CN110330622B - Fluorescent waterborne polyurethane and preparation method thereof - Google Patents
Fluorescent waterborne polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to fluorescent waterborne polyurethane and a preparation method thereof, belonging to the technical field of functional waterborne polyurethane synthesis. The preparation method of the fluorescent waterborne polyurethane comprises the following steps: mixing diisocyanate and fluorescein in an inert atmosphere, reacting at 50-70 ℃, adding oligomer dihydric alcohol, a hydrophilic chain extender and a catalyst, and heating to 70-90 ℃ for reaction to obtain a fluorescent waterborne polyurethane prepolymer containing terminal isocyanate; and cooling to 40-60 ℃, adjusting the solid content, adding a small molecular chain extender for reaction, and then adding a neutralizer for reaction to obtain the fluorescent polyurethane. The method for preparing the fluorescent waterborne polyurethane is beneficial to fully introducing the fluorescein to a polyurethane main chain, avoids influence on introduction of small fluorescein molecules caused by large polyurethane molecules due to viscosity and large molecular weight of oligomer dihydric alcohol and prepolymer, and can control the addition amount of the fluorescein to adjust the chromophore content of polyurethane molecules.
Description
Technical Field
The invention relates to fluorescent waterborne polyurethane and a preparation method thereof, belonging to the technical field of functional waterborne polyurethane synthesis.
Background
With the establishment of environmental regulations and consciousness, the waterborne polyurethane is a novel polyurethane system which takes water instead of an organic solvent as a dispersion medium, has the advantages of no pollution, good compatibility, excellent mechanical property, easy modification and the like, can be widely used for coatings, adhesives, fabric coatings, finishing agents, leather finishing agents and the like, and is gradually and widely researched and applied.
The fluorescent waterborne polyurethane is also a hotspot of research in recent years, and fluorescent molecules with conjugated double bonds and luminous efficiency are introduced to the main chain of the waterborne polyurethane in a chemical structure mode, so that the problems of poor fluorescence stability, fluorescence quenching phenomenon and high thermal mobility caused by direct physical blending of the waterborne polyurethane and a fluorescent material are solved.
The Chinese patent application with the application number of 2013102238683 discloses a preparation method of fluorescent dye-containing waterborne polyurethane, which comprises the steps of reacting a fluorescent dye with a benzene ring conjugated structure and hydroxyl or amino on the molecule with isocyanic acid radicals to be connected onto a polyurethane molecular chain to form a fluorescent polyurethane prepolymer, and further reacting to obtain the fluorescent waterborne polyurethane. The selected fluorescent dye is in a molecular structure of terminal hydroxyl or terminal amino and is subjected to end-capping reaction with isocyanic acid radical. The application number 2015107121406 discloses an environment-friendly fluorescent waterborne polyurethane and a preparation method thereof, wherein a fluorescent agent containing terminal hydroxyl is selected for chain extension, fluorescent groups on fluorescent agent molecules are utilized to excite the waterborne polyurethane to transition and emit light, and the adopted fluorescent agent is a carbon-carbon and carbon-nitrogen double bond plane conjugated structure. However, the products prepared by the prior art have small introduction amount of fluorescent molecules and lower fluorescence effect.
Disclosure of Invention
The first problem to be solved by the invention is to provide a preparation method of fluorescent waterborne polyurethane, by adopting the method, fluorescein can fully react, so that the fluorescein is fully introduced to a polyurethane main chain.
In order to solve the first technical problem of the present invention, the preparation method of the fluorescent waterborne polyurethane comprises the following steps:
a. mixing diisocyanate and fluorescein in an inert atmosphere, and reacting for 2-3 h at 50-70 ℃;
the fluorescein is a dihydroxy benzene ring conjugated structure; preferably a sulfur-containing bishydroxy benzene ring conjugated structure;
b. adding oligomer dihydric alcohol, a hydrophilic chain extender and a catalyst into the solution obtained after the reaction in the step a, and heating to 70-90 ℃ for reaction to obtain a fluorescent waterborne polyurethane prepolymer containing terminal isocyanate;
c. cooling the fluorescent waterborne polyurethane prepolymer obtained in the step b to 40-60 ℃, adjusting the solid content to 40-70%, adding a small molecular chain extender for reaction, and then adding a neutralizer for reaction to obtain fluorescent polyurethane;
wherein the molar ratio of-NCO groups in the diisocyanate to the total-OH groups in the oligomer diol and the micromolecule chain extender is 1.2-2.0: 1;
the weight ratio of-NCO group in diisocyanate, sulfur-containing fluorescein, hydrophilic chain extender, catalyst, micromolecule chain extender, neutralizer and fluorescent waterborne polyurethane prepolymer is as follows: 2 to 48:0.01 to 1:3 to 9:0.01 to 0.1:0.03 to 0.9:1 to 7: 100.
The inert gas atmosphere in the present invention means a gas which does not react with the raw materials, intermediates and products, such as nitrogen, and may be argon, helium, etc.
Preferably, the fluorescein is
Preferably, the diisocyanate is at least one of toluene diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 3,3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate, and 4,4 ' -dicyclohexylmethane diisocyanate.
Preferably, the hydrophilic chain extender is at least one of dimethylolpropionic acid and dimethylolbutyric acid; the catalyst is preferably at least one of dibutyltin dilaurate and stannous octoate; the chain extender is preferably at least one of 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, diethylene glycol, neopentyl glycol and 1, 4-cyclohexanediol; the neutralizing agent is preferably at least one of trimethylamine, triethylamine, tripropylamine, sodium hydroxide and ammonia water.
Preferably, the reaction time in the step b is 3-6 hours;
c, the time for adding the small molecular chain extender for reaction is preferably 2-5 h; the time for adding the neutralizing agent to react in the step c is preferably 0.5-2 h.
Preferably, the oligomer dihydric alcohol in the step b is polymerized by 4-60 monomers, preferably 4-20 monomers; preferably, the oligomer diol is one or two of polyethylene glycol, polycarbonate diol, polytetrahydrofuran diol, polycaprolactone diol, polybutylene adipate, polyhexamethylene adipate, polypropylene glycol and polytetramethylene glycol.
The oligomer diol contains no water, and the oligomer diol may be dried by conventional drying methods, such as vacuum drying under reduced pressure, to ensure no water.
Preferably, step c is carried out using a ketone or acetone to adjust the solids content.
Further, the method also comprises the step d, mixing the fluorescent polyurethane with water, emulsifying, and preparing fluorescent aqueous polyurethane emulsion; preferably, the fluorescent polyurethane is mixed with water, and the mixture is stirred and emulsified for 10-30 min at the speed of more than 1000rpm to obtain the fluorescent waterborne polyurethane emulsion.
Further, the method further comprises the step of evaporating and recovering the fluorescence-containing waterborne polyurethane emulsion ketone or acetone to obtain the fluorescence waterborne polyurethane with the solid content of 20-40%.
The second technical problem to be solved by the invention is to provide the fluorescent waterborne polyurethane, which is prepared by the method, and the introduction amount of the fluorescein micromolecules is 0.01-1% of the total mass of the fluorescent waterborne polyurethane.
Has the advantages that:
the method for preparing the fluorescent waterborne polyurethane is beneficial to fully introducing the fluorescein to a polyurethane main chain, avoids influence on introduction of small fluorescein molecules caused by large polyurethane molecules due to viscosity and large molecular weight of oligomer dihydric alcohol and prepolymer, and can control the addition amount of the fluorescein to adjust the chromophore content of polyurethane molecules.
The method has simple process, good reproducibility and adjustable soft and hard segments, and can obtain the waterborne polyurethane with the fluorescence characteristic in a small amount without excessive addition of the fluorescein because the fluorescein is fully reacted.
Drawings
FIG. 1 is an infrared spectrum of fluorescein isothiocyanate and a sulfur-containing fluorescent waterborne polyurethane prepolymer described in example 1 of the present invention.
FIG. 2 shows fluorescein isothiocyanate (. lamda.) according to example 1 of the present inventionex490nm, slit 8nm) and sulfur-containing fluorescent waterborne polyurethane (lambda)ex470nm, slit 10 nm).
FIG. 3 is a scanning electron micrograph (left) and a surface analysis chart (right) of elemental sulfur of the sulfur-containing fluorescent waterborne polyurethane prepared in example 3 of the present invention;
FIG. 4 is a graph of the mechanical data of the aqueous polyurethane (tensile strength: 25.6MPa) and of the sulfur-containing fluorescent aqueous polyurethane prepared in inventive example 3 (tensile strength: 32.7 MPa);
WPU-waterborne polyurethane; FWPU-fluorescent waterborne polyurethane; FITC-fluorescein isothiocyanate.
Detailed Description
In order to solve the first technical problem of the present invention, the preparation method of the fluorescent waterborne polyurethane comprises the following steps:
a. mixing diisocyanate and fluorescein in an inert atmosphere, and reacting for 2-3 h at 50-70 ℃;
the fluorescein is a dihydroxy benzene ring conjugated structure; preferably a sulfur-containing bishydroxy benzene ring conjugated structure;
b. adding oligomer dihydric alcohol, a hydrophilic chain extender and a catalyst into the solution obtained after the reaction in the step a, and heating to 70-90 ℃ for reaction to obtain a fluorescent waterborne polyurethane prepolymer containing terminal isocyanate;
c. cooling the fluorescent waterborne polyurethane prepolymer obtained in the step b to 40-60 ℃, adjusting the viscosity, adding a small molecular chain extender for reaction, and then adding a neutralizer for reaction to obtain fluorescent polyurethane;
wherein the molar ratio of-NCO groups in the diisocyanate to the total-OH groups in the oligomer diol and the micromolecule chain extender is 1.2-2.0: 1;
the weight ratio of-NCO group in diisocyanate, sulfur-containing fluorescein, hydrophilic chain extender, catalyst, micromolecule chain extender, neutralizer and fluorescent waterborne polyurethane prepolymer is as follows: 2 to 48:0.01 to 1:3 to 9:0.01 to 0.1:0.03 to 0.9:1 to 7: 100.
Preferably, the fluorescein is
Preferably, the diisocyanate is at least one of toluene diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 3,3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate, and 4,4 ' -dicyclohexylmethane diisocyanate.
Preferably, the hydrophilic chain extender is at least one of dimethylolpropionic acid and dimethylolbutyric acid; the catalyst is preferably at least one of dibutyltin dilaurate and stannous octoate; the chain extender is preferably at least one of 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, diethylene glycol, neopentyl glycol and 1, 4-cyclohexanediol; the neutralizing agent is preferably at least one of trimethylamine, triethylamine, tripropylamine, sodium hydroxide and ammonia water.
Preferably, the reaction time in the step b is preferably 3-6 h;
c, the time for adding the small molecular chain extender for reaction is preferably 2-5 h; the time for adding the neutralizing agent to react in the step c is preferably 0.5-2 h.
Preferably, the oligomer dihydric alcohol in the step b is polymerized by 4-60 monomers, preferably 4-20 monomers; preferably, the oligomer diol is one or two of polyethylene glycol, polycarbonate diol, polytetrahydrofuran diol, polycaprolactone diol, polybutylene adipate, polyhexamethylene adipate, polypropylene glycol and polytetramethylene glycol.
Preferably, step c is carried out using a ketone or acetone to adjust the solids content.
Further, the method also comprises the step d, mixing the fluorescent polyurethane with water, emulsifying, and preparing fluorescent aqueous polyurethane emulsion; preferably, the fluorescent polyurethane is mixed with water, and the mixture is stirred and emulsified for 10-30 min at the speed of more than 1000rpm to obtain the fluorescent waterborne polyurethane emulsion.
Further, the method further comprises the step of evaporating and recovering the fluorescence-containing waterborne polyurethane emulsion ketone or acetone to obtain the fluorescence waterborne polyurethane with the solid content of 20-40%.
The second technical problem to be solved by the invention is to provide the fluorescent waterborne polyurethane, which is prepared by the method, and the introduction amount of the fluorescein micromolecules is 0.01-1% of the total mass of the fluorescent waterborne polyurethane.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
Polycarbonate diol (number average molecular weight 1000) was dehydrated under reduced pressure at 120 ℃ for 2 hours, and 15.28ml of isophorone diisocyanate and 10mg of Fluorescein Isothiocyanate (FITC) were added to a 100ml flask under nitrogen protection to react at 60 ℃ for 2 hours.
Then, 30.00g of polycarbonate diol and 2.31g of dimethylolpropionic acid (a small amount of dimethylformamide is dissolved) are sequentially added, 0.02g of dibutyltin dilaurate is added, the temperature is increased to 80 ℃ for reaction for 4 hours, then the temperature is reduced to 50 ℃, 50ml of acetone is added, stirring and dissolving are carried out for 30 minutes, 0.23ml of 1, 4-butanediol is added, reaction is continued for 2 hours, and then 2.39ml of triethylamine is added for neutralization reaction for 30 minutes, so that the fluorescent polyurethane is obtained. And finally pouring the mixture into a beaker, adding 75ml of deionized water, carrying out high-speed emulsification at 1000rpm for 20min, and finally recovering acetone through a rotary evaporator to obtain the yellow-green aqueous polyurethane emulsion containing the sulfur fluorescein.
Fluorescein Isothiocyanate (FITC) in the reacted solution was detected, and the reaction rate of fluorescein isothiocyanate was 98.5%.
Example 2
Polytetrahydrofuran diol (number average molecular weight 2000) was dehydrated under reduced pressure at 120 ℃ for 2 hours, and 5.80ml of toluene diisocyanate and 8mg of Fluorescein Isothiocyanate (FITC) were added to a 100ml flask under nitrogen protection to react at 60 ℃ for 2 hours.
Then, 20.00g of polytetrahydrofuran diol and 1.90g of dimethylolpropionic acid (a small amount of dimethylformamide is dissolved) are sequentially added, 0.01g of dibutyltin dilaurate is added, the temperature is increased to 80 ℃ for reaction for 4 hours, then the temperature is reduced to 50 ℃, 50ml of acetone is added, stirring and dissolving are carried out for 30 minutes, 0.12ml of diethylene glycol is added, reaction is continued for 2 hours, and then 1.97ml of triethylamine is added for neutralization reaction for 30 minutes, so that the fluorescent polyurethane is obtained. And finally pouring the mixture into a beaker, adding 70ml of deionized water, carrying out high-speed emulsification for 20min at 1000rpm, and finally recovering acetone through a rotary evaporator to obtain the yellow-green aqueous polyurethane emulsion containing the sulfur fluorescein.
Fluorescein Isothiocyanate (FITC) in the reacted solution was detected, and the reaction rate of fluorescein isothiocyanate was 96.4%.
Example 3
Polycarbonate diol (number average molecular weight 1000) was dehydrated under reduced pressure at 120 ℃ for 2 hours, and 8.17ml of toluene diisocyanate and 15mg of Fluorescein Isothiocyanate (FITC) were added to a 100ml flask under nitrogen protection to react at 60 ℃ for 3 hours.
Then, 30.00g of polycarbonate diol and 2.80g of dimethylolbutyric acid (a small amount of dimethylformamide is dissolved) are sequentially added, 0.02g of dibutyltin dilaurate is added, the temperature is increased to 80 ℃ for reaction for 4 hours, then the temperature is reduced to 50 ℃, 50ml of acetone is added, stirring and dissolving are carried out for 30 minutes, 0.18ml of diethylene glycol is added, reaction is continued for 3 hours, and then 2.63ml of triethylamine is added for neutralization reaction for 1 hour, so that the fluorescent polyurethane is obtained. And finally pouring the mixture into a beaker, adding 65ml of deionized water, carrying out high-speed emulsification for 30min at 1000rpm, and finally recovering acetone through a rotary evaporator to obtain the yellow-green aqueous polyurethane emulsion containing the sulfur fluorescein.
Fluorescein Isothiocyanate (FITC) in the reacted solution was detected, and the reaction rate of fluorescein isothiocyanate was 97.3%.
Example 4
Polypropylene glycol (number average molecular weight 3000) was dehydrated under reduced pressure at 120 ℃ for 2 hours, and 10.16ml of isophorone diisocyanate and 20mg of Fluorescein Isothiocyanate (FITC) were added to a 100ml flask under nitrogen protection to react at 60 ℃ for 2 hours.
Then, 40.00g of polypropylene glycol and 1.79g of dimethylolpropionic acid (a small amount of dimethylformamide is dissolved) are sequentially added, 0.02g of dibutyltin dilaurate is added, the temperature is increased to 80 ℃ for reaction for 4 hours, then the temperature is reduced to 50 ℃, 50ml of acetone is added, stirring and dissolving are carried out for 30 minutes, 0.13ml of diethylene glycol is added, reaction is continued for 2 hours, and then 1.85ml of triethylamine is added for neutralization reaction for 30 minutes, so that the fluorescent polyurethane is obtained. And finally pouring the mixture into a beaker, adding 100ml of deionized water, emulsifying at a high speed of 1000rpm for 20min, and finally recovering acetone through a rotary evaporator to obtain the yellow-green aqueous polyurethane emulsion containing the sulfur fluorescein.
Fluorescein Isothiocyanate (FITC) in the reacted solution was detected, and the reaction rate of fluorescein isothiocyanate was 95.3%.
Comparative example 1
Polycarbonate diol (number average molecular weight 1000) was dehydrated under reduced pressure at 120 ℃ for 2 hours, 30.00g of polycarbonate diol, 2.31g of dimethylolpropionic acid (a small amount of dimethylformamide dissolved), 15.28ml of isophorone diisocyanate and 10mg of Fluorescein Isothiocyanate (FITC) were added to a 100ml flask under nitrogen protection, and after the temperature was raised to 80 ℃, 0.02g of dibutyltin dilaurate was further added to react for 6 hours. Then cooling to 50 ℃, adding 50ml of acetone, stirring and dissolving for 30min, adding 0.23ml of 1, 4-butanediol, continuing to react for 2h, and then adding 2.39ml of triethylamine, and carrying out neutralization reaction for 30min to obtain the fluorescent polyurethane. And finally pouring the mixture into a beaker, adding 75ml of deionized water, carrying out high-speed emulsification at 1000rpm for 20min, and finally recovering acetone through a rotary evaporator to obtain the yellow-green aqueous polyurethane emulsion containing the sulfur fluorescein.
Fluorescein Isothiocyanate (FITC) in the reacted solution was detected, and the reaction rate of fluorescein isothiocyanate was 91.7%.
Claims (12)
1. The preparation method of the fluorescent waterborne polyurethane is characterized by comprising the following steps:
a. mixing diisocyanate and fluorescein in an inert atmosphere, and reacting for 2-3 h at 50-70 ℃;
b. adding oligomer dihydric alcohol, a hydrophilic chain extender and a catalyst into the solution obtained after the reaction in the step a, and heating to 70-90 ℃ for reaction to obtain a fluorescent waterborne polyurethane prepolymer containing terminal isocyanate;
c. cooling the fluorescent waterborne polyurethane prepolymer obtained in the step b to 40-60 ℃, adjusting the solid content to 40-70% by adopting ketone or acetone, adding a small molecular chain extender for reaction, and then adding a neutralizer for reaction to obtain fluorescent polyurethane;
d. mixing and emulsifying fluorescent polyurethane and water to obtain fluorescent aqueous polyurethane emulsion, and evaporating and recovering ketone or acetone in the fluorescent aqueous polyurethane emulsion to obtain the fluorescent aqueous polyurethane with the solid content of 20-40%; the emulsification is stirred and emulsified for 10-30 min at the speed of more than 1000 rpm;
wherein the molar ratio of-NCO groups in the diisocyanate to the total-OH groups in the oligomer diol and the micromolecule chain extender is 1.2-2.0: 1;
the weight ratio of-NCO group in diisocyanate, sulfur-containing fluorescein, hydrophilic chain extender, catalyst, micromolecule chain extender, neutralizer and fluorescent waterborne polyurethane prepolymer is as follows: 2-48: 0.01-1: 3-9: 0.01-0.1: 0.03-0.9: 1-7: 100;
the fluorescein is as follows:
2. the method of claim 1, wherein the diisocyanate is at least one of toluene diisocyanate, 1, 5-naphthalene diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 3,3 ' -dimethyl-4, 4 ' -biphenyl diisocyanate, and 4,4 ' -dicyclohexylmethane diisocyanate.
3. The preparation method of the fluorescent waterborne polyurethane as claimed in claim 1 or 2, wherein the hydrophilic chain extender is at least one of dimethylolpropionic acid and dimethylolbutyric acid.
4. The method for preparing the fluorescent waterborne polyurethane as set forth in claim 1 or 2, wherein the catalyst is at least one of dibutyltin dilaurate and stannous octoate.
5. The method for preparing fluorescent waterborne polyurethane of claim 1 or 2, wherein the small-molecule chain extender is at least one of 1, 2-propanediol, 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, diethylene glycol, neopentyl glycol, and 1, 4-cyclohexanediol.
6. The method of claim 1 or 2, wherein the neutralizing agent is at least one of trimethylamine, triethylamine, tripropylamine, sodium hydroxide and ammonia.
7. The preparation method of the fluorescent waterborne polyurethane as claimed in claim 1 or 2, wherein the reaction time in step b is 3-6 h.
8. The preparation method of the fluorescent waterborne polyurethane as claimed in claim 1 or 2, wherein the time for the reaction of adding the small molecule chain extender in step c is 2-5 h.
9. The preparation method of the fluorescent waterborne polyurethane as claimed in claim 1 or 2, wherein the time for the addition of the neutralizing agent in the step c is 0.5-2 h.
10. The preparation method of the fluorescent waterborne polyurethane as claimed in claim 1 or 2, wherein the oligomer diol in step b is polymerized from 4 to 60 monomers.
11. The preparation method of the fluorescent waterborne polyurethane as claimed in claim 1 or 2, wherein the oligomer diol in step b is polymerized from 4 to 20 monomers.
12. The method of claim 1 or 2, wherein the oligomer diol is one or two of polyethylene glycol, polycarbonate diol, polytetrahydrofuran diol, polycaprolactone diol, polybutylene adipate, polyhexamethylene adipate and polypropylene glycol.
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| CN112662223A (en) * | 2020-12-18 | 2021-04-16 | 合众（佛山）化工有限公司 | Self-antibacterial double-component water-based fluorescent paint |
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