CN106634218A - Carbon quantum dot modified waterborne polyurethane gravure fluorescent ink and preparation method thereof - Google Patents
Carbon quantum dot modified waterborne polyurethane gravure fluorescent ink and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention discloses carbon quantum dot modified waterborne polyurethane gravure fluorescent ink which consists of the following raw materials in parts by weight: 0.6-1 part of 2-bromine-4-methylphenol, 4-6 parts of tung oil, 17-20 parts of glycerol, 0.1-0.2 part of sodium methylate, 6-8 parts of citric acid, 0.7-1 part of ethidene diamine, 50-60 parts of toluene diisocynate, 60-70 parts of polyester glycol, 0.8-2 pars of dibutyltin dilaurate, 1-2 parts of dimethylolpropionic acid, 2-3 parts of polyvinylpyrrolidone, 10-17 parts of aqueous pigment, 3-4 parts of lauryl sodium sulfate, 1-2 parts of simethicone, 2-3 parts of sodium lauroyl sarcosine, 2-3 parts of glyceryl monostearate, 1-2 parts of aluminum stearate, 0.4-1 part of dibenzothiazyl disulfide, 3-4 parts of tetrabutyl titanate, 0.1-0.4 part of alkylated diphenylamines, 0.3-1 part of 2-octyl-3(2H)-isothiazolone and 1-2 parts of ammonium metaborate.
Description
Technical field
The present invention relates to technical field of ink, more particularly to a kind of carbon quantum dot modified aqueous polyurethane gravure fluorescent ink
And preparation method thereof.
Background technology
Water color ink is the ink with water as solvent, and advantage of the water as solvent is：Nontoxic, free from extraneous odour, do not fire, and
The discharge capacity of VOC is greatly reduced, the pollution to environment is reduced, therefore has obtained development at full speed.And as water
A kind of water-based polyurethane ink in property ink, not only with water color ink safety and environmental protection the characteristics of, and have concurrently excellent resistance to
Mill property, the distinctive advantage of the polyurethane of resistance to water, chemical resistance and soft durometer adjustability, thus aqueous polyurethane is in ink
Application it is more and more extensive；But aqueous polyurethane is due to containing hydrophilic radical in molecular structure, thus with water-fast
Property congenital not enough weakness, the performance of aqueous polyurethane cannot match in excellence or beauty with traditional solvent borne polyurethane.Simultaneously with oil
The increasingly depleted of resource, people are sought for a kind of resource of natural reproducible to replace traditional non-renewable petroleum-type former
Expect to prepare Green Polymer Material；
Tung oil is the distinctive natural reproducible resource of China, and its abundance, environmental protection contains three in tung oil molecular structure
Unsaturated conjugated double bond, during aqueous polyurethane strand can be introduced into, using during film-forming tung oil it is oxidation cross-linked
Reaction makes linear aqueous polyurethane form certain cross-linked structure, not only can so improve the resistance to water of aqueous polyurethane with
And combination property, while application of the biomass renewable resource in polyurethane field can be improved, meet sending out for environmental protection
Exhibition is required；
Defect that resistance to water for aqueous polyurethane, solvent resistance aspect are present and comprehensive in order to further improve its
Can, many researchers have carried out fruitful initiative research work, and current research is concentrated mainly on modified to it
On.Cross-linking modified is to improve aqueous polyurethane water-resistance, solvent resistance, improve the most fruitful side such as mechanical property and hot property
Method.Based on this, the present invention utilizes the characteristic of the normal temperature oxidation self-crosslinking of tung oil base, by introducing tung oil base in polyurethane backbone
Tung oil-modified water-based polyurethane is prepared, and aqueous polyurethane printing-ink is prepared for as ink adhesive；
There is research to be prepared for high-quality fluorescent carbon quantum dot by microwave assisting method, and illustrate carbon quantum dot fluorescent ink and exist
Fluorescence character on skin and the fingerprint being imprinted on paper.The fluorescence quantum for being prepared is coated on paper, natural in air
It is dried, its fluorescent emission is remarkably reinforced (strengthen 40% by 14%).This phenomenon is with carbon quantum dot liquid deposition in glass, gold
Due to caused fluorescent quenching phenomenon contrast of reuniting in category, silicon chip or plastic-substrates.Also, the paper of carbon quantum dot coating
Still there is excitation wavelength dependence, this shows, this carbon quantum dot solution can be used as a kind of new fluorescent ink.Different from it
His fluorescent ink, carbon quantum dot ink has fluorescence exciting wavelength dependence this distinguishing feature, can replace traditional ink, uses
In false proof and information recognize carbon quantum dot have it is nontoxic, inexpensive, prepare simple, good biocompatibility and be easy to function of surface
The advantages of change, particularly its superior fluorescence property and biocompatibility so as in necks such as bio-imaging, sensing and photoelectric devices
Domain has a wide range of applications.But in view of carbon quantum dot in the fluorescent quenching being dried or the easy generation of state of aggregation is stronger so as to
It is restricted in the application of solid state fluorescence equipment.In order to keep the physics and chemical stability of carbon quantum dot, prevent its acid or
Reunite under ionic condition, the application of carbon quantum dot is typically necessary and is further combined it with host material, in conventional research
In be mostly semiconductor-quantum-point and polymer is combined, but it is usually be connected using non-covalent bond with the macromolecular of mark, knot
Structure is very unstable, in addition the environmental hazard of semiconductor-quantum-point itself, makes the fluorescent polymer that semiconductor-quantum-point is marked exist
The application in many fields such as biological medicine is restricted.As the green substitute of semiconductor-quantum-point, carbon quantum dot be polymerized
The compound of thing is arisen at the historic moment；
On the basis of the carbon quantum dot for preparing good fluorescence performance, itself and aqueous polyurethane are combined becomes a kind of new to the present invention
Type has the multi-functional plural gel of fluorescence and temperature-responsive concurrently, while overcome carbon quantum dot in the easy fluorescent quenching of solid-state
Shortcoming.Additionally, prepare carbon-based hydrogel nano ink by the method, and by coating or intaglio printing, on different substrates
Print phosphor pattern.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of carbon quantum dot modified aqueous polyurethane is recessed
Print fluorescent ink and preparation method thereof.
The present invention is achieved by the following technical solutions：
A kind of carbon quantum dot modified aqueous polyurethane gravure fluorescent ink, it is made up of the raw material of following weight parts：
2- bromo-4-methylphenol 0.6-1, tung oil 4-6, glycerine 17-20, sodium methoxide 0.1-0.2, citric acid 6-8, ethylenediamine
0.7-1, toluene di-isocyanate(TDI) 50-60, polyester diol 60-70, dibutyl tin laurate 0.8-2, dihydromethyl propionic acid
1-2, polyvinylpyrrolidone 2-3, aqueous pigment 10-17, lauryl sodium sulfate 3-4, dimethicone 1-2, lauroyl flesh
Propylhomoserin sodium 2-3, glycerin monostearate 2-3, aluminum stearate 1-2, dibenzothiazyl disulfide 0.4-1, butyl titanate 3-4,
Alkylated diphenylamine 0.1-0.4, octylisothiazolinone 0.3-1, ammonium metaborate 1-2.
A kind of preparation method of described carbon quantum dot modified aqueous polyurethane gravure fluorescent ink, comprises the following steps：
（1）Above-mentioned 2- bromo-4-methylphenols are added in glycerine, are stirred, mixed with above-mentioned tung oil, sodium methoxide, sent
Enter in reactor, be passed through nitrogen, the stirring reaction 4-5 hour at 200-210 DEG C, discharging adds reacting rear material weight
1.8-2 times of saturated sodium-chloride water solution, stratification takes upper strata oil solution, obtains tung oil-modified dihydroxylic alcohols；
（2）Above-mentioned citric acid, ethylenediamine are mixed, in being added to compound weight 38-40 times deionized water, polytetrafluoroethyl-ne is sent into
In alkene reaction kettle, 5-6 hours are incubated at 180-190 DEG C, cooling, takes supernatant at 10000-12000 rev/min of centrifugation 27-30 minute
Liquid, obtains carbon quantum dot solution；
（3）By above-mentioned octylisothiazolinone, sodium lauroyl sarcosine mix, be added to compound weight 36-40 times go from
In sub- water, the insulated and stirred 20-30 minute at 40-50 DEG C, above-mentioned butyl titanate is added, it is 70-80 DEG C to rise high-temperature, is added dropwise
The sulfuric acid of 3-4mol/l, regulation pH is 1-2, insulated and stirred 7-10 minute, is mixed with above-mentioned carbon quantum dot solution, is stirred to normal
Temperature, obtains sol-gel modified carbon quantum dot solution；
（4）Above-mentioned polyvinylpyrrolidone is added in the deionized water of its weight 200-300 times, with above-mentioned sol-gel modified carbon
Quantum dot solution mixes, and ultrasonic 2-3 minutes, obtains carbon quantum dot dispersion liquid；
（5）Above-mentioned dibenzothiazyl disulfide is added in the absolute ethyl alcohol of its weight 3-5 times, aluminum stearate is added, in 70-
Insulated and stirred 10-17 minute at 80 DEG C, obtain pre- mixed alcoholic liquid；
（6）Above-mentioned polyester diol, pre- mixed alcoholic liquid are mixed, 10-11 hours are dried in 100-105 DEG C of vacuum drying chamber,
Discharging cooling, in sending into reactor, is passed through nitrogen, and it is 40-50 DEG C to adjust temperature of reaction kettle, and above-mentioned toluene diisocynate is added dropwise
Ester, after completion of dropping 20-30 minutes are incubated, and add above-mentioned dibutyl tin laurate, ammonium metaborate, and liter high-temperature is 60-70
DEG C, insulation reaction 100-120 minute, dihydromethyl propionic acid is added, insulated and stirred 100-110 minute, add tung oil-modified binary
Alcohol, alkylated diphenylamine, stirring reaction 1-2 hour is cooled to room temperature, adds above-mentioned carbon quantum dot dispersion liquid, 2000-2300
Rev/min emulsification pretreatment 20-30 minutes, obtain modified emulsion；
（7）Above-mentioned modified emulsion is mixed with remaining each raw material, grinding is uniform, obtains final product.
It is an advantage of the invention that：The present invention adopts tung oil-modified dihydroxylic alcohols as the raw material of synthesis of polyurethane so that tung oil
Contain conjugated double bond in modified polyurethane system, autoxidation crosslinking occurs during film-forming so that linear
Crosslinking or partial cross-linked structure are formed in aqueous polyurethane molecular structure, so as to substantially increase the resistance to water of aqueous polyurethane；
Simultaneously crosslinking points are defined in molecular chain structure through modified aqueous polyurethane, become three-dimensional net structure, improved
Its heat resistance, the present invention on carbon quantum dot surface introduces amino by changing carbon matrix precursor-citric acid and ethylenediamine, fills out
Mend the defect on carbon quantum dot surface or make its surface produce energy potential well, make fluorescent emission more stable, so as to improve fluorescence quantum yield,
The fluorescence property for making carbon quantum dot is greatly improved, the present invention water color ink can by coating, gravure application black paper,
Different phosphor patterns printings are prepared on quartz plate, Kapton, pet film substrate different
Phosphor pattern
The ink physical extension performance of the present invention is good, and print image glossiness, color saturation are good, and integrated quality is superior.
Specific embodiment
A kind of carbon quantum dot modified aqueous polyurethane gravure fluorescent ink, it is made up of the raw material of following weight parts：
2 bromomethyl phenol 0.6, tung oil 4, glycerine 17, sodium methoxide 0.1, citric acid 6, ethylenediamine 0.7, toluene di-isocyanate(TDI)
50th, polyester diol 60, dibutyl tin laurate 0.8, dihydromethyl propionic acid 1, polyvinylpyrrolidone 2, aqueous pigment 10,
Lauryl sodium sulfate 3, dimethicone 1, sodium lauroyl sarcosine 2, glycerin monostearate 2, aluminum stearate 1, curing
Bisbenzothiazole 0.4, butyl titanate 3, alkylated diphenylamine 0.1, octylisothiazolinone 0.3, ammonium metaborate 1.
A kind of preparation method of described carbon quantum dot modified aqueous polyurethane gravure fluorescent ink, comprises the following steps：
（1）Above-mentioned 2 bromomethyl phenol is added in glycerine, is stirred, mixed with above-mentioned tung oil, sodium methoxide, be sent to
In reactor, nitrogen is passed through, stirring reaction 4 hours at 200 DEG C, discharging adds the saturation chlorine of 1.8 times of reacting rear material weight
Change sodium water solution, stratification takes upper strata oil solution, obtains tung oil-modified dihydroxylic alcohols；
（2）Above-mentioned citric acid, ethylenediamine are mixed, in being added to 38 times of deionized waters of compound weight, polytetrafluoroethylene (PTFE) is sent into
In reactor, 5 hours are incubated at 180 DEG C, cooling, 10000 revs/min are centrifuged 27 minutes, take supernatant, obtain carbon quantum dot molten
Liquid；
（3）Above-mentioned octylisothiazolinone, sodium lauroyl sarcosine are mixed, the deionized water of 36 times of compound weight is added to
In, insulated and stirred 20 minutes at 40 DEG C add above-mentioned butyl titanate, and it is 70 DEG C to rise high-temperature, and the sulfuric acid of 3mol/l is added dropwise,
It is 1 to adjust pH, and insulated and stirred 7 minutes mixes with above-mentioned carbon quantum dot solution, stirs to normal temperature, obtains sol-gel modified carbon quantum dot
Solution；
（4）Above-mentioned polyvinylpyrrolidone is added in the deionized water of 200 times of its weight, with above-mentioned sol-gel modified carbon quantum
Point solution mixing, ultrasound 2 minutes obtains carbon quantum dot dispersion liquid；
（5）Above-mentioned dibenzothiazyl disulfide is added in the absolute ethyl alcohol of 3 times of its weight, aluminum stearate is added, at 70 DEG C
Lower insulated and stirred 10 minutes, obtains pre- mixed alcoholic liquid；
（6）Above-mentioned polyester diol, pre- mixed alcoholic liquid are mixed, is dried 10 hours in 100 DEG C of vacuum drying chamber, discharged cold
But, send in reactor, be passed through nitrogen, it is 40 DEG C to adjust temperature of reaction kettle, and above-mentioned toluene di-isocyanate(TDI), completion of dropping is added dropwise
Afterwards 20 minutes are incubated, add above-mentioned dibutyl tin laurate, ammonium metaborate, it is 60 DEG C to rise high-temperature, 100 points of insulation reaction
Clock, adds dihydromethyl propionic acid, insulated and stirred 100 minutes to add tung oil-modified dihydroxylic alcohols, alkylated diphenylamine, stirring reaction 1
Hour, it is cooled to room temperature, add above-mentioned carbon quantum dot dispersion liquid, 2000 revs/min of emulsification pretreatments 20 minutes obtain modified emulsion；
（7）Above-mentioned modified emulsion is mixed with remaining each raw material, grinding is uniform, obtains final product.
The water color ink specimen page of the present invention is have printed using gravure printing adaptive instrument, water color ink does not have in printing process
Occur flying ink, the phenomenon of spanishing, ink is shifted well on ink roller, specimen page site is clear after print, mass colour is distinct；
Performance test：
Adhesive force：>=1 grade；
Glossiness：85°；
First dryness：17mm/30s；
Resistance to water：It is qualified.
Claims (2)
1. a kind of carbon quantum dot modified aqueous polyurethane gravure fluorescent ink, it is characterised in that it is by the original of following weight parts
Material composition：
2- bromo-4-methylphenol 0.6-1, tung oil 4-6, glycerine 17-20, sodium methoxide 0.1-0.2, citric acid 6-8, ethylenediamine
0.7-1, toluene di-isocyanate(TDI) 50-60, polyester diol 60-70, dibutyl tin laurate 0.8-2, dihydromethyl propionic acid
1-2, polyvinylpyrrolidone 2-3, aqueous pigment 10-17, lauryl sodium sulfate 3-4, dimethicone 1-2, lauroyl flesh
Propylhomoserin sodium 2-3, glycerin monostearate 2-3, aluminum stearate 1-2, dibenzothiazyl disulfide 0.4-1, butyl titanate 3-4,
Alkylated diphenylamine 0.1-0.4, octylisothiazolinone 0.3-1, ammonium metaborate 1-2.
2. a kind of preparation method of carbon quantum dot modified aqueous polyurethane gravure fluorescent ink as claimed in claim 1, it is special
Levy and be, comprise the following steps：
（1）Above-mentioned 2- bromo-4-methylphenols are added in glycerine, are stirred, mixed with above-mentioned tung oil, sodium methoxide, sent
Enter in reactor, be passed through nitrogen, the stirring reaction 4-5 hour at 200-210 DEG C, discharging adds reacting rear material weight
1.8-2 times of saturated sodium-chloride water solution, stratification takes upper strata oil solution, obtains tung oil-modified dihydroxylic alcohols；
（2）Above-mentioned citric acid, ethylenediamine are mixed, in being added to compound weight 38-40 times deionized water, polytetrafluoroethyl-ne is sent into
In alkene reaction kettle, 5-6 hours are incubated at 180-190 DEG C, cooling, takes supernatant at 10000-12000 rev/min of centrifugation 27-30 minute
Liquid, obtains carbon quantum dot solution；
（3）By above-mentioned octylisothiazolinone, sodium lauroyl sarcosine mix, be added to compound weight 36-40 times go from
In sub- water, the insulated and stirred 20-30 minute at 40-50 DEG C, above-mentioned butyl titanate is added, it is 70-80 DEG C to rise high-temperature, is added dropwise
The sulfuric acid of 3-4mol/l, regulation pH is 1-2, insulated and stirred 7-10 minute, is mixed with above-mentioned carbon quantum dot solution, is stirred to normal
Temperature, obtains sol-gel modified carbon quantum dot solution；
（4）Above-mentioned polyvinylpyrrolidone is added in the deionized water of its weight 200-300 times, with above-mentioned sol-gel modified carbon
Quantum dot solution mixes, and ultrasonic 2-3 minutes, obtains carbon quantum dot dispersion liquid；
（5）Above-mentioned dibenzothiazyl disulfide is added in the absolute ethyl alcohol of its weight 3-5 times, aluminum stearate is added, in 70-
Insulated and stirred 10-17 minute at 80 DEG C, obtain pre- mixed alcoholic liquid；
（6）Above-mentioned polyester diol, pre- mixed alcoholic liquid are mixed, 10-11 hours are dried in 100-105 DEG C of vacuum drying chamber,
Discharging cooling, in sending into reactor, is passed through nitrogen, and it is 40-50 DEG C to adjust temperature of reaction kettle, and above-mentioned toluene diisocynate is added dropwise
Ester, after completion of dropping 20-30 minutes are incubated, and add above-mentioned dibutyl tin laurate, ammonium metaborate, and liter high-temperature is 60-70
DEG C, insulation reaction 100-120 minute, dihydromethyl propionic acid is added, insulated and stirred 100-110 minute, add tung oil-modified binary
Alcohol, alkylated diphenylamine, stirring reaction 1-2 hour is cooled to room temperature, adds above-mentioned carbon quantum dot dispersion liquid, 2000-2300
Rev/min emulsification pretreatment 20-30 minutes, obtain modified emulsion；
（7）Above-mentioned modified emulsion is mixed with remaining each raw material, grinding is uniform, obtains final product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961666A (en) * | 2021-03-08 | 2021-06-15 | 西南石油大学 | Nano composite cross-linking agent for fracturing fluid and preparation method thereof |
| CN113249108A (en) * | 2021-05-14 | 2021-08-13 | 西南石油大学 | Ultrahigh-temperature-resistant fracturing fluid and preparation method thereof |
| CN115322775A (en) * | 2022-07-12 | 2022-11-11 | 公安部物证鉴定中心 | Fingerprint developing agent based on nitrogen-doped carbon quantum dots, preparation method and application |
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| CN103923647A (en) * | 2014-04-21 | 2014-07-16 | 中国石油大学(北京) | Nitrogen-doped high-luminescent carbon quantum dot and preparation method thereof |
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