CN110358366A - A kind of chemical stain fluorescent ink and preparation method and applications - Google Patents
A kind of chemical stain fluorescent ink and preparation method and applications Download PDFInfo
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- CN110358366A CN110358366A CN201910601929.2A CN201910601929A CN110358366A CN 110358366 A CN110358366 A CN 110358366A CN 201910601929 A CN201910601929 A CN 201910601929A CN 110358366 A CN110358366 A CN 110358366A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
- C09D11/17—Writing inks characterised by colouring agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
Abstract
A kind of fluorescence color-change ink, by dye molecule 2,5- diaminostilbene, 4- dibenzoic acid butyl ester, dye dispersant and solvent are formulated, and fluorescent ink painting are written on unbleached paper, yellow is presented in font, and issues yellow fluorescence under the ultraviolet light irradiation of 365nm;Font color can change color under the action of ink auxiliary agent; the painting of ink auxiliary agent is written in above-mentioned font; it is chemically reacted in situ on paper; different new fluorescences is generated according to the difference of acylating reagent concentration in ink auxiliary agent, green, blue-fluorescence can be presented in font under ultraviolet light irradiation.The fluorescent dye 2,5- diaminostilbene, 4- dibenzoic acid butyl ester preparation process is easy, write on paper be in yellow fluorescence, it is swift in response between ink auxiliary agent, with the increase of ink assistant concentration, font color can be crossfaded into green to colourless by yellow under natural light, and fluorescence color can be by the orange-yellow green that crossfades into blue under ultraviolet light irradiation.
Description
Technical field
The invention belongs to fluorescence luminescent material field, the preparation of especially a kind of single phenyl ring fluorescent dye and fluorescence discoloration
The preparation method of ink.
Background technique
Anti-fake fluorescent material can show bright-coloured fluorescent effect after the light wave excitation of certain specific wavelength.And work as light
After source removes, this luminescent behavior stops at once.As social market development and commodity counterfeit prevention need, fluorescence falsification preventing design of material
Quick development has been obtained in many fields.The existing organic fluorescence small molecule discoloration strong mutagens color of mechanism, molten mutagens color are photic
Discoloration etc..
Power mutagens color fluorescent molecule under the stimulation of external pressure or mechanical force, photophysical property (it is such as ultraviolet-
Visible absorbance, fluorescent emission etc.) reversible conversion can occur.This molecular configuration, accumulation mode of the transformation based on fluorescent molecule
It can change under external force stimulation with intermolecular force, such as the conversion of planes of molecules, singlet excitons, crystal form-nothing
Sizing, unformed-crystal form, the conversion of crystal form-crystal form etc..Such as Araki in 2007 et al. reports a kind of acetyl containing there are four
The derivative of the pyrene of amine, methanol, which is added, into the chloroformic solution of the compound is precipitated compound, forms white solid, has strong
Blue emission property, when power acts on this solid, color changes yellowly by white, and yellow solid has green fluorescence hair
It penetrates.Referring to: Sagara Y, Mutai T, Yoshikawa I, et al.Material design for piezochromic
luminescence:hydrogen-bond-directed assemblies of a pyrene derivative.[J]
.Journal of the American Chemical Society, 2007,129 (6): 1520-1.LIU et al. reports click
D- π-A type beta-diketon the boron difluoride complex TCBM and CBM of azoles modification, there is pressure to cause fluorescence discoloration property for they.CBM is in machine
Tool power stimulates lower launch wavelength from 548nm red shift to 572nm, and luminescent color becomes orange from yellow.It is connected with tertiary butyl groups
TCBM, its pressure cause fluorescence discoloration behavior fairly obvious, and the TCBM sample of synthesis issues strong green fluorescence, emission maximum wave
It grows after 547nm, grinding, luminescent color becomes orange, and maximum emission peak is in 597nm, red shift 50nm.This is because tert-butyl
Space steric effect to arrange molecule in crystal more open, it is more sensitive to environmental stimuli, cause TCBM to provide high comparison
The pressure of degree causes fluorescence discoloration behavior.Referring to: LIU M, ZHAI L, SUN J, et al.Multi-color solid-state
luminescence of difluoroboronβ-diketonate complexes bearing carbazole with
mechanofluorochromism and thermofluorochromism[J].Dyes Pigm,2016,128,271-278.
In 2017, SUN et al. synthesized the Schiff boron difluoride complex TPOB of tert-butyl carbazole modification.The crystal energy of synthesis
Enough emit yellow fluorescence, launch wavelength is located at 570nm, and after grinding, luminescent color becomes orange red, and launch wavelength red shift is arrived
590nm.Powder after grinding is heated, solid luminescent has been restored to yellow fluorescence again, regrinding, and becomes orange
Red fluorescence, illustrating that TPOB pressure causes fluorescence discoloration is a kind of reversible process.Referring to: SUN J, SUN J, MI W, et al.Self-
assembling and piezofluorochromic propertiesof tert-butylcarbazole-based
Schiff bases and the difluoroboron complex[J].Dyes Pigm,2017,136,633-640.
Molten mutagens color be lead to the absorption spectrum of organic dye molecule since the polarity of vehicle substance changes, or
It is that distinct variation occurs for emission spectrum, then the colour developing of organic fluorescent dye substance solution can be induced to change.Molten mutagens color
Fluorescent material generally all has D- π-A conjugated structure, and one or more strong electron-withdrawing groups are introduced in conjugated molecule, can be very big
Increase electron-withdrawing ability in degree, promote intramolecule electric charge transfer, causes molecular dipole away from being biased to.Based on intramolecular electricity
The principle of lotus transfer, by changing solvent polarity, dipole moment of the molecule in excitation state increases, to be conducive to generate molten mutagens color
Phenomenon.Using triphenylamine as parent, it is modified to obtain the material with electron donor-acceptor structure, there is apparent molten mutagens color
Property, with the increase of molecular conjugation degree, dipole moment otherness becomes larger, molten cause metachrosis enhancing.Referring to Gupta V D,
Tathe A B,Padalkar V S,et al.Red emitting solid state fluorescent
triphenylamine dyes:Synthesis,photo-physical property and DFT study[J].Dyes&
Pigments, 2013,97 (3): the designs such as 429-439.Meisner Q J have synthesized 2- (2'- hydroxy phenyl) benzoxazoles point
Son, structure have the property of Intramolecular electron transfer, excited state intramolecular proton transfer.It is influenced, is being swashed by molecular structure
State is sent out there are two types of structure enol form and keto-acid, the Ground-state Structures that solvent polarity will affect molecule change, so as to cause excitation state
Structure change.Therefore, according to the difference of medium and excitation wavelength, the transmitting of enol form, keto-acid and anionic form can be simultaneously
Occur, color gamut is respectively blue, green and orange/red.It, can be with by the reasonable selection to medium and excitation wavelength
Obtain the white tertiary colour that CIE coordinate is (0.33,0.33).Referring to: Meisner Q J, Younes A H, Yuan Z, et
al.Excitation-Dependent Multiple Fluorescence of a Substituted 2-(2'-
Hydroxyphenyl)benzoxazole[J].The journal of physical chemistry.A,2018,122
(47):9209.
It is photochromic to refer to that a certain compound intramolecular under the irradiation of certain wavelength light chemically reacts, molecular structure
The B configuration of another color, the change of simultaneous compound absorption spectra are transformed to by the A configuration with a kind of color
Change.B configuration can be restored to original A configuration again under the irradiation of another wavelength light or under the action of heat.Usual A configuration only exists
There is an absorption near ultraviolet band, and B configuration is presented new absorption peak in visible region, thus two kinds of types cognition show it is visibly different
Color.Spiro-pyrans, spirooxazine are exactly typical photochromic compound.The design of Liu Lang professor seminar has synthesized 1,3- hexichol
Base -4- (3- bromo biphenyl) -5- hydroxypyrazoles 4- Carbaphen, white powder will become Huang under the ultraviolet light of 365nm
Color powder, white powder is very sensitive to light, and the yellow form formed after sunlight irradiates a few minutes can save 3 in the dark
Month or more, it is highly stable.Yellow powder heats a few minutes in 110 DEG C of oven can revert to white.Referring to: Liu L,
Xie X,Jia D,et al.Synthesis and Properties of a Novel Photochromic Compound
with Modulated Fluorescence in the Solid State[J].The Journal of Organic
Chemistry, 2010,75 (14): the designs such as 4742-4747.Shao B have synthesized a kind of molecule of photochromic hydrazine derivate
Switch, there are two types of isomer 1Z (hydrogen bond closo body) 1E (hydrogen bond disconnection type body), as the ultraviolet light 1Z of 442nm
Hydrogen bond is broken into 1E when toluene solution, and ultraviolet absorption maximum is transferred to 343nm from 395nm, solution from it is faint yellow be converted to it is colourless.
1Z state is restored under the either ultraviolet light of 340nm when heating.Referring to: Shao B, Baroncini M, Qian H, et
al.Solution and Solid-State Emission Toggling of a Photochromic Hydrazone[J]
.Journal of the American Chemical Society,2018,140(39):12323-12327.
Chemical stain refers to that a certain fluorescent chemicals by the chemical reagent fast reaction with other unstressed configuration performances, obtain
Another new stable fluorescent chemicals realize discoloration in situ.New fluorescent chemicals are synthesized by chemical stain, are had certainly
Oneself stablizes unique structure, compared with dye molecule before: electronic structure, intramolecular hydrogen bond, the van der Waals interaction of system
It is all different, therefore colour developing, ultraviolet and fluorescence spectrum performance change, realizes chemical stain.
The behavior of power mutagens color, molten mutagens color, light to discoloration can be restored to after ambient pressure, solvent, luminous environment change
State originally has invertibity.Therefore these off-color materials have unstability, are limited in the application such as commodity counterfeit prevention
System.Chemical stain behavior does not have invertibity, and product chemistry property is stablized, and is suitble to production application.However it is rarely reported and mentions
Solve the problems, such as that fluorescence off-color material performance is not sufficiently stable with chemical stain mechanism mechanism out.
Summary of the invention
There is a problem of unstable present invention aim to address above-mentioned off-color material, a kind of chemical stain fluorescent ink is provided
Water and preparation method and applications.
The ink is made of two kinds of components, and a kind of group is divided into fluorescent dye solution, and another group is divided into active chemical agent
Solution.Wherein the main component of fluorescent dye solution is a kind of simple fluorescent material a of structure, 2,5- diaminostilbenes, 4- hexichol
Butyl formate.The fluorescent dye is to be reacted to generate succinic acid succinyl dibutyl ester with sodium hydride by dibutyl succinate, is then existed
Product is obtained under the action of ammonium acetate and elemental sulfur.Obtained dyestuff is dissolved in organic solvent, addition dye dispersant is made into glimmering
Light ink.Fluorescent ink painting is written on unbleached paper, yellow is presented in font, and Huang is issued under the ultraviolet light irradiation of 365nm
Color fluorescence;And the main component of another component is the active acylating reagent of unstressed configuration, and it can be by 2,5- diaminostilbene, 4- hexichol
Acylating reagent is dissolved in organic solvent painting and write in above-mentioned font, occurred in situ on paper by the aminoacylates in butyl formate
Chemical reaction, different new fluorescent material b or c is generated according to the difference of acylating reagent concentration, font is under ultraviolet light irradiation
Green or blue-fluorescence can be presented.
Technical solution of the present invention:
1, chemical stain fluorescent ink
By a kind of simple dye molecule of structure, that is, single phenyl ring fluorescent material 2,5- diaminostilbene, 4- dibenzoic acid butyl ester
(that is, fluorescent material a), dye dispersant (SRE-4190, SRE-4029, SRE-48000-60, SRE-4703W, SRE-
42000, SRE-4023AX) and organic solvent (chloroform, acetone, methylene chloride, ethyl acetate, tetrahydrofuran, acetonitrile, second
Alcohol, methanol, dimethyl sulfoxide, N, N- dimethyl sulfoxide) it collectively constitutes;It is write with this ink, font color can be helped in ink
Change color under the action of agent, wherein molecular structure of dye formula is as follows:
2,5- diaminostilbene in the chemiluminescence color-change ink, 4- dibenzoic acid butyl ester, organic solvent, dyestuff point
The amount ratio of powder is (0.0062-0.0125g): (3-5mL): (0-2mL).Ultrasound is allowed to be uniformly dispersed.
The ink auxiliary agent includes ink auxiliary agent I and ink auxiliary agent II;Ink auxiliary agent I, by acylating reagent (chloro-carbonic acid-
2,2,2- trichloro ethyl ester, chloroacetic chloride, propionyl chloride, butyl chloride, acetic anhydride, propionic andydride, trifluoroacetic anhydride) and organic solvent (trichlorine
Methane, acetone, methylene chloride, ethyl acetate, tetrahydrofuran, acetonitrile, ethyl alcohol, methanol, petroleum ether, n-hexane) it is uniformly mixed and matches
It makes, the concentration of acylating reagent is identical as fluorescent material a concentration in fluorescence color-change ink;Ink auxiliary agent II, by acylating reagent
It is uniformly mixed and is formulated with organic solvent, the concentration of acylating reagent is the 5-50 of fluorescent material a concentration in fluorescence color-change ink
Times.
2, (fluorescent material a) 2,5- diaminostilbene, the 4- dibenzoic acid of the dye molecule in the chemical stain fluorescent ink
The preparation method of butyl ester, steps are as follows:
1) 2-3 equivalent sodium hydride the synthesis of 2,5- diamino dibutyl terephthalate: is sequentially added in single-necked flask
With 50-150mL ether (or methyl tertiary butyl ether(MTBE), N, dinethylformamide, N, N- dimethyl acetamide, tetrahydrofuran, second two
Diethylene glycol dimethyl ether, diethylene glycol dimethyl ether), 0.1-5mL n-butanol, 5.8g (25m moL, 1 equivalent) fourth two is then slowly added dropwise
Dibutyl phthalate.It is warming up to 40-100 DEG C, after reacting 4hr.With 20-100mL water and 3-10mL acetic acid (concentrated sulfuric acid, hydrochloric acid, phosphoric acid,
Nitric acid) quenching reaction.Suction filtration obtains solid product.
2) ammonium acetate for weighing solid 1.56g (5m mol, 1 equivalent) and 2-10 equivalent that step 1) obtains is mixed into 4-
In 50mL n-butanol (or N, dinethylformamide, N, N- dimethyl acetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether)
90-150 DEG C is heated to reflux 8 hours.The elemental sulfur of 0.4-4.0 equivalent is added after fully reacting, 70-150 DEG C of heating reaction 10 is small
When.It is filtered after cooling and obtains orange/yellow solid product fluorescent material a, that is, the dye molecule 2,5- in chemical stain fluorescent ink
Diaminostilbene, 4- dibenzoic acid butyl ester.Reaction process is as follows:
3, the synthesis of fluorescent material b
Take 2,5- diaminostilbene, 4- dibenzoic acid butyl ester 0.308g (1m moL, 1 equivalent), 1-2 equivalent N, N- diisopropyl
Ethamine, which is dissolved under 10-100mL methylene chloride (or chloroform, acetonitrile, acetone, ethyl acetate) ice bath, to be stirred, and 1.0-2.5 is taken to work as
Amount acylating reagent is slowly dropped in reaction system, is stirred 1-6 hours at room temperature.Reaction liquid successively use isometric water,
The hydrochloric acid of 0.1mol/L, the sodium bicarbonate solution of saturation, saturation sodium chloride solution wash twice respectively.Anhydrous sodium sulfate is dry
It is dry.Pillar layer separation obtains fluorescent material b.Synthetic route is as follows:
4, the synthesis of fluorescent material c
Take 2,5- diaminostilbene, 4- dibenzoic acid butyl ester 0.308g (1m moL, 1 equivalent), 1-2 equivalent N, N- diisopropyl
Ethamine, which is dissolved under 10-100mL methylene chloride (or chloroform, acetonitrile, acetone, ethyl acetate) ice bath, to be stirred, and 2.0-5.0 is taken to work as
Amount acylating reagent is slowly dropped in reaction system, is stirred 1-6 hours at room temperature.Reaction liquid successively use isometric water,
The hydrochloric acid of 0.1mol/L, the sodium bicarbonate solution of saturation, saturation sodium chloride solution wash twice respectively.Anhydrous sodium sulfate is dry
It is dry.Pillar layer separation obtains fluorescent material c.Synthetic route is as follows:
5, the application of chemical stain fluorescent ink
1) preparation of fluorescent ink: taking 2,5- diaminostilbene, and 4- dibenzoic acid butyl ester and dye dispersant are dissolved in organic molten
Agent is uniformly mixed, wherein 2,5- diaminostilbenes, 4- dibenzoic acid butyl ester, organic solvent, dye dispersant amount ratio be
(0.0062-0.0125g): (3-5mL): (0-2mL).Ultrasound is allowed to be uniformly dispersed.
2) a kind of application of the fluorescence color-change ink, is write on unbleached paper, font under natural light with the ink of preparation
Yellow is presented, issues yellow fluorescence in the ultraviolet light irradiation of 365nm.Detect that launch wavelength exists with sepectrophotofluorometer
559nm sets excitation wavelength as 375nm.
It is write in above-mentioned font with ink auxiliary agent I painting, in the fluorescent material a in fluorescence color-change ink and ink auxiliary agent I
Non-fluorescence active acylating reagent reacts in situ, generates fluorescent material b (synthesis process is as described above) at one's own department or unit, natural light
Lower font becomes green, issues green fluorescence in the ultraviolet light irradiation of 365nm.Launch wavelength is detected with sepectrophotofluorometer
In 493nm, excitation wavelength 375nm.
It is write in font with ink auxiliary agent II painting, it is non-in the fluorescent material a in fluorescence color-change ink and ink auxiliary agent II
The acylating reagent of fluorescence activity reacts in situ, fluorescent material c (synthesis process is as described above) is generated at one's own department or unit, under natural light
Font becomes colourless, issues blue-fluorescence under the ultraviolet light irradiation of 365nm.Launch wavelength is detected with sepectrophotofluorometer
In 467nm, excitation wavelength 375nm.
The invention has the advantages that the fluorescent dye 2,5- diaminostilbene, 4- dibenzoic acid butyl ester preparation process is easy, fluorescence
Luminescent properties are excellent, have and are swift in response between solid fluorescence performance and ink auxiliary agent, with the increase of ink assistant concentration,
Font color can be crossfaded into green to colourless by yellow under natural light, and fluorescence color can be crossfaded by orange-yellow under ultraviolet light irradiation
Green to blue, can on paper in-situ preparation fluorescent material b, c.
Detailed description of the invention
Fig. 1 is fluorescence a, the nuclear magnetic spectrogram of 2,5- diamino dibutyl terephthalates.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of fluorescent material b.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of fluorescent material c.
Fig. 4 is the ultraviolet spectra spectrogram of fluorescent material a, b, c.
Fig. 5 is the fluorescence spectrum spectrogram of fluorescent material a, b, c.
Fig. 6 is the application example of fluorescence color-change ink.
Fig. 7 is the fluorescence spectra of yellowish green blue three kinds of fluorescence color fonts.
Fig. 8 is the chromatic diagram of fluorescent material a, b, c.
Specific embodiment
Embodiment 1:
A kind of chemical stain fluorescent ink, its main component are 2,5- diaminostilbene, 4- dibenzoic acid butyl ester (fluorescence
Matter a), dye dispersant SRE-4190, acetone are uniformly mixed, and fluorescence color-change ink are made, wherein 2,5- diaminostilbenes, 4- hexichol
Butyl formate, organic solvent, dye dispersant amount ratio be 0.0125g:3mL:2mL.
One, the synthesis of fluorescent dye
2,5- diaminostilbene, 4- dibenzoic acid butyl ester structure are as follows:
The fluorescent dye preparation method is as described below,
1,2,5- diamino dibutyl terephthalate (synthesis of fluorescent material a), specific steps are as follows:
1) sodium hydride 2.5g (63m moL, 2.5 equivalents) and 50mL ether 2,5- diamino dibutyl terephthalate: are taken
Sequentially into 100mL single-necked flask, stir.2mL n-butanol, 5.8g (25m moL, 1 equivalent) succinic acid two is successively slowly added dropwise
Butyl ester.It connects condenser pipe, connect bubbler, temperature programming reacts the heating of stopping in 4 hours to 40 DEG C.20mL water and 5mL acetic acid are quenched instead
It answers.Suction filtration obtains solid product.
2) step 1) solid 1.56g (5m mol, 1 equivalent), ammonium acetate 1.93g (25m mol, 5 equivalents), 10mL bis- are weighed
Into 50mL single-necked flask, 150 DEG C are heated to reflux 8 hours methyl sulfoxide.It samples contact plate and monitors reaction process, add after fully reacting
Enter elemental sulfur 0.176g (5.5m mol, 1.1 equivalents), is down to 100 DEG C and continues heating 10 hours.After complete reaction, stop adding
Heat filters after cooling and obtains orange/yellow solid product fluorescent material a.
Fig. 1 is the nuclear magnetic resonance spectroscopy spectrogram of 2,5- diamino dibutyl terephthalate.Show in figure:1HNMR
(400MHz,DCCl3) δ 7.28 (s, 1H), 5.07 (s, 2H), 4.28 (t, J=6.6Hz, 2H), 1.74 (dq, J=8.6,
6.7Hz, 2H), 1.52-1.42 (m, 2H), 0.98 (t, J=7.4Hz, 3H), which are shown, has successfully synthesized 2,5- diaminostilbene,
4- dibenzoic acid butyl ester.
2, fluorescent dye b is synthesized: take 2,5- diaminostilbene, 4- dibenzoic acid butyl ester 0.308g (1m mol, 1 equivalent),
50mL ethyl acetate, n,N-diisopropylethylamine 0.3g (2.3m mol, 1.15 equivalents) are stirred under ice bath into 100mL single port bottle
It mixes.It takes chloroacetic chloride 1.6g (2m mol, 1 equivalent) in 5mL ethyl acetate, is slowly dropped in reaction system, stirs 3 at room temperature
Hour.Post-processing: reaction liquid successively use water (50mL × 2), 0.1mol/L hydrochloric acid (50mL × 2), saturation sodium bicarbonate
Sodium chloride solution (50mL × 2) washing of solution (50mL × 2), saturation.Anhydrous sodium sulfate is dry.Pillar layer separation obtains fluorescence
Substance b.
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of fluorescent dye b.Show in figure:1H NMR(400MHz,DCCl3)δ10.06
(s,1H),8.83(s,1H),7.36(s,1H),5.59(s,2H),4.83(s,2H),4.37–4.33(m,2H),4.33–4.28
(m, 2H), 1.78 (qd, J=7.4,3.6Hz, 4H), 1.47 (dtd, J=16.6,7.4,1.9Hz, 4H), 0.99 (td, J=
7.4,4.0Hz, 6H) shows to have synthesized fluorescent dye b.
3, fluorescent dye c is synthesized: take 2,5- diaminostilbene, 4- dibenzoic acid butyl ester 0.308g (1m mol, 1 equivalent),
50mL ethyl acetate, n,N-diisopropylethylamine 0.3g (2.3m mol, 1.15 equivalents) are stirred under ice bath into 100mL single port bottle
It mixes.It takes chloroacetic chloride 4.8g (6m mol, 3 equivalents) in 5mL ethyl acetate, is slowly dropped in reaction system, stirs 3 at room temperature
Hour.Post-processing: reaction liquid successively use water (50mL × 2), 0.1mol/L hydrochloric acid (50mL × 2), saturation sodium bicarbonate
Sodium chloride solution (50mL × 2) washing of solution (50mL × 2), saturation.Anhydrous sodium sulfate is dry.Pillar layer separation obtains fluorescence
Substance c.
Fig. 3 is the nuclear magnetic resonance spectroscopy spectrogram of fluorescent dye c.Show in figure:1H NMR(400MHz,DCCl3δ10.56(s,
1H), 9.10 (s, 1H), 4.85 (s, 2H), 4.39 (t, J=6.8Hz, 2H), 1.81 (dd, J=8.5,6.3Hz, 2H), 1.54-
1.46 (m, 2H), 1.00 (t, J=7.4Hz, 3H) show to have synthesized fluorescent dye c.
Fig. 4 is the ultraviolet spectra spectrogram of fluorescent material a, b, c.Test condition: the 4 × 10 of fluorescent material a, b, c-5mol/L
Dichloromethane solution.As can be seen from Figure 4 fluorescent material a, b, c three UV absorption wavelength is respectively 434nm, 400nm,
367nm.Fluorescent material a, b, c UV absorption wavelength successively blue shift.
The fluorescence spectrum spectrogram of Fig. 5 fluorescent material a, b, c.Test condition: the 4 × 10 of fluorescent material a, b, c-5Mol/L bis-
Chloromethanes solution.Fluorescent material a, b, c three's fluorescence radiation wavelength is respectively 534nm, 473nm, 434nm.Fluorescent material a, b, c
Fluorescence radiation wavelength successively blue shift.
Two, the preparation and application of chemical stain fluorescent ink
1, the application of the fluorescent material a --- for preparing chemical tenebrescent ink, method is: weighing
0.0125g 2,5- diaminostilbene, 4- dibenzoic acid butyl ester dyestuff and 2mL dye dispersant SRE-4190 are dissolved in 3mL acetone, surpass
Sound is allowed to be uniformly dispersed.Ink is dipped with writing brush, and " TUST " is write on unbleached paper.Font shows yellow under natural light, uses
The ultraviolet light font of 365nm, font issue yellow fluorescence (see Fig. 6 a).Detect that its solid is glimmering with sepectrophotofluorometer
In 558nm, (excitation wavelength 375nm is shown in Fig. 7 line a) to light maximum emission wavelength.Fluorescence spectrum of the fluorescent material a on unbleached paper
There is certain red shift compared in methylene chloride.
2, the preparation and application of ink auxiliary agent.
Ink auxiliary agent I: it takes 0.0016g chloroacetic chloride to be dissolved in 5mL petroleum ether and is uniformly mixed, being made into concentration is 8 × 10-3moL/L
Chloroacetic chloride solution.Ink auxiliary agent I painting is dipped to write on above-mentioned font " UST ", font becomes green by yellow under natural light,
The fluorescence of green is issued under the ultraviolet light irradiation of 365nm (see Fig. 6 b).Its solid fluorescence is detected with sepectrophotofluorometer
In 493nm, (excitation wavelength 375nm is shown in Fig. 7 line b) to maximum emission wavelength.It can thus be concluded that fluorescent material a and chloroacetic chloride are in situ out
Reaction generates fluorescent material b.
Ink auxiliary agent II: it takes 0.016g chloroacetic chloride to be dissolved in 5mL petroleum ether and is uniformly mixed, be made into 8 × 10-2The acetyl of moL/L
Solutions of chlorine.Ink auxiliary agent II painting is dipped to write on " S ", font becomes colourless by green under natural light, and it is approximate stealthy, in 365nm
Ultraviolet light irradiation under issue blue fluorescence (see Fig. 6 c).Its solid fluorescence launch wavelength is detected with sepectrophotofluorometer
In 467nm, (excitation wavelength 375nm is shown in Fig. 7 line c).It can thus be concluded that fluorescent material a and high concentration chloroacetic chloride reaction in-situ are raw out
At fluorescent material c.
Fig. 6 is the application example of fluorescence color-change ink.A left figure is the picture for inking word " TUST " and being presented in Fig. 6,
Font is yellow;Right figure is that under the irradiation of ultraviolet lamp, font issues yellow fluorescence.B left figure is write on ink auxiliary agent I painting
The picture that " UST " font is presented, it is green for scribbling rear font;Right figure is under the irradiation of ultraviolet light, to scribble rear font hair
Green fluorescence out.C left figure is to be applied to write on the picture that " S " font is presented with ink auxiliary agent II, scribbles rear font close to colourless;It is right
Figure is under the irradiation of ultraviolet light, to scribble rear font and issue blue-fluorescence.D left figure is to write on the 4th font " T " with ink painting
The picture presented scribbles rear font and becomes yellow again;Right figure is under the irradiation of ultraviolet light, it is glimmering to scribble rear font sending yellow
Light.From Fig. 6 d it can be seen that under the action of ink and ink auxiliary agent, font color successively realizes yellow, green under natural light
Color, colourless transformation;The transformation of yellow, green, blue-fluorescence is successively realized under ultraviolet light irradiation;It is realized from molecular level
Fluorescent material a arrives to fluorescent material b the transformation of fluorescent material c again.
Fig. 7 is the fluorescence emission spectrogram of compound of yellowish green blue three-color font.When fixed excitation wavelength is 375nm, yellow
Largest font launch wavelength is 559nm, and green font maximum emission wavelength is 493nm, and colourless largest font launch wavelength is
467nm.Thus solid fluorescence generates fluorescent material b, ink it follows that ink auxiliary agent I is coated in the font of ink a writing
Auxiliary agent II is coated in the font of ink a writing and generates fluorescent material c.
Fig. 8 is the chromatic diagram of fluorescent material a, b, c.It is followed successively by fluorescent material a, b, c fluorescence chromatic diagram from right to left.Intuitively
Embody the fluorescent emission properties of compound.
Embodiment 2:
2,5- diaminostilbene, 4- dibenzoic acid butyl ester structural formula are as follows:
The fluorescent dye preparation method is as described below,
1, the synthesis of fluorescent material a:
1) synthesis of 2,5- diamino dibutyl terephthalate: take sodium hydride 2.5g (63m moL, 2.5 equivalents) and
50mL N, N- dimethyl acetamide are stirred sequentially into 100mL single-necked flask.3mL n-butanol, 5.8g is successively slowly added dropwise
(25m moL, 1 equivalent) dibutyl succinate.It connects condenser pipe, connect bubbler, temperature programming reacts to 80 DEG C and stops within 4 hours adding
Heat.20mL water and 10mL phosphoric acid quenching reaction.Suction filtration obtains solid product.
2) weigh step 1) solid 1.56g (5m mol, 1 equivalent), ammonium acetate 3.96g (50m mol, 10 equivalents),
Into 50mL single-necked flask, 100 DEG C are heated to reflux 8 hours for 10mLN, dinethylformamide.It samples contact plate and monitors reaction process,
Elemental sulfur 0.176g (5.5m mol, 1.1 equivalents) are added after fully reacting, is down to 90 DEG C and continues heating 10 hours.Wait react
Quan Hou stops heating, filters after cooling and obtain orange/yellow solid product fluorescent material a.
2, fluorescent dye b is synthesized: take 2,5- diaminostilbene, 4- dibenzoic acid butyl ester 0.308g (1m mol, 1 equivalent),
50mL ethyl acetate, n,N-diisopropylethylamine 0.3g (2.3m mol, 1.15 equivalents) are stirred under ice bath into 100mL single port bottle
It mixes.It takes chloroacetic chloride 1.6g (2m mol, 1 equivalent) in 5mL ethyl acetate, is slowly dropped in reaction system, stirs 3 at room temperature
Hour.Post-processing: reaction liquid successively use water (50mL × 2), 0.1mol/L hydrochloric acid (50mL × 2), saturation sodium bicarbonate
Sodium chloride solution (50mL × 2) washing of solution (50mL × 2), saturation.Anhydrous sodium sulfate is dry.Pillar layer separation obtains fluorescence
Substance b.
3, fluorescent dye c is synthesized: take 2,5- diaminostilbene, 4- dibenzoic acid butyl ester 0.308g (1m mol, 1 equivalent),
50mL ethyl acetate, n,N-diisopropylethylamine 0.3g (2.3m mol, 1.15 equivalents) are stirred under ice bath into 100mL single port bottle
It mixes.It takes chloroacetic chloride 4.8g (6m mol, 3 equivalents) in 5mL ethyl acetate, is slowly dropped in reaction system, stirs 3 at room temperature
Hour.Post-processing: reaction liquid successively use water (50mL × 2), 0.1mol/L hydrochloric acid (50mL × 2), saturation sodium bicarbonate
Sodium chloride solution (50mL × 2) washing of solution (50mL × 2), saturation.Anhydrous sodium sulfate is dry.Pillar layer separation obtains fluorescence
Substance c.
Embodiment 3:
The application of the fluorescent material a --- for preparing chemical tenebrescent ink, method is: weighing 0.0125g
2,5- diaminostilbenes, 4- dibenzoic acid butyl ester dyestuff and 0.5mL dye dispersant SRE-4029 are dissolved in 4.5mL methylene chloride, surpass
Sound is allowed to be uniformly dispersed.Ink is dipped with writing brush, and " TUST " is write on unbleached paper.Font shows yellow under natural light, uses
The ultraviolet light font font of 365nm issues the fluorescence of yellow.Its solid fluorescence maximum is detected with sepectrophotofluorometer
Launch wavelength is at 558nm (excitation wavelength 375nm).
Embodiment 4:
The application of the fluorescent material a --- for preparing chemical tenebrescent ink, method is: weighing 0.0100g
2,5- diaminostilbenes, 4- dibenzoic acid butyl ester dyestuff and 0mL dye dispersant SRE-4029 are dissolved in 5mL acetone, and ultrasound is allowed to point
It dissipates uniform.Ink is dipped with writing brush, and " TUST " is write on unbleached paper.Font shows yellow under natural light, with the purple of 365nm
Outer light irradiation font font issues the fluorescence of yellow.
Embodiment 5:
The application of the fluorescent material a --- for preparing chemical tenebrescent ink, method is: weighing 0.0125g
2,5- diaminostilbene, 4- dibenzoic acid butyl ester dyestuff and 0.5mL dye dispersant SRE-48000-60 are dissolved in 4.5mL acetic acid second
Ester, ultrasound are allowed to be uniformly dispersed.Ink is dipped with writing brush, and " TUST " is write on unbleached paper.Font shows Huang under natural light
Color issues the fluorescence of yellow with the ultraviolet light font font of 365nm.
Embodiment 6:
The preparation and application of ink auxiliary agent.
Ink auxiliary agent I: it takes 0.0016g chloroacetic chloride to be dissolved in 5mL n-hexane and is uniformly mixed, being made into concentration is 8 × 10-3moL/L
Chloroacetic chloride solution.It dips ink auxiliary agent I to apply in the above-mentioned font " UST " write on, font becomes green by yellow under natural light
Color issues the fluorescence of green under the ultraviolet light irradiation of 365nm.
Ink auxiliary agent II: it takes 0.016g chloroacetic chloride to be dissolved in 5mL n-hexane and is uniformly mixed, be made into 8 × 10-2The acetyl of moL/L
Solutions of chlorine.Ink auxiliary agent II painting is dipped to write on " S ", font becomes colourless by green under natural light, and it is approximate stealthy, in 365nm
Ultraviolet light irradiation under issue blue fluorescence.
Claims (9)
1. a kind of chemical stain fluorescent ink, it is characterised in that: by a kind of simply single phenyl ring fluorescent material 2 of structure, 5- bis-
Amino-Isosorbide-5-Nitrae-dibenzoic acid butyl ester dye molecule that is, fluorescent material a, dye dispersant and organic solvent are collectively constituted, through super
Sound is allowed to be uniformly dispersed;It is write with this ink, font color can change color under the action of ink auxiliary agent;Wherein contaminate
Expect that molecular structural formula is as follows:
2. chemical stain fluorescent ink according to claim 1, which is characterized in that the organic solvent has to be described
Solvent be chloroform, acetone, methylene chloride, ethyl acetate, tetrahydrofuran, acetonitrile, ethyl alcohol, methanol, dimethyl sulfoxide or
N, N- dimethyl sulfoxide;Dye dispersant is SRE-4190, SRE-4029, SRE-48000-60, SRE-4703W, SRE-42000
Or SRE-4023AX;2,5- diaminostilbene, 4- dibenzoic acid butyl ester, organic solvent, dye dispersant amount ratio be
(0.0062-0.0125g): (3-5mL): (0-2mL).
3. chemical stain fluorescent ink according to claim 1, which is characterized in that the ink auxiliary agent includes that ink helps
Agent I and ink auxiliary agent II;Ink auxiliary agent I is uniformly mixed with organic solvent by acylated examination and is formulated, the concentration of acylating reagent and
Fluorescent material a concentration is identical in fluorescence color-change ink;Ink auxiliary agent II, be uniformly mixed with organic solvent preparation by acylating reagent and
At the concentration of acylating reagent is 5-50 times of fluorescent material a concentration in fluorescence color-change ink.
4. chemical stain fluorescent ink according to claim 3, which is characterized in that the acylating reagent is chloro-carbonic acid-
2,2,2- trichloro ethyl ester, chloroacetic chloride, propionyl chloride, butyl chloride, acetic anhydride, propionic andydride or trifluoroacetic anhydride;The organic solvent
For chloroform, acetone, methylene chloride, ethyl acetate, tetrahydrofuran, acetonitrile, ethyl alcohol, methanol, petroleum ether or n-hexane.
5. the dye molecule 2,5- diaminostilbene in a kind of chemical stain fluorescent ink as described in claim 1,4- dibenzoic acid
The preparation method of butyl ester, its step are as follows:
1) 2-3 equivalent sodium hydride and 50- the synthesis of 2,5- diamino dibutyl terephthalate: are sequentially added in single-necked flask
0.1-5mL n-butanol, 5.8g that is, 25m moL, the dibutyl succinate of 1 equivalent, heating is then slowly added dropwise in 150mL ether
To 40-100 DEG C, after reacting 4hr.With 20-100mL water and 3-10mL acetic acid quenching reaction, suction filtration obtains solid product;
2) the solid 1.56g i.e. 5m mol that step 1) obtains is weighed, the ammonium acetate of 1 equivalent and 2-10 equivalent is mixed into 4-50mL
It is heated to reflux 8 hours for 90-150 DEG C in n-butanol.The elemental sulfur of 0-2 equivalent, 70-150 DEG C of heating reaction are added after fully reacting
10 hours.It is filtered after cooling and obtains orange/yellow solid product fluorescent material a, that is, the dye molecule in chemical stain fluorescent ink
2,5- diaminostilbene, 4- dibenzoic acid butyl ester.
6. preparation method according to claim 5, which is characterized in that ether described in step 1) can be substituted for methyl- tert
Butyl ether, N, dinethylformamide, N, N- dimethyl acetamide, tetrahydrofuran, glycol dimethyl ether or diethylene glycol two
Methyl ether;The acetic acid can be substituted for the concentrated sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid;
N-butanol described in step 2 can be substituted for N, dinethylformamide, N, N- dimethyl acetamide, dimethyl sulfoxide
Or diethylene glycol dimethyl ether.
7. a kind of application of the chemical stain fluorescent ink as described in any one of claims 1 to 3, it is characterised in that: with the ink
Water writes on unbleached paper, and font is yellow, issues yellow fluorescence under the ultraviolet light of 365nm;It is examined with sepectrophotofluorometer
Launch wavelength is measured in 559nm, excitation wavelength 375nm.
8. application according to claim 7, it is characterised in that: write in above-mentioned font with ink auxiliary agent I painting, under natural light
Font becomes green by yellow, and the fluorescence of green is issued under the ultraviolet light irradiation of 365nm;It is detected with sepectrophotofluorometer
Launch wavelength is in 493nm, excitation wavelength 375nm.
9. application according to claim 7, it is characterised in that: it is write in above-mentioned font with ink auxiliary agent II painting, it is natural
Font becomes colourless by yellow under light, and the fluorescence of blue is issued under the ultraviolet grade of 365nm;It is detected with sepectrophotofluorometer
Launch wavelength is in 467nm, excitation wavelength 375nm.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0536083A1 (en) * | 1991-09-30 | 1993-04-07 | Ciba-Geigy Ag | Process for the synthesis of dialkyl succinylsuccinate esters and their conversion to dialkyl 2,5-diarylamino-3,6-dihydroterephthalate esters |
EP0764630A1 (en) * | 1995-09-25 | 1997-03-26 | Ciba SC Holding AG | Process for the preparation of dialkyl succinylsuccinates |
CN104276953A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院大连化学物理研究所 | Method for preparing dialkyl 1,4-cyclohexanedicarboxylate |
CN106831763A (en) * | 2016-12-18 | 2017-06-13 | 浙江江山化工股份有限公司 | A kind of preparation method of quinacridone and its derivative |
-
2019
- 2019-07-05 CN CN201910601929.2A patent/CN110358366A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0536083A1 (en) * | 1991-09-30 | 1993-04-07 | Ciba-Geigy Ag | Process for the synthesis of dialkyl succinylsuccinate esters and their conversion to dialkyl 2,5-diarylamino-3,6-dihydroterephthalate esters |
EP0764630A1 (en) * | 1995-09-25 | 1997-03-26 | Ciba SC Holding AG | Process for the preparation of dialkyl succinylsuccinates |
CN104276953A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院大连化学物理研究所 | Method for preparing dialkyl 1,4-cyclohexanedicarboxylate |
CN106831763A (en) * | 2016-12-18 | 2017-06-13 | 浙江江山化工股份有限公司 | A kind of preparation method of quinacridone and its derivative |
Non-Patent Citations (2)
Title |
---|
蔡小飞等: "喹吖啶酮类颜料及其功能化研究进展", 《染料与染色》 * |
黄长干: "《有机合成化学》", 30 August 2017, 合肥工业大学出版社 * |
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