Preparation method of fluorine-containing acrylate modified polyurethane emulsion with fluorescent property
Technical Field
The invention relates to the technical field of fluorescent polymers, in particular to a preparation method of fluorine-containing acrylate modified polyurethane emulsion with fluorescence property.
Background
Fluorescent materials are widely used in many fields such as sensors, probes, imaging, and display because of their excellent luminescence properties. Meanwhile, in some fields, in order to improve safety or creative and fashionable senses, some products are also required to have fluorescence emitting performance. The aqueous polyurethane material takes water as a dispersion medium, and the formed dispersion liquid contains a small amount of or no solvent, so that the novel polyurethane material has good wear resistance and adhesive property, and also has the advantages of environmental protection, no toxicity, good safety, good applicability, energy conservation, low cost and the like. Therefore, it is one of the trends in the development of fluorescent materials to use aqueous polyurethane as a substrate for fluorescent materials.
At present, relevant documents on fluorescent substance modified waterborne polyurethane materials are reported in the literature, and the following two ways are mainly available.
Firstly, fluorescent substances exist in the polyurethane material in a doped (blended) form:
dissolving fluorescent micromolecule 4-amino-4' - (N, N-diphenyl) by DMF (dimethyl formamide) for relieving Zhixi madder and the likeAmino) -1, 2-stilbene (ADAS)
Then adding waterborne polyurethane, adding water and mixing uniformly to prepare the waterborne polyurethane fluorescent material [ functional polymer science, 2014,27(04): 426-431-]。
Sunshimui et al prepared { [ Tb (L) { [ using in situ polymerization method)2(H2O)2](Hdmpy)(H2O)2Functional material (2012 and 12):1569-]。
Plum snow and the like are firstly modified by mercaptoacetic acid on CdTe quantum dots, and then Fe is prepared through the electrostatic interaction of the CdTe quantum dots and cationic polyurethane3O4CdTe/polyurethane nanocomposite (macromolecules, 2012 and 6):606-]。
The fluorescent substances in the scheme exist in polyurethane in a doped form, and the fluorescent small molecules are easy to migrate, fall off and decompose due to poor compatibility of the fluorescent substances and the polyurethane material, so that the fluorescent property is poor. And simultaneously, the comprehensive properties (such as elongation at break, wear resistance, caking property and the like) of the polyurethane material are deteriorated.
Secondly, fluorescent substances are combined in a polyurethane molecular chain by chemical bond bonding:
korean et al firstly complex α N, N-dihydroxyethyl-aniline-Terpyridine (TPYOH) with metal ions, and the complex is used as a catalyst and an initiator for caprolactone polymerization to obtain fluorescent polycaprolactone, wherein the structural formula of the fluorescent polycaprolactone is as follows:
then the mixture reacts with isocyanate to prepare fluorescent polyurethane (compound fertilizer: Anhui university, 2017)]。
The rhodamine fluorescent dye is modified by Zhou and the like to enable the rhodamine fluorescent dye to have two isocyanate groups, and the structural formula of the rhodamine fluorescent dye is as follows:
then the rhodamine is successfully introduced into the polyurethane chain by the reaction with the polyol to prepare the rhodamine modified polyurethaneA polyurethane emulsion with fluorescent function [ journal of Macromolecular Science Part A,2012,49(10): 890-896-]。
7-amino-4-trifluoromethyl coumarin (AFC) is synthesized by plum-hazel and the like by adopting a one-step method, and the structural formula of the 7-amino-4-trifluoromethyl coumarin (AFC) is shown as follows:
it is introduced into polyurethane as a blocking agent to prepare fluorescent polyurethane [ chemical engineering progress, 2015,34(11):4001-]。
Yellow Wen synthesizes a fluorescent polyacrylate which is used as a chain extender and has the following structural formula:
a polyurethane material is prepared (Chinese university of science and technology, 2017)]。
The fluorescent materials in the scheme are combined in a polyurethane molecular chain in a chemical bond bonding mode, and through the linkage effect of chemical bonds, fluorescent groups can be combined in polyurethane molecules more firmly, so that the incompatibility of the fluorescent materials and the polyurethane material is avoided, the migration, falling and decomposition of the fluorescent molecules are avoided, and the service life of the fluorescent polyurethane material is greatly prolonged.
However, the structure of the waterborne polyurethane contains more hydrophilic groups, so that the waterproof and waterproof performances of the waterborne polyurethane are poor. In addition, as the fluorescent chromophore generally consists of a large number of conjugated double bond benzene rings or heterocycles, the fluorescent polyurethane material containing the structure has poor weather resistance, and the problems of yellowing, reduced gloss and the like easily occur under the condition of ultraviolet illumination. At present, few proposals in the existing literature can improve the waterproof performance and the weather resistance of the fluorescent polyurethane material at the same time.
Therefore, how to ensure that the fluorescent polyurethane material has excellent fluorescence performance and can effectively improve the waterproof performance and the weather resistance of the fluorescent polyurethane material has important significance.
Disclosure of Invention
The invention provides a preparation method of fluorine-containing acrylate modified polyurethane emulsion with fluorescence property, and the fluorescent polyurethane material has excellent fluorescence property and can effectively improve the waterproof property and weather resistance of the fluorescent polyurethane material.
In order to achieve the purpose, the preparation method of the fluorine-containing acrylate modified polyurethane emulsion with the fluorescence property sequentially comprises the following steps:
step one, synthesis of a fluorescent chain extender:
slowly dripping an acetone solution of methacryloyl chloride into an acetone solution containing triethylamine and 7-hydroxycoumarin under the condition of ice-water bath, controlling the dripping to be finished within 0.5h, and reacting for 12h at 25 ℃; after the reaction is completed, slowly adding water to quench the reaction, heating to 60 ℃, slowly dropwise adding an ethanol solution of diethanolamine, and stirring and reacting for 8 hours under the condition of condensation reflux; after the reaction is finished, removing the solvent by rotary evaporation under the conditions of 50 ℃ and-0.1 MPa to obtain the fluorescent chain extender;
step two, synthesizing a fluorescent polyurethane prepolymer with NCO end capping:
reacting isophorone diisocyanate and polycaprolactone diol serving as raw materials with dibutyl dilaurate serving as a catalyst at 80 ℃ for 1h, dissolving the fluorescent chain extender obtained in the step one and 2, 2-dimethylolpropionic acid in acetone according to a certain molar ratio, adding the mixture, and reacting for 2.5h to obtain an-NCO-terminated polyurethane prepolymer;
step three, synthesizing the fluorine-containing acrylate modified polyurethane emulsion with the fluorescent property:
dissolving trimethylolpropane in acetone, dropwise adding the solution into the system obtained in the second step, and reacting for 2 hours at 80 ℃; adding a grafting agent, and reacting for 1h until the-NCO group disappears; then the temperature is reduced to 40 ℃, and acetone is added for dilution and viscosity reduction for 0.5 h. And then adding triethylamine, neutralizing for 0.5h, removing the condensation and nitrogen, adding deionized water, and stirring at a high speed for 1.5h to obtain the fluorescent polyurethane emulsion. Adding sodium dodecyl sulfate 3% of the total mass of the acrylic monomers after complete emulsification, slowly heating to 80 ℃, adding potassium persulfate 1% of the total mass of the acrylic monomers under the protection of nitrogen, and adding a mixture of mercaptoethanol and isopropanol (m is 1% of the total mass of the acrylic monomers)R12SH:mIPA1:10) and then a mixture of fluoroacrylate and butyl acrylate was slowly added dropwise. After the reaction is carried out for 2.5h under the condition of heat preservation, NaHCO is used3Neutralizing to obtain the fluorine-containing acrylate modified polyurethane emulsion with fluorescent property.
The molar ratio of the fluorescent chain extender to the 2, 2-dimethylolpropionic acid in the second step is as follows: 1:1, 2:1, 3:1, 4:1 or 5: 1.
The grafting agent in the third step is one of hydroxyethyl methacrylate and hydroxyethyl acrylate.
The mass ratio of the fluorine-containing acrylate to the butyl acrylate in the step three is 1:1, 2:1 or 3:1
The fluorine-containing acrylate in the third step is one of trifluoroethyl methacrylate, hexafluorobutyl methacrylate and dodecafluoroheptyl methacrylate.
Compared with the prior art, the invention has the beneficial effects that:
1. the polyurethane coating has photoluminescent properties: according to the invention, the self-made dihydric alcohol with the fluorescent group is used as a chain extender for preparing the polyurethane material, the fluorescent group is connected into a polyurethane chain through a chemical bond, and the polyurethane chain is not easy to fall off and decompose, and has stable luminous performance under the stimulation of external light.
2. Improving the water resistance of the waterborne polyurethane: the mixture of fluorine-containing acrylate and butyl acrylate is used as a monomer, polyacrylate for modified polyurethane is prepared through a free radical reaction, a large amount of fluorine elements are introduced into the side chain of the composite material, and after the fluorine-containing chain segments migrate to the surface of the coating, the outer surface of the coating is more fully covered and protected, and fluorine has lower surface energy, so that the waterproof performance of the coating is effectively improved.
3. The weather resistance of the polyurethane material is improved: the acrylic ester modified waterborne polyurethane coating solves the problem of poor weather resistance of the fluorescent polyester material; the formed core-shell structure takes polyurethane containing fluorescent groups as a core and takes polyacrylic ester containing fluorine as a shell, which is beneficial to the migration of fluorine to the surface and can protect the fluorescent groups and the polyurethane in the structure.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention include, but are not limited to, the scope shown in the following examples.
A preparation method of fluorine-containing acrylate modified polyurethane emulsion (total mass is 1000 parts) with fluorescence performance comprises the following steps:
(1) and (3) synthesis of a fluorescent chain extender: a solution of 1:1 molar amount of triethylamine and 7-hydroxycoumarin in acetone (25% strength) was added slowly dropwise to an equimolar amount of a solution of chlorine methacrylate in acetone (20% strength) under ice-bath conditions. The dropwise addition is completed within 0.5h, and the reaction is carried out for 12h at 25 ℃. After the reaction was completed, water was slowly added to quench the reaction, and after heating to 60 ℃, an ethanol solution of diethanolamine in an equimolar amount (concentration: 25%) was added dropwise, and the reaction was stirred under reflux for 8 hours. After the reaction is finished, removing the solvent by rotary evaporation at the temperature of 50 ℃ and under the pressure of-0.1 MPa to obtain the fluorescent chain extender;
(2) -synthesis of NCO-terminated fluorescent polyurethane prepolymer: putting 42-90 parts of isophorone diisocyanate, 63-135 parts of polycaprolactone diol and dibutyltin dilaurate into a flask, reacting for 1 hour at 80 ℃, dissolving 2-9 parts of 2, 2-dimethylolpropionic acid (DMPA) and 15-25 parts of the fluorescent chain extender obtained in the step (1) in acetone with the mass being 5 times of that of the chain extender according to a given molar ratio, adding the solution into a system, and reacting for 2.5 hours to obtain an-NCO end-capped fluorescent polyurethane prepolymer;
(3) synthesizing a fluorine-containing acrylate modified polyurethane emulsion with fluorescent property: dissolving 2-6 parts of trimethylolpropane in 8 times of acetone by mass, dropwise adding the solution into the polyurethane prepolymer prepared in the step (2), and reacting for 2 hours at 80 ℃; and adding 7-16 parts of a grafting agent, reacting for 1 hour, and determining by a di-n-butylamine titration method until-NCO groups disappear. Then the temperature is reduced to 40 ℃, and acetone is added for dilution and viscosity reduction for 0.5 h. And then adding 1-7 parts of triethylamine, neutralizing for 0.5h, slowly dropwise adding 317-661 parts of deionized water, and stirring at a high speed for 1.5h to obtain the fluorescent polyurethane emulsion. After complete emulsification, 2-21 parts of sodium dodecyl sulfate is added, the temperature is slowly raised to 80 ℃, nitrogen is used for protection, and 0.6-6 parts of potassium persulfate and 0.0 part of potassium persulfate are added6-0.5 part of mercaptoethanol and 0.6-5 parts of isopropanol, and then slowly dropwise adding a mixture of 25-381 parts of fluorine-containing acrylate and 25-135 parts of butyl acrylate. After the reaction is carried out for 2.5 hours under the condition of heat preservation, 0.2-1.6 parts of NaHCO is used3Neutralizing to obtain the fluorine-containing acrylate modified polyurethane emulsion with fluorescent property.
The principle of the preparation method of the invention is as follows:
the reaction equation for synthesizing the fluorescent chain extender in the step (1) is as follows:
the reaction equation for synthesizing the-NCO-terminated fluorescent polyurethane prepolymer in the step (2) is as follows:
the reaction equation for synthesizing the fluorine-containing acrylate modified polyurethane emulsion with fluorescent property in the step (3) is as follows.
The invention is further illustrated by the following specific examples.
The reagents in the examples need to be dried before use, the relative molecular mass of the polycaprolactone diol is 1000, and the WPU-PA composite emulsion is the fluorine-containing acrylate modified polyurethane emulsion with fluorescence property.
The first embodiment is as follows:
1.012g (0.0100mol) of triethylamine and 1.621g (0.0100mol) of 7-hydroxycoumarin are accurately weighed, dissolved in 10g of acetone, added into a three-neck flask, 1.045g (0.0100mol) of methacryloyl chloride is dissolved in 5g of acetone under the ice bath condition and slowly dripped into the flask within 0.5h, and then reacted for 12h at 25 ℃. After the reaction was completed, water was slowly added to quench the reaction, and after heating to 60 ℃, 1.051g (0.0100mol) of diethanolamine dissolved in 5g of ethanol was added dropwise, and the reaction was stirred under reflux for 8 hours. And (3) after the reaction is finished, removing the solvent by rotary evaporation at the temperature of 50 ℃ and the pressure of-0.1 MPa to obtain the fluorescent chain extender for later use.
13.337g (0.0600mol) of isophorone diisocyanate and 20.000g (0.0200mol) of polycaprolactone diol are accurately weighed and added into a three-neck flask2Heating and stirring under the conditions of protection and condensation reflux, adding 3 drops of dibutyltin dilaurate when the temperature of a system reaches 80 ℃, reacting for 1h, then dissolving 3.353g (0.0100mol) of the fluorescent chain extender obtained in the step (1) and 1.341g (0.0100mol) of 2, 2-dimethylolpropionic acid in 20g of acetone, adding into a flask, and continuously reacting for 2.5h to prepare an-NCO-terminated fluorescent polyurethane prepolymer;
dissolving 0.894g (0.0067mol) of trimethylolpropane in 5g of acetone, dropwise adding the solution into the system in the step (2), and reacting for 2h at 80 ℃; 2.322g (0.0200mol) of hydroxyethyl acrylate were added and reacted for 1 hour until the-NCO group disappeared by di-n-butylamine titration. Then the temperature is reduced to 40 ℃, and a certain amount of acetone is added for dilution and viscosity reduction for 0.5 h. Then 1.012g (0.0100mol) of TEA is added to neutralize for 0.5h, and 98.609g of deionized water is slowly dropped and stirred at high speed for 1.5h to prepare the fluorescent polyurethane emulsion with double bond end capping.
After the emulsification is completed, 0.399g of sodium dodecyl sulfate is added, the temperature is slowly raised to 80 ℃, nitrogen is protected, 0.100g of potassium persulfate, 0.009g of mercaptoethanol and 0.090g of isopropanol are added, then 3.831g of a mixture of trifluoroethyl methacrylate and 3.831g of butyl acrylate is slowly dropped into the mixture, after the heat preservation reaction is carried out for 2.5 hours, 0.031g of NaHCO is added3Neutralizing to obtain the fluorine-containing acrylate modified polyurethane emulsion with fluorescent property.
Example two:
1.349g (0.0133mol) of triethylamine and 2.162g (0.0133mol) of 7-hydroxycoumarin are accurately weighed, dissolved in 14g of acetone, added into a three-neck flask, 1.394g (0.0133mol) of methacryloyl chloride is dissolved in 7g of acetone under the ice bath condition, slowly and dropwise added into the flask within 0.5h, and then reacted for 12h at 25 ℃. After the reaction was completed, water was slowly added to quench the reaction, and after heating to 60 ℃, 1.402g (0.0133mol) of diethanolamine dissolved in 7g of ethanol was added dropwise, and the reaction was stirred under reflux for 8 hours. And (3) after the reaction is finished, removing the solvent by rotary evaporation at the temperature of 50 ℃ and the pressure of-0.1 MPa to obtain the fluorescent chain extender for later use.
13.337g (0.0600mol) of isophorone diisocyanate and 20.000g (0.0200mol) of polycaprolactone diol are accurately weighed and added into a three-neck flask2Heating and stirring under the conditions of protection and condensation reflux, adding 3 drops of dibutyltin dilaurate when the temperature of a system reaches 80 ℃, reacting for 1h, dissolving 4.471g (0.0133mol) of the fluorescent chain extender obtained in the step (1) and 0.894g (0.0067mol) of 2, 2-dimethylolpropionic acid in 20g of acetone, adding into a flask, and continuously reacting for 2.5h to obtain an-NCO-terminated fluorescent polyurethane prepolymer;
dissolving 0.894g (0.0067mol) of trimethylolpropane in 5g of acetone, dropwise adding the solution into the system in the step (2), and reacting for 2h at 80 ℃; 2.322g (0.0200mol) of hydroxyethyl acrylate were added and reacted for 1 hour until the-NCO group disappeared by di-n-butylamine titration. Then the temperature is reduced to 40 ℃, and a certain amount of acetone is added for dilution and viscosity reduction for 0.5 h. Then 0.675g (0.0067mol) of TEA is added to neutralize for 0.5h, and 99.286g of deionized water is slowly dropped and stirred at high speed for 1.5h to prepare the fluorescent polyurethane emulsion with double bond end capping.
After the emulsification is completed, 1.611g of sodium dodecyl sulfate is added, the temperature is slowly raised to 80 ℃, nitrogen is protected, 0.403g of potassium persulfate, 0.037g of mercaptoethanol and 0.366g of isopropanol are added, then 25.300g of a mixture of hexafluorobutyl methacrylate and 12.650g of butyl acrylate is slowly dropped, after the heat preservation reaction is carried out for 2.5 hours, 0.125g of NaHCO is added3Neutralizing to obtain the fluorine-containing acrylate modified polyurethane emulsion with fluorescent property.
Example three:
1.518g (0.0150mol) of triethylamine and 2.432g (0.0150mol) of 7-hydroxycoumarin are accurately weighed, dissolved in 16g of acetone, added into a three-neck flask, 1.568g (0.0150mol) of methacryloyl chloride is dissolved in 8g of acetone under the ice bath condition and slowly dripped into the flask within 0.5h, and then reacted for 12h at 25 ℃. After the reaction was completed, water was slowly added to quench the reaction, and after heating to 60 ℃, 1.577g (0.0150mol) of diethanolamine dissolved in 8g of ethanol was added dropwise, and the reaction was stirred under reflux for 8 hours. And (3) after the reaction is finished, removing the solvent by rotary evaporation at the temperature of 50 ℃ and the pressure of-0.1 MPa to obtain the fluorescent chain extender for later use.
13.337g (0.0600mol) of isophorone diisocyanate and 20.000g (0.0200mol) of polycaprolactone diol are accurately weighed and added into a three-neck flask2Heating and stirring under the conditions of protection and condensation reflux, adding 3 drops of dibutyltin dilaurate when the temperature of a system reaches 80 ℃, reacting for 1h, dissolving 5.030g (0.0150mol) of the fluorescent chain extender obtained in the step (1) and 0.671g (0.0050mol) of 2, 2-dimethylolpropionic acid in 20g of acetone, adding into a flask, and continuously reacting for 2.5h to prepare an-NCO end-capped fluorescent polyurethane prepolymer; dissolving 0.894g (0.0067mol) of trimethylolpropane in 5g of acetone, dropwise adding the solution into the system in the step (2), and reacting for 2h at 80 ℃; 2.322g (0.0200mol) of hydroxyethyl acrylate were added and reacted for 1 hour until the-NCO group disappeared by di-n-butylamine titration. Then the temperature is reduced to 40 ℃, and a certain amount of acetone is added for dilution and viscosity reduction for 0.5 h. Then 0.506g (0.0050mol) of TEA is added to neutralize for 0.5h, and 99.776g of deionized water is slowly added dropwise and stirred at high speed for 1.5h to prepare the double-bond-terminated fluorescent polyurethane emulsion.
After the emulsification is completed, 6.470g of sodium dodecyl sulfate is added, the temperature is slowly raised to 80 ℃, nitrogen is protected, 1.618g of potassium persulfate, 0.147g of mercaptoethanol and 1.470g of isopropanol are added, then a mixture of 119.574g of dodecafluoroheptyl methacrylate and 42.180g of butyl acrylate is slowly added dropwise, after the heat preservation reaction is carried out for 2.5 hours, 0.503g of NaHCO is added3Neutralizing to obtain the fluorine-containing acrylate modified polyurethane emulsion with fluorescent property.