CN115449019A - Photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion and preparation method and application thereof - Google Patents
Photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
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Abstract
The invention discloses a photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion and a preparation method and application thereof.A dihydroxyl coumarin with photoresponse is introduced into aqueous polyurethane, the end of the dihydroxyl coumarin is capped by hydroxyl acrylate, then the polyurethane is combined with a fluorine-containing acrylate monomer and an acrylate monomer, modified nanocellulose is used as a Pickering stabilizer, and the photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion is prepared by a Pickering emulsion polymerization method; the invention eliminates the influence of the traditional surfactant on the performance of products, is beneficial to improving the water and oil repellency of polymers, improves the compatibility of polyurethane and polyacrylate by using hydroxyl acrylate as a chemical connecting bridge, and endows the coumarin group with the photoresponse self-repairing performance of polyurethane acrylate.
Description
Technical Field
The invention belongs to the technical field of functional materials, relates to a high polymer material, and particularly relates to a photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion as well as a preparation method and application thereof.
Background
The Polyacrylate (PA) has good mechanical property, light resistance, weather resistance and acid and alkali corrosion resistance, is rich in raw materials, low in price and simple in synthesis process, and meanwhile, a polymer coating film has good toughness and strong aging resistance, so that the PA is widely applied to the fields of leather finishing, building coatings, woods, adhesives and the like. Polyurethane (PU) has the advantages of excellent strength, flexibility, wear resistance, chemical corrosion resistance and the like, and in recent years, with the increasing perfection of environmental regulations and laws, people are increasingly conscious of the environment, and the development of a low-toxicity, environment-friendly and energy-saving Waterborne Polyurethane (WPU) material becomes a research hotspot. The polyurethane acrylate (WPUA) obtained by combining the waterborne polyurethane and the polyacrylate can meet the application requirement of high performance, is used for the aspects of textile treatment, biomedicine and the like, and has extremely high economic value. However, WPUA is poor in hydrophobicity and thermal stability due to the presence of a hydrophilic group, and therefore, the water and oil repellency is improved by modifying the WPUA with a fluorine-containing polymer.
Pickering emulsion polymerization is an emulsion polymerization mode for stabilizing an oil-water interface by using solid particles, has the advantages of low toxicity or no toxicity, low cost, no pollution, green environmental protection and the like compared with the traditional emulsion polymerization, and is widely used for preparing composite materials with special structures and functions. The fluorine-containing polyurethane acrylate emulsion is prepared by taking the nanocellulose as a Pickering stabilizer through a Pickering emulsion polymerization method, so that the adverse effect of a small molecular emulsifier on the performances of the emulsion and the film can be solved, the rough structure of the emulsion can be combined with low surface energy, and the water and oil repellency of the fluorine-containing polymer film can be improved.
The self-repairing material can repair the internal damage generated in the forming processing and using processes, thereby eliminating the hidden danger caused by material damage to a certain extent and realizing the recycling of the material. Photoresponsive self-repair is a repair that uses light as a stimulus to change the structure of a polymer. The coumarin is a photosensitive group with wide application, can generate reversible photocrosslinking and photocleavage reaction under the condition of ultraviolet illumination, and can endow the coumarin with photoresponse self-repairing performance by introducing the coumarin into a polymer material. In the past years, photoresponsive self-repairing has been applied to various polymer systems, however, the photoresponsive self-repairing performance of polyurethane acrylate has not been researched at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion, and the preparation method and the application thereof, and the photoresponse self-repairing performance of the polyurethane acrylate is endowed.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion comprises the following steps:
step 1, weighing 5-15% of polyisocyanate, 15-30% of polyol, 1-5% of micromolecule chain extender containing hydrophilic group, 1-5% of bishydroxycoumarin, 0.2-3% of micromolecule chain extender, 1-4% of hydroxy acrylate, 0.5-2% of triethylamine and 50-70% of deionized water according to mass fraction;
step 2, mixing the polyisocyanate, the polyol, the hydrophilic group-containing micromolecule chain extender, the bishydroxycoumarin and the micromolecule chain extender weighed in the step 1, and stirring at the temperature of 50-90 ℃ for 2-7 hours to obtain a prepolymer containing a terminal isocyanate group;
step 3, adding hydroxyl acrylic ester into the prepolymer containing the end isocyanate group obtained in the step 2, and stirring for 1-5 hours at the temperature of 40-80 ℃ to obtain a double-bond end-capped polyurethane prepolymer;
step 4, adding triethylamine into the double-bond-terminated polyurethane prepolymer obtained in the step 3, stirring for 0.5-1.5 h at the temperature of 20-40 ℃, adding deionized water, and stirring for 1-3 h at the temperature of 15-30 ℃ to obtain double-bond-terminated waterborne polyurethane emulsion;
step 5, amphiphilic block modified nano-cellulose powder and deionized water are weighed according to the mass ratio of 4-12: 1400-2800, and modified nano-cellulose dispersion liquid is formed under the action of an ultrasonic cell crusher;
weighing two acrylate monomers and fluorine-containing acrylate monomers according to the mass ratio of 27-72: 18-63: 2-15, weighing modified nano-cellulose dispersion liquid according to the mass ratio of the total monomers to the modified nano-cellulose dispersion liquid of 10-30: 40-60, and mechanically stirring and mixing at high speed to obtain pre-emulsion;
weighing initiator and deionized water according to the mass ratio of 7: 300-450, and uniformly mixing to obtain initiator aqueous solution;
and 6, under the condition of argon protection, adding the double-bond end-capped aqueous polyurethane emulsion prepared in the step 4 and the pre-emulsion prepared in the step 5 into a reactor according to the mass ratio of 3-20: 20-35, heating to 70-85 ℃, dropwise adding an initiator aqueous solution within 60-120 min under mechanical stirring, wherein the initiator aqueous solution accounts for 0.8-1.5% of the total monomer mass, keeping the temperature and stirring at 80-90 ℃ for 60-120 min, and finally discharging cold water to obtain the fluorine-containing polyurethane acrylate emulsion.
The invention also has the following technical characteristics:
preferably, the polyisocyanate comprises toluene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
Preferably, the polyol comprises a polyether polyol or a polyester polyol.
Preferably, the small molecule chain extender containing hydrophilic groups comprises dimethylolpropionic acid, dimethylolbutyric acid, ethyldihydroxyethanesulfonate or ethylenediamine ethanesulfonate.
Preferably, the small-molecule chain extender comprises 1, 4-butanediol, glycerol, dimethylolpropane or glycol amine.
Preferably, the hydroxy acrylate comprises hydroxyethyl acrylate or hydroxyethyl methacrylate.
Preferably, the acrylate monomer in step 5 comprises methyl acrylate, methyl methacrylate, butyl methacrylate or butyl acrylate;
the fluorine-containing acrylate monomer comprises hexafluorobutyl methacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate or dodecafluoroheptyl acrylate;
the initiator comprises potassium persulfate or ammonium persulfate.
Preferably, the power of the ultrasonic cell crusher in the step 5 is 15-35%, and the dispersion time is 5-15 min; mechanically stirring for 30-60 min.
The invention also discloses the photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion prepared by the method and the application of the photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion as a leather finishing agent.
Compared with the prior art, the invention has the following technical effects:
the amphiphilic block copolymer modified nanocellulose is used as the Pickering emulsifier to replace a micromolecular emulsifier, so that the influence of the traditional surfactant on the performance of the product is eliminated, the modified nanocellulose is combined with the fluorine-containing polymer, and the coarse structure constructed by the nanocellulose is combined with the low surface energy of the fluorine-containing polymer, so that the water and oil repellency of the polymer is improved;
according to the invention, the polyurethane containing double bonds is obtained by capping the polyurethane with the hydroxy acrylate, the hydroxy acrylate is used as a chemical connection bridge to improve the compatibility of the polyurethane and the polyacrylate, and the coumarin group can perform reversible photocracking and photodimerization reactions under the irradiation of 254nm and 365nm ultraviolet light to heal scratches, so that the polyurethane acrylate has a photoresponse self-repairing property, and a new thought is provided for the intelligent application of the polyurethane acrylate emulsion;
the photoresponse type self-repairing polyurethane acrylate prepared by the invention is used as a leather finishing agent, and can endow the leather with good water-repellent oil-repellent and self-repairing performances.
Drawings
FIG. 1 is a DLS test result chart of a photoresponse type self-repairing polyurethane acrylate composite emulsion prepared by the invention;
FIG. 2 is a comparative graph of self-repairing effects of photo-responsive self-repairing urethane acrylate coating films prepared by the invention.
Detailed Description
The present invention will be explained in further detail with reference to examples.
Example 1
Step 1, weighing 6.0% of isophorone diisocyanate, 19.0% of polyester polyol, 1.4% of dimethylolpropionic acid, 1.0% of bishydroxycoumarin, 0.3% of 1, 4-butanediol, 1.4% of hydroxyethyl methacrylate, 0.9% of triethylamine and 70.0% of deionized water according to mass fraction;
step 2, mixing and stirring the polyester polyol, the dimethylolpropionic acid, the isophorone diisocyanate, the bishydroxycoumarin and the 1, 4-butanediol weighed in the step 1 at 85 ℃ for 5 hours to obtain a prepolymer containing a terminal isocyanate group;
step 3, adding the weighed hydroxyethyl methacrylate into the prepolymer containing the terminal isocyanate group obtained in the step 2, and stirring at 55 ℃ for 2.5 hours to obtain a double-bond-terminated polyurethane prepolymer;
step 4, adding the weighed triethylamine into the double-bond-terminated polyurethane prepolymer obtained in the step 3, stirring for 1 hour at 30 ℃, adding the weighed deionized water, and stirring for 1 hour at 20 ℃ to obtain double-bond-terminated waterborne polyurethane emulsion;
step 5, respectively weighing amphiphilic block modified nano cellulose powder and deionized water according to the mass ratio of 1: 250, and dispersing for 15min by using an ultrasonic cell crusher with the power of 15% to form dispersion liquid; respectively weighing butyl acrylate, methyl methacrylate and hexafluorobutyl acrylate according to the mass ratio of 3: 2: 1, and mechanically stirring with the nano-cellulose dispersion liquid at the speed of 1000r/min for 60min to obtain a pre-emulsion;
respectively weighing potassium persulfate and deionized water according to the mass ratio of 1: 50, and uniformly mixing to obtain an initiator aqueous solution;
and 6, under the condition of argon protection, adding the double-bond-terminated aqueous polyurethane emulsion prepared in the step 4 and the pre-emulsion prepared in the step 5 into a reactor according to the mass ratio of 1: 3, heating to 80 ℃, dropwise adding an initiator aqueous solution within 100min under mechanical stirring, wherein the initiator aqueous solution accounts for 1.2% of the total monomer mass, keeping the temperature and stirring for 90min at 85 ℃, and finally discharging cold water to obtain the fluorine-containing polyurethane acrylate emulsion.
The particle size of the photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion prepared in example 1 was tested, and the DLS test result is shown in FIG. 1, wherein the particle size is 130.2nm, the particle size distribution index is 0.063, the particle size is small and the distribution is uniform, and the emulsion stability is good.
The photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion prepared in the example 1 is scratched by a scalpel, then the surface scratches are observed by using a microscope with super depth of field, the self-repairing effect is shown in a comparison graph of a figure 2, most scratches on the surface of the coating disappear after being irradiated by ultraviolet light of 254nm and 365nm, and the photoresponse type self-repairing fluorine-containing polyurethane acrylate prepared by the invention has the photoresponse self-repairing performance.
Example 2
Step 1, weighing 22.0% of polyether polyol, 1.5% of dimethylolbutyric acid, 13.0% of hexamethylene diisocyanate, 2.0% of bishydroxycoumarin, 1.0% of 1, 4-butanediol, 4.0% of hydroxyethyl acrylate, 1.5% of triethylamine and 55.0% of deionized water according to mass fraction;
step 2, mixing and stirring the polyether polyol, the dimethylolbutyric acid, the hexamethylene diisocyanate, the bishydroxycoumarin and the 1, 4-butanediol weighed in the step 1 at 70 ℃ for 6 hours to obtain a prepolymer containing a terminal isocyanate group;
step 3, adding the weighed hydroxyethyl acrylate into the prepolymer containing the terminal isocyanate group obtained in the step 2, and stirring at 70 ℃ for 1.5 hours to obtain a double-bond-terminated polyurethane prepolymer;
step 4, adding the weighed triethylamine into the double-bond-terminated polyurethane prepolymer obtained in the step 3, stirring for 0.5h at 40 ℃, adding deionized water, and stirring for 1.5h at 30 ℃ to obtain double-bond-terminated waterborne polyurethane emulsion;
and 5, preparing the raw materials in a mass ratio of 3:675, respectively weighing modified nano cellulose powder and deionized water, and dispersing for 10min by using an ultrasonic cell crusher with the power of 25% to form dispersion liquid; respectively weighing butyl acrylate, methyl methacrylate and hexafluorobutyl acrylate according to the mass ratio of 3.6: 2.4: 1, and mechanically stirring with the nano-cellulose dispersion liquid at the speed of 1200r/min for 40min to obtain a pre-emulsion;
respectively weighing potassium persulfate and deionized water according to the mass ratio of 1: 60, and uniformly mixing to obtain an initiator aqueous solution;
and step 6, under the condition of argon protection, adding the double-bond-terminated aqueous polyurethane emulsion prepared in the step 4 and the pre-emulsion prepared in the step 5 into a reactor according to the mass ratio of 3:35, heating to 80 ℃, dropwise adding an initiator aqueous solution within 80min under mechanical stirring, wherein the mass of the potassium persulfate aqueous solution is 1.0% of the mass of the mixed monomer, keeping the temperature and stirring for 100min at 85 ℃, and finally discharging cold water to obtain the fluorine-containing polyurethane acrylate emulsion.
Example 3
Step 1, weighing 16.0% of polyether polyol, 1.3% of dimethylolbutyric acid, 7.6% of toluene diisocyanate, 1.0% of bishydroxycoumarin, 0.5% of ethylene glycol amine, 2.5% of hydroxyethyl methacrylate, 1.1% of triethylamine and 70.0% of deionized water according to mass fraction;
step 2, mixing and stirring the polyether polyol, the dimethylolbutyric acid, the isophorone diisocyanate, the bishydroxycoumarin crosslinked by 365nm ultraviolet light for 10min and the glycol amine weighed in the step 1 at 65 ℃ for 7h to obtain a prepolymer containing a terminal isocyanate group;
step 3, adding the weighed hydroxyethyl methacrylate into the prepolymer containing the terminal isocyanate group obtained in the step 2, and stirring for 2 hours at 60 ℃ to obtain a double-bond-terminated polyurethane prepolymer;
step 4, adding the weighed triethylamine into the double-bond-terminated polyurethane prepolymer obtained in the step 3, stirring for 0.5min at 40 ℃, adding deionized water, and stirring for 1.5h at 20 ℃ to obtain double-bond-terminated waterborne polyurethane emulsion;
step 5, mixing the raw materials in a mass ratio of 1:550, respectively weighing modified nano cellulose powder and deionized water, and dispersing for 5min by using an ultrasonic cell crusher with power of 35% to form dispersion liquid; respectively weighing butyl acrylate, methyl methacrylate and hexafluorobutyl acrylate according to the mass ratio of 2.4: 1.6: 1, and mechanically stirring with the nano-cellulose dispersion liquid at the speed of 1500r/min for 30min to obtain pre-emulsion;
respectively weighing potassium persulfate and deionized water according to the mass ratio of 7: 300, and uniformly mixing to obtain an initiator aqueous solution;
and step 6, under the condition of argon protection, adding the double-bond-terminated aqueous polyurethane emulsion prepared in the step 4 and the pre-emulsion prepared in the step 5 into a reactor according to the mass ratio of 1: 1, heating to 80 ℃, dropwise adding an initiator aqueous solution within 60min at a mechanical stirring speed, wherein the mass of a potassium persulfate solution is 1.4% of the mass of the mixed monomers, keeping the temperature and stirring for 60min at 85 ℃, and finally discharging in cold water to obtain the fluorine-containing polyurethane acrylate emulsion.
Example 4
Step 1, weighing 30% of polyether polyol, 5% of ethylenediamine ethanesulfonate, 5% of toluene diisocyanate, 5% of bishydroxycoumarin, 0.2% of dimethylolpropane, 4% of hydroxyethyl methacrylate, 0.5% of triethylamine and 50.3% of deionized water according to mass fraction;
step 2, mixing and stirring the polyether polyol, the ethylenediamine ethanesulfonate, the toluene diisocyanate, the bishydroxycoumarin which is crosslinked for 10min by 365nm ultraviolet light and the dimethylolpropane which are weighed in the step 1 at 50 ℃ for 6h to obtain a prepolymer containing terminal isocyanate groups;
step 3, adding the weighed hydroxyethyl methacrylate into the prepolymer containing the terminal isocyanate group obtained in the step 2, and stirring at 40 ℃ for 5 hours to obtain a double-bond-terminated polyurethane prepolymer;
step 4, adding the weighed triethylamine into the double-bond-terminated polyurethane prepolymer obtained in the step 3, stirring for 1.5min at 20 ℃, adding deionized water, and stirring for 3h at 15 ℃ to obtain double-bond-terminated waterborne polyurethane emulsion;
step 5, mixing the raw materials in a mass ratio of 1:700, respectively weighing modified nano cellulose powder and deionized water, and dispersing for 5min by using an ultrasonic cell crusher with the power of 35% to form dispersion liquid; respectively weighing methyl acrylate, butyl methacrylate and dodecafluoroheptyl methacrylate according to the mass ratio of 27: 18: 2, and mechanically stirring with the nano-cellulose dispersion liquid at the speed of 1500r/min for 50min to obtain pre-emulsion;
respectively weighing potassium persulfate and deionized water according to the mass ratio of 7: 450, and uniformly mixing to obtain an initiator aqueous solution;
and step 6, under the protection of argon, adding the double-bond-terminated aqueous polyurethane emulsion prepared in the step 4 and the pre-emulsion prepared in the step 5 into a reactor according to the mass ratio of 20: 35, heating to 70 ℃, dropwise adding an initiator aqueous solution within 80min at a mechanical stirring speed, wherein the mass of the potassium persulfate solution is 0.8% of the mass of the mixed monomers, keeping the temperature and stirring for 80min at 80 ℃, and finally discharging in cold water to obtain the fluorine-containing polyurethane acrylate emulsion.
Example 5
Step 1, weighing 15% of polyether polyol, 1% of ethylene dihydroxy ethanesulfonate, 15% of toluene diisocyanate, 3% of bishydroxycoumarin, 3% of glycerol, 1% of hydroxyethyl methacrylate, 2% of triethylamine and 61% of deionized water according to mass fraction;
step 2, mixing and stirring the polyether polyol, the ethyldihydroxy ethanesulfonate, the toluene diisocyanate, the bishydroxycoumarin which is crosslinked for 10min by 365nm ultraviolet light and the glycerol which are weighed in the step 1 at 90 ℃ for 2h to obtain a prepolymer containing terminal isocyanate groups;
step 3, adding the weighed hydroxyethyl methacrylate into the prepolymer containing the terminal isocyanate group obtained in the step 2, and stirring at 80 ℃ for 1h to obtain a double-bond-terminated polyurethane prepolymer;
step 4, adding the weighed triethylamine into the double-bond-terminated polyurethane prepolymer obtained in the step 3, stirring for 1min at 35 ℃, adding deionized water, and stirring for 1h at 30 ℃ to obtain double-bond-terminated waterborne polyurethane emulsion;
step 5, according to the mass ratio of 3:350 respectively weighing modified nano cellulose powder and deionized water, and dispersing for 5min by using an ultrasonic cell crusher with power of 35% to form dispersion liquid; weighing methyl acrylate, butyl methacrylate and dodecafluoroheptyl acrylate according to the mass ratio of 72: 63: 15, and mechanically stirring with the nano-cellulose dispersion liquid at the speed of 1500r/min for 50min to obtain pre-emulsion;
respectively weighing potassium persulfate and deionized water according to the mass ratio of 7: 400, and uniformly mixing to obtain an initiator aqueous solution;
and 6, under the condition of argon protection, adding the double-bond-terminated aqueous polyurethane emulsion prepared in the step 4 and the pre-emulsion prepared in the step 5 into a reactor according to the mass ratio of 3: 20, heating to 85 ℃, dropwise adding an initiator aqueous solution within 120min at a mechanical stirring speed, wherein the mass of the potassium persulfate solution is 1.5% of the mass of the mixed monomer, keeping the temperature and stirring for 120min at 90 ℃, and finally discharging in cold water to obtain the fluorine-containing polyurethane acrylate emulsion.
Other embodiments are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention.
Claims (10)
1. The preparation method of the photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion is characterized by comprising the following steps of:
step 1, weighing 5-15% of polyisocyanate, 15-30% of polyol, 1-5% of micromolecule chain extender containing hydrophilic group, 1-5% of bishydroxycoumarin, 0.2-3% of micromolecule chain extender, 1-4% of hydroxyl acrylate, 0.5-2% of triethylamine and 50-70% of deionized water according to mass fraction;
step 2, mixing the polyisocyanate, the polyol, the hydrophilic group-containing micromolecule chain extender, the bishydroxycoumarin and the micromolecule chain extender weighed in the step 1, and stirring at the temperature of 50-90 ℃ for 2-7 hours to obtain a prepolymer containing a terminal isocyanate group;
step 3, adding hydroxyl acrylate into the prepolymer containing the terminal isocyanate group obtained in the step 2, and stirring at the temperature of 40-80 ℃ for 1-5 h to obtain a double-bond-terminated polyurethane prepolymer;
step 4, adding triethylamine into the double-bond end-capped polyurethane prepolymer obtained in the step 3, stirring for 0.5-1.5 h at the temperature of 20-40 ℃, adding deionized water, and stirring for 1-3 h at the temperature of 15-30 ℃ to obtain double-bond end-capped aqueous polyurethane emulsion;
step 5, amphiphilic block modified nano-cellulose powder and deionized water are weighed according to the mass ratio of 4-12: 1400-2800, and modified nano-cellulose dispersion liquid is formed under the action of an ultrasonic cell crusher;
weighing two acrylate monomers and fluorine-containing acrylate monomers according to the mass ratio of 27-72: 18-63: 2-15, weighing modified nano-cellulose dispersion liquid according to the mass ratio of the total monomers to the modified nano-cellulose dispersion liquid of 10-30: 40-60, and mechanically stirring and mixing at a high speed to obtain pre-emulsion;
weighing initiator and deionized water according to the mass ratio of 7: 300-450, and uniformly mixing to obtain initiator aqueous solution;
and step 6, under the protection of argon, adding the double-bond-terminated aqueous polyurethane emulsion prepared in the step 4 and the pre-emulsion prepared in the step 5 into a reactor according to the mass ratio of 3-20: 20-35, heating to 70-85 ℃, dropwise adding an initiator aqueous solution within 60-120 min under mechanical stirring, wherein the initiator aqueous solution accounts for 0.8-1.5% of the total monomer mass, keeping the temperature and stirring at 80-90 ℃ for 60-120 min, and finally discharging cold water to obtain the fluorine-containing polyurethane acrylate emulsion.
2. The method for preparing the photo-responsive self-repairing fluorine-containing polyurethane acrylate composite emulsion of claim 1, wherein the polyisocyanate comprises toluene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
3. The method of claim 1, wherein the polyol comprises a polyether polyol or a polyester polyol.
4. The method for preparing the photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion as claimed in claim 1, wherein the small molecule chain extender containing a hydrophilic group comprises dimethylolpropionic acid, dimethylolbutyric acid, ethyldihydroxyethanesulfonate or ethylenediamine ethanesulfonate.
5. The method for preparing a photoresponsive self-repairing fluorine-containing polyurethane acrylate composite emulsion according to claim 1, wherein the small molecule chain extender comprises 1, 4-butanediol, glycerol, dimethylolpropane or glycol amine.
6. The method of claim 1, wherein the hydroxy acrylate comprises hydroxyethyl acrylate or hydroxyethyl methacrylate.
7. The method for preparing the photo-responsive self-repairing fluorine-containing polyurethane acrylate composite emulsion of claim 1, wherein the acrylate monomer of step 5 comprises methyl acrylate, methyl methacrylate, butyl methacrylate or butyl acrylate;
the fluorine-containing acrylate monomer comprises hexafluorobutyl methacrylate, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate or dodecafluoroheptyl acrylate;
the initiator comprises potassium persulfate or ammonium persulfate.
8. The method for preparing the photoresponse type self-repairing fluorine-containing polyurethane acrylate composite emulsion according to claim 1, wherein the power of the ultrasonic cell crusher in the step 5 is 15-35%, and the dispersion time is 5-15 min; the high-speed mechanical stirring is carried out for 30-60 min at the rotating speed of 1000-1500 r/min.
9. A photo-responsive self-repairing fluorine-containing polyurethane acrylate composite emulsion prepared by the method of any one of claims 1-8.
10. Use of the photo-responsive self-healing fluorinated polyurethane acrylate composite emulsion according to claim 9 as a leather finishing agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116333235A (en) * | 2023-04-10 | 2023-06-27 | 深圳永昌和科技有限公司 | Photo-curing acrylic resin material for 3D printing and preparation method thereof |
| CN116574448A (en) * | 2023-04-07 | 2023-08-11 | 中国林业科学研究院林产化学工业研究所 | Plant oil-based self-repairing water-based photo-curing coating with stable nanocellulose and preparation method thereof |
-
2022
- 2022-09-19 CN CN202211135832.5A patent/CN115449019A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116574448A (en) * | 2023-04-07 | 2023-08-11 | 中国林业科学研究院林产化学工业研究所 | Plant oil-based self-repairing water-based photo-curing coating with stable nanocellulose and preparation method thereof |
| CN116333235A (en) * | 2023-04-10 | 2023-06-27 | 深圳永昌和科技有限公司 | Photo-curing acrylic resin material for 3D printing and preparation method thereof |
| CN116333235B (en) * | 2023-04-10 | 2024-01-12 | 深圳永昌和科技有限公司 | Photo-curing acrylic resin material for 3D printing and preparation method thereof |
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