CN111072520A - Modified curcumin with carbon-carbon double bond, prepared environment-friendly fluorescent water-based acrylic resin and preparation method - Google Patents
Modified curcumin with carbon-carbon double bond, prepared environment-friendly fluorescent water-based acrylic resin and preparation method Download PDFInfo
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Abstract
The fluorescent micromolecules have the defects of poor compatibility with a matrix, easy fading, easy migration of dyeing, insufficient color fastness, uneven distribution of chromophoric groups, insufficient brightness of colors, easy elution and the like in the use process. The invention takes diisocyanate compound as cross linker, curcumin and acrylamide are added in sequence for reaction, and curcumin is grafted on acrylamide to prepare fluorescent acrylamide micromolecule monomer; adding an acrylate monomer and an emulsifier for emulsification, adding an inorganic peroxide initiator to initiate free radical emulsion polymerization, cooling, and adding ammonia water for neutralization to prepare the environment-friendly fluorescent water-based acrylic resin emulsion with the solid content of 25-35%. The invention takes diisocyanate compound as cross linker, introduces curcumin into the molecular chain of the water-based acrylic resin in a chemical bonding mode, endows the water-based acrylic resin with fluorescence effect, and solves a plurality of problems caused by the preparation of the fluorescence-type water-based acrylic resin by a blending method.
Description
Technical Field
The invention relates to the technical field of acrylic resin, in particular to environment-friendly fluorescent water-based acrylic resin and a preparation method thereof.
Background
Fluorescent micromolecules often have the defects of poor compatibility with a matrix, easy fading, easy dye migration, low color fastness, uneven distribution of chromophoric groups, insufficient brightness of colors, easy elution and the like in the using process, so the research of fluorescent macromolecules is gradually in the hot field.
The water-based acrylic resin has the advantages of translucency, high cost performance, good adhesion, tough formed film, light resistance and aging resistance of a coating, flat and bright film, transparency, flexibility, elasticity, good sanitary performance, dry and wet wiping resistance, good compatibility and convenient use. In recent years, the composition has been widely used in the fields of paints, textile coating agents, and the like. Fluorescent micromolecules are introduced into the water-based acrylic resin in a chemical bonding mode, so that the environment-friendly fluorescent water-based acrylic resin material with excellent performance can be prepared.
Disclosure of Invention
The invention aims to provide an environment-friendly fluorescent water-based acrylic resin and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the preparation method of the environment-friendly fluorescent water-based acrylic resin is characterized by comprising the following steps:
the method comprises the following steps:
the method comprises the following steps: adding 10-30 g of acrylate monomer without active hydrogen, 0.1-0.5 g of anionic emulsifier, 0.05-0.3 g of nonionic emulsifier and 30-40 g of water into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to be 40-60 ℃, and fully emulsifying for 30-50 min under stirring to obtain PA emulsion.
Step two: 5-10 g of acrylate monomer without active hydrogen, 0-0.20% of curcumin and 0.02-0.08 g of diisocyanate compound based on the mass of all acrylate monomers in the system are added into a four-neck flask provided with standard synthetic reaction equipment (a thermometer, a condenser pipe and a mechanical stirring device), and the temperature is raised to 70-80 ℃ for reaction for 1-2 h.
Step three: heating to 90-110 ℃, adding 1-3 g of acrylate monomer containing active hydrogen and 2-4 mL of acetone, and reacting for 1-3 h.
Step four: cooling to 50-70 ℃, then adding 0.1-0.3 g of anionic emulsifier, 0.05-0.15 g of nonionic emulsifier and 10-15 g of water, increasing the stirring speed, reacting for 30-50 min, and fully emulsifying. Reducing the stirring speed, and weighing 1-2% of the total mass of the acrylate monomers in the second step and the third step as the following monomers: dissolving the water in a mass ratio of 1: 100, adding the dissolved water into a four-mouth bottle, and reacting for 30-50 min to prepare seed emulsion;
step five: weighing an inorganic peroxide initiator accounting for 1-2% of the mass of the monomer in the step one, and mixing the monomer: dissolving the water in a mass ratio of 1: 100, and respectively dropwise adding the inorganic peroxide aqueous solution and the seed emulsion PA on the four-neck flask by using two constant-pressure separating funnels at the same time, controlling the dropwise adding speed and finishing the dropwise adding within 2-4 h. Plugging the bottle opening, reacting for 1-2h, and adjusting the pH to 7-7.5 by using ammonia water to obtain the environment-friendly fluorescent water-based acrylic resin emulsion.
In the first step and the second step, the acrylate monomer without active hydrogen is selected from methyl acrylate, butyl acrylate and methyl methacrylate.
The invention adopts an external emulsification method, and can form oil-in-water emulsion by selecting an emulsifier, which comprises the following specific steps:
in the first and fourth steps, the anionic emulsifier is selected from dodecyl sulfonic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium didodecyl phenyl ether disulfonate.
In the first step and the fourth step, the nonionic emulsifier is selected from fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene, fatty acid polyoxyethylene ester and polyoxyethylene alkylolamide.
In the second step, the diisocyanate compound is selected from isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.
In the third step, the active hydrogen-containing acrylate monomer refers to acrylate monomers having amino groups, hydroxyl groups and other groups with high reactivity with isocyanate groups, such as hydroxyethyl acrylate, acrylamide, hydroxypropyl acrylate, N-hydroxymethyl acrylamide and hydroxypropyl methacrylate, preferably hydroxyethyl acrylate and acrylamide.
In the fourth step, the inorganic peroxide initiator is selected from hydrogen peroxide, ammonium persulfate and potassium persulfate.
The environment-friendly fluorescent water-based acrylic resin emulsion is prepared by the preparation method of the environment-friendly fluorescent water-based acrylic resin.
The invention has the following advantages:
1. according to the invention, isophorone diisocyanate is taken as a cross-linking agent, fluorescent micromolecules are introduced into a molecular chain of the waterborne acrylic resin in a chemical bonding manner, the problems of easiness in falling off, nonuniform distribution, poor stability and the like of the micromolecules are solved, and in addition, the waterborne acrylic resin takes water as a solvent, is safe and environment-friendly and has a wide application prospect.
2. The water-based acrylic resin can be used as carrier resin, the carrier resin is attachment of fluorescent dye, and the water-based acrylic resin has the main functions of helping the fluorescent dye to spread color, improving the compatibility of the fluorescent dye and downstream resin and protecting the performance of the fluorescent dye. The carrier resin is usually strong polar resin, and the molecules contain strong polar groups such as amino, hydroxyl, ether bond, amide and the like, so that on one hand, the carrier resin has a color-assisting effect and increases the fluorescence efficiency; on the other hand, the fluorescent dye has good compatibility with the fluorescent dye, and is beneficial to the uniform dispersion of the dye.
3. The water-based acrylic resin coating is endowed with a fluorescent effect, and when the water-based acrylic resin coating is applied to leather and fabric coating, the color and luster light sensation degree, the fashion degree and the aesthetic degree can be improved, and the requirements of people on functionalized and differentiated products are met.
Drawings
FIG. 1 is a schematic diagram of the synthesis process of the environment-friendly fluorescent waterborne acrylic resin.
FIG. 2 is a fluorescence emission spectrum of the environmentally-friendly fluorescent aqueous acrylic resin with different curcumin contents.
The fluorescence intensity of the fluorescent acrylic resin (CUR-PR) dispersion increased with the increase of the Curcumin (CUR) content, and reached a maximum at a content of 0.18%, after which the fluorescence intensity of the CUR-PR showed a significant tendency to decrease when the content was increased to 0.20%. That is, the concentration self-quenching effect exists in the CUR-PR dispersion liquid, because at a larger concentration, the interaction between CUR-PR molecules is enhanced, and the presence of dimers of the CUR excited-state molecules and ground-state molecules is caused, and the energy of the first electron excited singlet state of the monomer is higher than the energy of the first electron excited singlet state of the dimer, so that the dimer may quench fluorescence by resonance energy transfer or radiation, and the fluorescence intensity may be decreased.
FIG. 3 is an ultra-depth of field microscopic view of the environmentally friendly fluorescent aqueous acrylic resin with different curcumin contents.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
The invention relates to a preparation method of environment-friendly fluorescent water-based acrylic resin, which comprises the following steps:
the method comprises the following steps: adding 10-30 g of acrylate monomer without active hydrogen, 0.1-0.5 g of anionic emulsifier, 0.05-0.3 g of nonionic emulsifier and 30-40 g of water into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to be 40-60 ℃, and fully emulsifying for 30-50 min under stirring to obtain PA emulsion.
Step two: 5-10 g of acrylate monomer without active hydrogen, 0-0.20% of curcumin and 0.02-0.08 g of diisocyanate compound based on the mass of all acrylate monomers in the system are added into a four-neck flask provided with standard synthetic reaction equipment (a thermometer, a condenser pipe and a mechanical stirring device), and the temperature is raised to 70-80 ℃ for reaction for 1-2 h.
Step three: heating to 90-110 ℃, adding 1-3 g of acrylate monomer containing active hydrogen and 2-4 mL of acetone, and reacting for 1-3 h.
Step four: cooling to 50-70 ℃, then adding 0.1-0.3 g of anionic emulsifier, 0.05-0.15 g of nonionic emulsifier and 10-15 g of water, increasing the stirring speed, reacting for 30-50 min, and fully emulsifying. Reducing the stirring speed, and weighing an inorganic peroxide initiator accounting for 1-2% of the total mass of the acrylate monomers in the second step and the third step, wherein the inorganic peroxide initiator comprises the following monomers: dissolving the water in a mass ratio of 1: 100, adding the dissolved water into a four-mouth bottle, and reacting for 30-50 min to prepare seed emulsion;
step five: weighing an inorganic peroxide initiator accounting for 1-2% of the mass of the monomer in the step one, and mixing the monomer: dissolving the water in a mass ratio of 1: 100, and respectively dropwise adding the inorganic peroxide aqueous solution and the emulsion PA on the four-neck flask by using two constant-pressure separating funnels at the same time, controlling the dropwise adding speed, and finishing the dropwise adding within 2-4 hours. Plugging the bottle opening, reacting for 1-2h, and adjusting the pH to 7-7.5 by using ammonia water to obtain the environment-friendly fluorescent water-based acrylic resin emulsion.
In the first step and the second step, the acrylate monomer without active hydrogen is selected from methyl acrylate, butyl acrylate and methyl methacrylate.
In the first and fourth steps, the anionic emulsifier is selected from dodecyl sulfonic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium didodecyl phenyl ether disulfonate.
In the first step and the fourth step, the nonionic emulsifier is selected from fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene, fatty acid polyoxyethylene ester and polyoxyethylene alkylolamide.
In the second step, the diisocyanate compound is selected from isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.
In the third step, the acrylic ester monomer containing active hydrogen is selected from hydroxyethyl acrylate and acrylamide.
In the fourth step, the inorganic peroxide initiator is selected from hydrogen peroxide, ammonium persulfate and potassium persulfate.
Example 1:
the method comprises the following steps: adding 10.5g of methyl acrylate, 7g of butyl acrylate, 3.5g of acrylamide, 0.42g of sodium dodecyl benzene sulfonate, 0.21g of fatty alcohol-polyoxyethylene ether and 35g of water into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to 50 ℃, and fully emulsifying for 40min under stirring to obtain the PA emulsion.
Step two: 4.5g of methyl acrylate, 3g of butyl acrylate, 0.08 percent of curcumin and 0.029g of isophorone diisocyanate in the mass of the total acrylic ester monomers in the system are added into a four-neck flask provided with standard synthetic reaction equipment (a thermometer, a condenser tube and a mechanical stirring device), and the temperature is raised to 75 ℃ for reaction for 1 hour.
Step three: the temperature was raised to 100 ℃ and 1.5g of acrylamide and 2mL of acetone were added to the mixture to react for 1 hour.
Step four: cooling to 60 ℃, then adding 0.18g of sodium dodecyl benzene sulfonate, 0.09g of fatty alcohol-polyoxyethylene ether and 15g of water, increasing the stirring speed, reacting for 30min, and fully emulsifying. Reducing the stirring speed, weighing 0.18g of ammonium persulfate and 18g of water to prepare an ammonium persulfate aqueous solution, adding the ammonium persulfate aqueous solution into a four-mouth bottle, and reacting for 30 min;
step five: 0.42g of ammonium persulfate and 42g of water are weighed to prepare an ammonium persulfate aqueous solution, and the ammonium persulfate aqueous solution and the emulsion PA are respectively and simultaneously dripped on the four-neck flask by using two constant-pressure separating funnels, the dripping speed is controlled, and the dripping is finished within 3 hours. Plugging the bottle mouth, reacting for 1h, and adjusting the pH to 7.5 by using ammonia water to prepare the environment-friendly fluorescent aqueous acrylic resin emulsion with the solid content of 25%.
Example 2:
the method comprises the following steps: adding 10.5g of methyl acrylate, 7g of butyl acrylate, 3.5g of acrylamide, 0.28g of sodium dodecyl benzene sulfonate, 0.14g of fatty alcohol-polyoxyethylene ether and 35g of water into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to 50 ℃, and fully emulsifying for 30min under stirring to obtain the PA emulsion.
Step two: 4.5g of methyl acrylate, 3g of butyl acrylate, 0.10 percent of curcumin and 0.036g of isophorone diisocyanate based on the mass of the total acrylic ester monomers in the system are added into a four-neck flask provided with standard synthetic reaction equipment (a thermometer, a condenser tube and a mechanical stirring device) and heated to 75 ℃ for reaction for 1 hour.
Step three: the temperature was raised to 90 ℃ and 1.5g of acrylamide and 2mL of acetone were added to the mixture to react for 1 hour.
Step four: cooling to 70 ℃, then adding 0.12g of sodium dodecyl benzene sulfonate, 0.06g of fatty alcohol-polyoxyethylene ether and 15g of water, increasing the stirring speed, reacting for 40min, and fully emulsifying. Reducing the stirring speed, weighing 0.09g of ammonium persulfate and 9g of water to prepare an ammonium persulfate aqueous solution, and adding the ammonium persulfate aqueous solution into a four-mouth bottle to react for 40 min;
step five: 0.21g of ammonium persulfate and 21g of water are weighed to prepare an ammonium persulfate aqueous solution, and the ammonium persulfate aqueous solution and the emulsion PA are respectively and simultaneously dripped on the four-neck flask by using two constant-pressure separating funnels, the dripping speed is controlled, and dripping is finished within 2 hours. Plugging the bottle mouth, reacting for 1h, and adjusting the pH to 7.5 by using ammonia water to prepare the environment-friendly fluorescent aqueous acrylic resin emulsion with the solid content of 29 percent.
Example 3:
the method comprises the following steps: adding 10.5g of methyl acrylate, 7g of butyl acrylate, 3.5g of acrylamide, 0.56g of sodium dodecyl benzene sulfonate, 0.28g of fatty alcohol-polyoxyethylene ether and 35g of water into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to 50 ℃, and fully emulsifying for 40min under stirring to obtain the PA emulsion.
Step two: 4.5g of methyl acrylate, 3g of butyl acrylate, 0.12 percent of curcumin and 0.044g of isophorone diisocyanate based on the mass of the total acrylic ester monomers in the system are added into a four-neck flask provided with standard synthetic reaction equipment (a thermometer, a condenser tube and a mechanical stirring device), and the temperature is raised to 75 ℃ for reaction for 1 hour.
Step three: the temperature was raised to 90 ℃ and 1.5g of acrylamide and 3mL of acetone were added to the mixture to react for 1 hour.
Step four: cooling to 65 ℃, then adding 0.24g of sodium dodecyl benzene sulfonate, 0.12g of fatty alcohol-polyoxyethylene ether and 15g of water, increasing the stirring speed, reacting for 40min, and fully emulsifying. Reducing the stirring speed, weighing 0.135g of ammonium persulfate and 13.5g of water to prepare an ammonium persulfate aqueous solution, adding the ammonium persulfate aqueous solution into a four-mouth bottle, and reacting for 40 min;
step five: 0.315g of ammonium persulfate and 31.5g of water are weighed to prepare an ammonium persulfate aqueous solution, and the ammonium persulfate aqueous solution and the emulsion PA are respectively and simultaneously dripped on the four-neck flask by using two constant-pressure separating funnels, the dripping speed is controlled, and the dripping is finished within 2.5 hours. Plugging the bottle mouth, reacting for 2h, and adjusting the pH to 7.5 by using ammonia water to prepare the environment-friendly fluorescent water-based acrylic resin emulsion with the solid content of 27%.
Example 4:
the method comprises the following steps: adding 10.5g of methyl acrylate, 7g of butyl acrylate, 3.5g of acrylamide, 0.56g of sodium dodecyl benzene sulfonate, 0.28g of fatty alcohol-polyoxyethylene ether and 35g of water into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to 50 ℃, and fully emulsifying for 40min under stirring to obtain the PA emulsion.
Step two: 4.5g of methyl acrylate, 3g of butyl acrylate, 0.15 percent of curcumin and 0.054g of isophorone diisocyanate based on the mass of the total acrylic ester monomers in the system are added into a four-neck flask provided with standard synthetic reaction equipment (a thermometer, a condenser tube and a mechanical stirring device), and the temperature is raised to 75 ℃ for reaction for 1 hour.
Step three: the temperature was raised to 100 ℃ and 1.5g of acrylamide and 4mL of acetone were added to the mixture to react for 1 hour.
Step four: cooling to 70 ℃, then adding 0.24g of sodium dodecyl benzene sulfonate, 0.12g of fatty alcohol-polyoxyethylene ether and 15g of water, increasing the stirring speed, reacting for 40min, and fully emulsifying. Reducing the stirring speed, weighing 0.09g of ammonium persulfate and 9g of water to prepare an ammonium persulfate aqueous solution, adding the ammonium persulfate aqueous solution into a four-mouth bottle, and reacting for 40 min;
step five: 0.21g of ammonium persulfate and 21g of water are weighed to prepare an ammonium persulfate aqueous solution, and the ammonium persulfate aqueous solution and the emulsion PA are respectively and simultaneously dripped on the four-neck flask by using two constant-pressure separating funnels, the dripping speed is controlled, and the dripping is finished within 3 hours. Plugging a bottle mouth, reacting for 1h, and adjusting the pH to 7.5 by using ammonia water to prepare the environment-friendly fluorescent water-based acrylic resin emulsion with the solid content of 31 percent.
Example 5:
the method comprises the following steps: adding 10.5g of methyl acrylate, 7g of butyl acrylate, 3.5g of acrylamide, 0.42g of sodium dodecyl benzene sulfonate, 0.21g of fatty alcohol-polyoxyethylene ether and 35g of water into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to 55 ℃, and fully emulsifying for 40min under stirring to obtain the PA emulsion.
Step two: 4.5g of methyl acrylate, 3g of butyl acrylate, 0.18 percent of curcumin and 0.065g of isophorone diisocyanate in the mass of the total acrylic ester monomers in the system are added into a four-neck flask provided with standard synthetic reaction equipment (a thermometer, a condenser tube and a mechanical stirring device), and the temperature is raised to 75 ℃ for reaction for 1 hour.
Step three: the temperature was raised to 100 ℃ and 1.5g of acrylamide and 3mL of acetone were added to the mixture to react for 1 hour.
Step four: cooling to 60 ℃, then adding 0.18g of sodium dodecyl benzene sulfonate, 0.09g of fatty alcohol-polyoxyethylene ether and 15g of water, increasing the stirring speed, reacting for 50min, and fully emulsifying. Reducing the stirring speed, weighing 0.09g of ammonium persulfate and 9g of water to prepare an ammonium persulfate aqueous solution, adding the ammonium persulfate aqueous solution into a four-mouth bottle, and reacting for 50 min;
step five: 0.21g of ammonium persulfate and 21g of water are weighed to prepare an ammonium persulfate aqueous solution, and the ammonium persulfate aqueous solution and the emulsion PA are respectively and simultaneously dripped on the four-neck flask by using two constant-pressure separating funnels, the dripping speed is controlled, and the dripping is finished within 2.5 hours. Plugging the bottle mouth, reacting for 1.5h, and adjusting the pH to 7.5 by ammonia water to prepare the environment-friendly fluorescent aqueous acrylic resin emulsion with the solid content of 30 percent.
Example 6:
the method comprises the following steps: adding 20g of methyl acrylate, 7g of butyl acrylate, 3g of methyl methacrylate, 0.5g of sodium dodecyl sulfate, 0.05g of polyoxyethylene alkylolamide and 30g of water into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of the magnetic stirrer to be 40 ℃, and fully emulsifying for 50min under stirring to obtain the PA emulsion.
Step two: 10g of methyl acrylate, 0.02g of curcumin and 0.02g of hexamethylene diisocyanate accounting for 0.02 percent of the mass of the total acrylic ester monomers in the system are added into a four-neck flask provided with standard synthetic reaction equipment (a thermometer, a condenser tube and a mechanical stirring device) and heated to 70 ℃ for reaction for 1 hour.
Step three: the temperature is raised to 90 ℃, 1g of N-methylolacrylamide and 2mL of acetone are added, and the reaction is carried out for 2 hours.
Step four: cooling to 50 ℃, then adding 0.1g of sodium dodecyl benzene sulfonate, 0.15g of polyoxyethylene fatty acid ester and 13g of water, increasing the stirring speed, reacting for 40min, and fully emulsifying. Reducing the stirring speed, weighing 0.1g of ammonium persulfate and 10g of water to prepare an ammonium persulfate aqueous solution, adding the ammonium persulfate aqueous solution into a four-mouth bottle, and reacting for 50 min;
step five: 0.3g of ammonium persulfate and 30g of water are weighed to prepare an ammonium persulfate aqueous solution, and the ammonium persulfate aqueous solution and the emulsion PA are respectively and simultaneously dripped on the four-neck flask by using two constant-pressure separating funnels, the dripping speed is controlled, and dripping is finished within 2 hours. Plugging the bottle mouth, reacting for 1h, and adjusting the pH to 7 by using ammonia water to prepare the environment-friendly fluorescent water-based acrylic resin emulsion.
Example 7:
the method comprises the following steps: adding 10g of hydroxyethyl acrylate, 0.1g of sodium dodecyl sulfate, 0.3g of alkylphenol polyoxyethylene and 40g of water into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of a magnetic stirrer to be 60 ℃, and fully emulsifying for 30min under stirring to obtain PA emulsion.
Step two: 5g of methyl acrylate, 0.20 percent of curcumin, 0.06g of toluene diisocyanate and 0.02g of diphenylmethane diisocyanate in the mass of the total acrylic monomer in the system are added into a four-neck flask provided with standard synthetic reaction equipment (a thermometer, a condenser tube and a mechanical stirring device) and heated to 80 ℃ for reaction for 2 hours.
Step three: the temperature is raised to 110 ℃, 1g of hydroxypropyl acrylate, 2g of hydroxyethyl acrylate and 4mL of acetone are added, and the reaction is carried out for 3 h.
Step four: cooling to 70 ℃, then adding 0.3g of sodium didodecyl phenyl ether disulfonate, 0.05g of fatty alcohol-polyoxyethylene ether and 10g of water, increasing the stirring speed, reacting for 30min, and fully emulsifying. Reducing the stirring speed, weighing 0.1g of ammonium persulfate and 10g of water to prepare an ammonium persulfate aqueous solution, adding into a four-mouth bottle, and reacting for 30 min;
step five: 0.2g of ammonium persulfate and 20g of water are weighed to prepare an ammonium persulfate aqueous solution, and the ammonium persulfate aqueous solution and the emulsion PA are respectively and simultaneously dripped on the four-neck flask by using two constant-pressure separating funnels, the dripping speed is controlled, and dripping is finished within 4 hours. Plugging the bottle mouth, reacting for 2h, and adjusting the pH to 7.5 by using ammonia water to prepare the environment-friendly fluorescent water-based acrylic resin emulsion.
Claims (10)
1. The preparation method of the modified curcumin with carbon-carbon double bonds is characterized by comprising the following steps:
the modified curcumin with carbon-carbon double bonds is obtained by introducing carbon-carbon double bonds in an acrylate monomer into a curcumin structure through the reaction of an isocyanate group and hydroxyl in the curcumin and the reaction of the isocyanate group and active hydrogen in the acrylate monomer containing the active hydrogen by utilizing diisocyanate or polyisocyanate.
2. The method of claim 1, wherein the diisocyanate is one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate; the reaction temperature of hydroxyl and isocyanate group in curcumin is 70-80 ℃, and the reaction time is 1-2 h; the active hydrogen-containing acrylate monomer is one or more of hydroxyethyl acrylate, acrylamide, hydroxypropyl acrylate, N-hydroxymethyl acrylamide and hydroxypropyl methacrylate, the reaction temperature of the isocyanate group and the active hydrogen-containing acrylate monomer is 90-110 ℃, the reaction time is 1-3 hours, and a proper amount of solvent is added during the reaction.
3. Modified curcumin having a carbon-carbon double bond prepared by the method of claim 1 or 2.
4. The preparation method of the environment-friendly fluorescent water-based acrylic resin is characterized by comprising the following steps:
adding curcumin and diisocyanate or polyisocyanate into an acrylate monomer without active hydrogen, so that hydroxyl in the curcumin reacts with the diisocyanate or polyisocyanate to be connected with an isocyanate group;
adding an acrylate monomer containing active hydrogen, reacting the isocyanate group with the acrylate monomer containing active hydrogen, and connecting a carbon-carbon double bond;
adding an emulsifier and water, and fully emulsifying the system to prepare a seed emulsion;
and (2) slowly dripping an initiator and the PA emulsion into the seed emulsion simultaneously by adopting a seed emulsion polymerization method, and fully reacting to obtain the environment-friendly fluorescent water-based acrylic resin.
5. The method of claim 4, wherein the acrylate monomer containing active hydrogen is added before the acrylate monomer containing active hydrogen is added, and the acrylate monomer containing no active hydrogen is added as a solvent and is used for further preparing the seed emulsion.
6. The method as claimed in claim 4, wherein the amount of curcumin is 0 to 0.20% by mass of the total mass of the active hydrogen-containing acrylate monomer and the acrylate monomer in the seed emulsion.
7. The method of claim 4, wherein the PA emulsion is obtained by a process comprising: uniformly mixing 10-30 g of acrylate monomer, 0.1-0.5 g of anionic emulsifier, 0.05-0.3 g of nonionic emulsifier and 30-40 g of water, and stirring and emulsifying at 40-60 ℃ for 30-50 min to obtain PA emulsion; the acrylic ester monomer is an acrylic ester monomer without active hydrogen or an acrylic ester monomer containing active hydrogen.
8. The method of claim 4, wherein the emulsifier comprises an anionic emulsifier and a nonionic emulsifier; the anionic emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium didodecyl phenyl ether disulfonate; the nonionic emulsifier is one or more of fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, fatty acid-polyoxyethylene ester and polyoxyethylene alkylolamide; the initiator is one or more of hydrogen peroxide, ammonium persulfate and potassium persulfate.
9. The method of claim 4, comprising the steps of:
the method comprises the following steps: adding 10-30 g of acrylate monomer, 0.1-0.5 g of anionic emulsifier, 0.05-0.3 g of nonionic emulsifier and 30-40 g of water into a three-neck flask provided with a thermometer, a stirrer and a glass bottle stopper, uniformly mixing, adjusting the temperature of a magnetic stirrer to be 40-60 ℃, and fully emulsifying for 30-50 min under stirring to obtain PA emulsion;
step two: adding 5-10 g of acrylate monomer without active hydrogen, 0-0.20% of curcumin and 0.02-0.08 g of diisocyanate compound in mass of the monomer into a four-neck flask provided with a thermometer, a condenser and a mechanical stirring device, and heating to 70-80 ℃ for reaction for 1-2 hours;
step three: heating to 90-110 ℃, adding 1-3 g of acrylate monomer containing active hydrogen and 2-4 mL of acetone, and reacting for 1-3 h;
step four: cooling to 50-70 ℃, then adding 0.1-0.3 g of anionic emulsifier, 0.05-0.15 g of nonionic emulsifier and 10-15 g of water, increasing the stirring speed, reacting for 30-50 min, and fully emulsifying; reducing the stirring speed, and weighing an inorganic peroxide initiator accounting for 1-2% of the total mass of the acrylate monomers in the second step and the third step, wherein the inorganic peroxide initiator comprises the following monomers: the water mass ratio is 1: dissolving the mixture by 100 degrees, adding the mixture into a four-mouth bottle, and reacting for 30-50 min to prepare seed emulsion;
step five: weighing an inorganic peroxide initiator accounting for 1-2% of the mass of the monomer in the step one, and mixing the monomer: the water mass ratio is 1: dissolving 100, respectively dropwise adding an inorganic peroxide aqueous solution and PA emulsion into the seed emulsion obtained in the fourth step on a four-neck flask by using two constant-pressure separating funnels, controlling the dropwise adding speed, and finishing dropping within 2-4 h; plugging a bottle opening, reacting for 1-2h, and adjusting the pH to 7-7.5 by using ammonia water to prepare the environment-friendly fluorescent water-based acrylic resin emulsion;
the acrylic ester monomer is an acrylic ester monomer without active hydrogen or an acrylic ester monomer containing active hydrogen;
the acrylate monomer without active hydrogen is one or more of methyl acrylate, butyl acrylate and methyl methacrylate; the acrylate monomer containing active hydrogen is one or more of hydroxyethyl acrylate, acrylamide, hydroxypropyl acrylate, N-hydroxymethyl acrylamide and hydroxypropyl methacrylate;
the anionic emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and sodium didodecyl phenyl ether disulfonate;
the nonionic emulsifier is one or more of fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, fatty acid-polyoxyethylene ester and polyoxyethylene alkylolamide;
the diisocyanate compound is one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate;
the inorganic peroxide initiator is one or more of hydrogen peroxide, ammonium persulfate and potassium persulfate.
10. The environment-friendly fluorescent water-based acrylic resin obtained by the method of any one of claims 4 to 9.
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