallize and precipitate a product, and performing vacuum drying to obtain the hyperbranched hydroxyl resin;
(2) dripping a mixture of xylylene diisocyanate (the dosage is 12 times of the molar weight of castor oil) and dibutyltin dilaurate (the dosage is 0.13 percent of the weight of the hyperbranched hydroxyl resin) into the hyperbranched hydroxyl resin prepared in the step (1) in a constant-temperature water bath at 23 ℃, adjusting the dripping speed to be controlled to be 1.8h, heating to 73 ℃, stirring and reacting for 2.4h to obtain an intermediate product;
(3) dissolving all the intermediate products obtained in the step (2) by using tetrahydrofuran (the dosage is 35% of the weight of the intermediate product prepared in the step (2)), dropwise adding polyethylene glycol acrylate with the molecular weight of 1000 (the dosage is 12 times of the molar quantity of castor oil, and the dropwise adding speed is 1mL/min) and p-hydroxyanisole (the dosage is 0.2% of the weight of the polyethylene glycol acrylate), controlling the temperature to be 73 ℃, reacting for 1.6h, and rotationally evaporating to remove the solvent to obtain the hyperbranched castor oil based aqueous UV curing prepolymer.
Example 5
(1) Sequentially adding metered dimethylolpropionic acid, castor oil (the molar ratio of the castor oil to the dimethylolpropionic acid is 1:9) and tetrabutyl titanate (the dosage is 1.8 percent of the molar quantity of the dimethylolpropionic acid), stirring, heating to 125 ℃, performing vacuum dehydration reaction for 3.0h, then cooling to 66 ℃, adding a certain amount of cyclohexanone (the dosage is 12 times of the total mass of the dimethylolpropionic acid and the castor oil) for dissolution, then placing the mixture at 8 ℃, adding a certain amount of 2-methylhexane (the dosage is 15 times of the total mass of the dimethylolpropionic acid and the castor oil) to crystallize, precipitate and separate out a product, and performing vacuum drying to obtain the hyperbranched hydroxyl resin;
(2) dripping a mixture of dicyclohexyl hexane diisocyanate (the dosage is 12 times of the molar weight of castor oil) and dibutyltin dilaurate (the dosage is 0.14 percent of the weight of the hyperbranched hydroxyl resin) into the hyperbranched hydroxyl resin prepared in the step (1) in a constant-temperature water bath at 18 ℃, adjusting the dripping speed to be controlled to be 1.7h, heating to 69 ℃, stirring and reacting for 2.5h to obtain an intermediate product;
(3) dissolving all the intermediate products obtained in the step (2) with butanone (the dosage is 15% of the weight of the intermediate products prepared in the step (2)), dropwise adding polyethylene glycol acrylate with the molecular weight of 60 (the dosage is 12.6 times of the molar amount of castor oil, and the dropwise adding speed is 5mL/min) and p-hydroxyanisole (the dosage is 0.1% of the weight of the polyethylene glycol acrylate), controlling the temperature at 74 ℃ for reaction for 1.6h, and then rotationally evaporating to remove the solvent to obtain the hyperbranched castor oil based aqueous UV curing prepolymer.
Example 6
(1) Sequentially adding metered dimethylolpropionic acid, castor oil (the molar ratio of the castor oil to the dimethylolpropionic acid is 1:9) and p-toluenesulfonic acid (the dosage is 2.4 percent of the molar quantity of the dimethylolpropionic acid), stirring, heating to 145 ℃, performing vacuum dehydration reaction for 2.0h, then cooling to 70 ℃, adding a certain amount of cyclohexanone (the dosage is 14 times of the total mass of the dimethylolpropionic acid and the castor oil) for dissolving, then placing at 10 ℃, adding a certain amount of cyclohexane (the dosage is 12 times of the total mass of the dimethylolpropionic acid and the castor oil) to crystallize, precipitate and separate out a product, and performing vacuum drying to obtain the hyperbranched hydroxyl resin;
(2) dripping a mixture of toluene diisocyanate (the dosage is 12 times of the molar weight of castor oil) and dibutyltin dilaurate (the dosage is 0.10 percent of the weight of the hyperbranched hydroxyl resin) into the hyperbranched hydroxyl resin prepared in the step (1) in a constant-temperature water bath at 18 ℃, adjusting the dripping speed to be controlled to be 1.8h, heating to 58 ℃, stirring and reacting for 3.0h to obtain an intermediate product;
(3) dissolving all the intermediate products obtained in the step (2) by using tetrahydrofuran (the dosage is 35% of the weight of the intermediate products prepared in the step (2)), dropwise adding polyethylene glycol acrylate with the molecular weight of 800 (the dosage is 13 times of the molar quantity of castor oil, and the dropwise adding speed is 7mL/min) and p-hydroxyanisole (the dosage is 0.5% of the polyethylene glycol acrylate), controlling the temperature to be 62 ℃, reacting for 2.4h, and then performing rotary evaporation to remove the solvent to obtain the hyperbranched castor oil based aqueous UV curing prepolymer.
Comprehensive performance test of products of various embodiments
Respectively adding 200g of hyperbranched castor oil based water-based UV curing prepolymer prepared in each example into 10g of water-based photoinitiator (the water-based photoinitiator is Irgacure 2959 of Cuba, Switzerland (CIBA) Fine chemical Co., Ltd.) with the same amount and the same kind, adding 200g of deionized water, dispersing at a high speed of 1500r/min for 10min by using a disc disperser to prepare a water-based UV curing coating, coating the coating on a tinplate by using a coating machine, and forming a UV curing film by comparing the storage stability of the water-based UV curing coating and various performances of the curing film.
Storage stability test of the aqueous UV-curable coating was carried out according to method of test method for storage stability of coating (GB/T6753.3-1986). Adhesion test the adhesion test was performed according to the method of the scratch test for paint, varnish and lacquer film (GB/T9286-1998). Hardness test the hardness test was carried out according to the method of determination of paint film hardness by the colored paint and varnish pencil method (GB/T6739-2006). Water resistance is characterized by water absorption and is tested according to the method of paint film water resistance determination (GB/T1733-1993).
Mechanical properties analysis the cured film was tested using an AGS-X1 kN universal tester manufactured by Shimadzu corporation, japan, crosshead speed: 10 mm/min; sample size: 40 mm. times.10 mm. times.0.5 mm. The measured tensile strength and elongation at break of the cured film are shown in Table 1.
The abrasion resistance of the coating film is tested according to the method of national standard GB/T1768 and 2006 "method for measuring abrasion resistance of colored paint and varnish by rotating rubber grinding wheel method". The test method is that a rubber grinding wheel fixed on a wear tester is used for rubbing the dry paint film, the wear resistance is expressed by the mass loss of the paint film after a specified number of rubbing cycles, and generally, the smaller the mass loss is, the better the wear resistance of the paint film is. Sample size: 40 mm. times.10 mm. times.0.5 mm.
TABLE 1 results of comprehensive Properties test of examples
As can be seen from the data in Table 1, the hyperbranched castor oil-based waterborne UV-curable prepolymer prepared by the invention has excellent hydrophilic property, so that the waterborne UV-curable coating prepared by the hyperbranched castor oil-based waterborne UV-curable prepolymer has good storage stability and is unchanged after being stored for six months. The hyperbranched castor oil-based aqueous UV curing prepolymer prepared by the invention has very high functionality and extremely high crosslinking degree during curing film forming, so that the obtained dry film has the advantages of high hardness, high tensile strength, low water absorption, good adhesive force, good wear resistance and the like.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of hyperbranched castor oil based water-based UV curing prepolymer is characterized by comprising the following steps:
(1) adding dimethylolpropionic acid, castor oil and an esterification catalyst into a reaction kettle, stirring, heating to 120-150 ℃, performing vacuum dehydration reaction for 2-3 hours, then cooling to 65-75 ℃, adding a solvent for dissolution, then adding a separating agent into the reaction kettle at 5-15 ℃ to crystallize, precipitate and separate a product, and performing vacuum drying to obtain the hyperbranched hydroxyl resin; the molar ratio of the castor oil to the dimethylolpropionic acid is 1: 9;
(2) dripping a mixture of diisocyanate and a catalyst into the hyperbranched hydroxyl resin prepared in the step (1) at 15-25 ℃, adjusting the dripping speed to be controlled within 1-2 h, heating to 50-80 ℃, stirring and reacting for 2-3 h to obtain an intermediate product; the diisocyanate is aromatic and/or aliphatic isocyanate; the molar ratio of the initial castor oil to the diisocyanate is 1: 12;
(3) dissolving all the intermediate products obtained in the step (2) by using a solvent, dropwise adding polyethylene glycol acrylate and a polymerization inhibitor, controlling the temperature to be 60-78 ℃, reacting for 1.5-2.5 h, and performing rotary evaporation to remove the solvent to obtain a hyperbranched castor oil-based aqueous UV curing prepolymer; the polyethylene glycol acrylate is liquid, and the number average molecular weight of the polyethylene glycol acrylate is 600-1000; the usage amount of the castor oil is 12-13 times of the molar amount of the castor oil used in the step (1) in terms of molar parts.
2. The preparation method of the hyperbranched castor oil-based aqueous UV-curable prepolymer according to claim 1, wherein in the step (1), the amount of the esterification catalyst is 1-3% of the molar amount of dimethylolpropionic acid.
3. The preparation method of the hyperbranched castor oil-based aqueous UV-curable prepolymer according to claim 1, wherein in the step (1): the solvent is at least one of acetone, methyl ethyl ketone, methyl isopropyl ketone and cyclohexanone, and the dosage of the solvent is 10-15 times of the total mass of dimethylolpropionic acid and castor oil; the precipitating agent is at least one of cyclohexane, n-hexane, heptane, 2-methylhexane and octane, and the dosage of the precipitating agent is 10-15 times of the total mass of the dimethylolpropionic acid and the castor oil; the esterification catalyst is at least one of N, N' -diisopropylcarbodiimide, dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, p-toluenesulfonic acid and tetrabutyl titanate.
4. The method for preparing a hyperbranched castor oil-based aqueous UV-curable prepolymer as claimed in claim 1, wherein the diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, and dicyclohexyl hexane diisocyanate.
5. The method for preparing the hyperbranched castor oil-based aqueous UV-curable prepolymer as claimed in claim 1, wherein the catalyst in step (2) is dibutyltin dilaurate, and the catalyst is 0.1-0.15 parts by weight based on 100 parts by weight of the hyperbranched hydroxyl resin.
6. The method for preparing hyperbranched castor oil-based aqueous UV-curable prepolymer according to claim 1, wherein the solvent in step (3) is at least one of acetone, butanone and tetrahydrofuran; 10-50 parts by weight of the solvent based on 100 parts by weight of the intermediate product prepared in the step (2);
the polymerization inhibitor in the step (3) is p-hydroxyanisole or/and hydroquinone; the polymerization inhibitor is 0.1-0.5 part by weight based on 100 parts by weight of polyethylene glycol acrylate.
7. The preparation method of the hyperbranched castor oil-based aqueous UV curing prepolymer as claimed in claim 1, wherein the dropping speed of the solution in steps (2) and (3) is 1-15 mL/min.
8. A hyperbranched castor oil based aqueous UV curable prepolymer made by the method of any one of claims 1 to 7.
9. Use of the hyperbranched castor oil-based aqueous UV curable prepolymer of claim 8 in the field of coatings and inks.
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| CN112048077B (en) * | 2020-08-31 | 2022-02-01 | 华南农业大学 | Castor oil-based aqueous photocuring nonionic emulsion and preparation method and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397719A (en) * | 2016-10-09 | 2017-02-15 | 华南农业大学 | Castor-oil-based hyperbranched UV curable polyurethane acrylate and preparation method and application thereof |
| CN106854432A (en) * | 2015-12-09 | 2017-06-16 | 万华化学集团股份有限公司 | A kind of radiation solidified aqueous coating resin and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106854432A (en) * | 2015-12-09 | 2017-06-16 | 万华化学集团股份有限公司 | A kind of radiation solidified aqueous coating resin and preparation method thereof |
| CN106397719A (en) * | 2016-10-09 | 2017-02-15 | 华南农业大学 | Castor-oil-based hyperbranched UV curable polyurethane acrylate and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高固含量 UV 固化水性PUA 的制备及性能;李菁熠等;《精细化工》;20080930;第35卷(第9期);1615-1620页 * |
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