CN106832175A - A kind of double hydroxyl fluorescence chain extenders and its preparation and application based on carbazole derivates - Google Patents
A kind of double hydroxyl fluorescence chain extenders and its preparation and application based on carbazole derivates Download PDFInfo
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Abstract
The invention belongs to the technical field of organic material, a kind of double hydroxyl fluorescence chain extenders based on carbazole derivates and its preparation and application are disclosed.Methods described is：(1) in the basic conditions, with organic solvent as reaction medium, carbazole is reacted with propargyl bromide, subsequent treatment, is obtained the propinyl carbazole of intermediate 9；The carbazole is 1 with propargyl bromide mol ratio:1.1~2；(2) in the atmosphere of inert gas and under conditions of catalyst and reducing agent, the propinyl carbazole of intermediate 9 and double hydroxy azides are reacted in solvent, subsequent treatment, is obtained the double hydroxyl fluorescence chain extenders based on carbazole derivates.The chain extender yield is high, and with fluorescence intensity higher, resistance to ultraviolet stability is good, for manufacturing fluorescence WPU emulsions.
Description
Technical field
The invention belongs to the technical field of organic material, it is related to a kind of double hydroxyl fluorescence chain extenders based on carbazole derivates
And preparation method thereof, and as the method for chain extender synthesis copoly type fluorescence WPU.
Background technology
Polyurethane (PU) as a kind of synthetic resin of function admirable, with application widely.Traditional PU materials lead to
Organic solvent dissolved dilution is often utilized, when film forming solidifies, a large amount of organic solvent volatilizations cause serious environmental pollution.By PU points
It is dispersed in water, exists in the form of an emulsion, with excellent environmental-protecting performance.And the fluorescent material based on aqueous polyurethane is also by frequency
Numerous applies at aspects such as anti-counterfeiting technology, ink, life science, information storage and national defence.
Although fluorescence polyurethane material has been widely used, research of the people to fluorescence polyurethane material also has a lot
Aspect is needed to be studied.Such as, in terms of the synthesis of fluorescence polyurethane, traditional way is typically will be inorganic or organic glimmering
It is prepared by light small molecule dyes and polyaminoester emulsion and the blending of various auxiliary agents.Polymer emulsion and pigment or dyestuff blending are obtained
Color aqueous polymeric articles be widely used in fields such as aqueous paint, water-based inks, but due to pigment
Or there is a problem of poor compatibility between dyestuff and waterborne polymeric, frequently can lead to many problems and occur, for example, pigment is in storage
When being separated out during depositing, used the problems such as color and luster skewness, product color fastness to light and fastness to brushing difference.
And pass through chemical reaction and small molecule fluorescent material is connected in polyurethane, polyurethane is modified so that altogether
Poly- type fluorescence polyurethane has many excellent performances, such as high mechanical strength, solvent resistance are good, heat-resisting, resistance to migration, easy film forming
With the characteristic good such as machinability, it is often more important that with organic molecule dyestuff to the strong absorbent and chromophoric characteristic of light.
The content of the invention
The present invention is intended to provide a kind of fluorescent dye based on carbazole derivates (the double hydroxyls i.e. based on carbazole derivates are glimmering
Light chain extender) and preparation method thereof, and be applied in aqueous fluorescent polyurethane building-up process as small molecule chain extender.Institute
The technical problem to be solved is to confer to make it have fluorescence property while dyestuff pair hydroxyl, and steady with good ultraviolet resistance
It is qualitative.
Carbazole is a kind of heterocyclic organic compounds containing nitrogen.Some are introduced in carbazole molecules has the small of specific function
Group is chemically modified and can obtain various structures and the different carbazole derivates of function, with stronger bluish violet fluorescence, its
Derivative has bigger range of application with respect to carbazole.
The purpose of the present invention is achieved through the following technical solutions：
Double hydroxyl fluorescence chain extenders based on carbazole derivates, its chemical structural formula is one kind in formula I~III：
The synthesis of fluorescence chain extender raw material based on carbazole in the present invention, in being prepared with propargyl bromide generation substitution reaction
Mesosome, then there is click-reaction with double hydroxy azides, obtain the double hydroxyl fluorescence chain extenders based on carbazole derivates.
The preparation method of the double hydroxyl fluorescence chain extenders based on carbazole derivates, comprises the following steps：
(1) in the basic conditions, with organic solvent as reaction medium, carbazole is reacted with 3- propargyl bromides, follow-up place
Reason, obtains intermediate 9- propinyl carbazoles；The carbazole is 1 with 3- propargyl bromides mol ratio:1.1~2；
(2) in the atmosphere of inert gas and under conditions of catalyst and reducing agent, by intermediate 9- propinyl carbazoles
Reacted in solvent with double hydroxy azides, subsequent treatment, obtained the double hydroxyl fluorescence chain extensions based on carbazole derivates
Agent.
Double hydroxy azides described in step (2) are one kind in formula I~III：
Organic solvent described in step (1) is dimethylformamide DMF, dimethyl sulfoxide (DMSO) DMSO or tetrahydrofuran THF；
The condition reacted described in step (1) is to be reacted 12~24 hours in 30~60 DEG C；
Alkalescence condition described in step (1) refers to add highly basic in system.
The highly basic is the one kind in NaOH, potassium hydroxide；The addition of the highly basic is 3- propargyl bromide moles
1~3 times；
Subsequent treatment described in step (1) refers to after the completion of reacting, to add water, is stood, and precipitation is recrystallized, and is filtered, and is done
It is dry.
The recrystallization refers to be recrystallized using hexamethylene or cyclohexanone, and the dry condition is 50~80 DEG C and does
Dry 12~24h.
Solvent described in step (2) is one in dimethylformamide DMF, dimethyl sulfoxide (DMSO) DMSO, tetrahydrofuran THF or water
More than kind；The catalyst is stannous chloride, cuprous bromide or cuprous iodide, and the reducing agent is sodium ascorbate or citric acid
Sodium；
Intermediate 9- propinyls carbazole described in step (2) is (1~2.5) with the mol ratio of double hydroxy azides:1；
Inert gas described in step (2) is nitrogen, and the condition reacted described in step (2) is to react 1 in 25~50 DEG C
~2 hours；
Catalyst described in step (2) and the mol ratio of intermediate 9- propinyl carbazoles are (1~3) in step (2):10,
Reducing agent is (1~3) with the mol ratio of intermediate 9- propinyl carbazoles:15；
Subsequent treatment described in step (2) refers to after the completion of reacting, to add water, is stood, and precipitation is recrystallized, and is filtered, and is done
It is dry.The recrystallization refers to be recrystallized using hexamethylene or cyclohexanone, and the dry condition is 50~80 DEG C of dryings 12
~24h.
Double hydroxyl fluorescence chain extenders based on carbazole derivates prepared by the present invention, not only yield is high, and product has
Fluorescence intensity higher, resistance to ultraviolet stability is good, can be used to manufacture fluorescence WPU.
Double hydroxyl fluorescence chain extenders based on carbazole derivates are used to prepare fluorescence WPU (aqueous fluorescent polyurethane breasts
Liquid)；Specifically include following steps：
(1) PPG is removed water, the PPG after being removed water；The water removal refers to be heated to
120~130 DEG C, 2~3h of insulation water removal；
(2) under agitation, in 60~75 DEG C, to catalyst is added dropwise in the PPG after water removal, it is subsequently added
Polyisocyanates, at 60~80 DEG C, 1~1.5h of insulation reaction is warming up to 80~85 DEG C to control temperature, insulation reaction 1.5~
2.5h, obtains pre-product；
(3) carboxylic monomer and double hydroxyl fluorescence chain extenders based on carbazole derivates are dissolved in organic solvent, then
It is added dropwise in step (2) pre-product, 2~3h is reacted in 80~85 DEG C；Add acetone control system viscosity 200~
300mPa.s, cooling adds nertralizer to carry out neutralization reaction, obtains neutralized reaction product；
(4) to adding water, high speed shearing emulsification, desolvation to obtain aqueous fluorescent polyaminoester emulsion in neutralized reaction product
(WPU)。
The PPG is polyoxypropyleneglycol, Polyoxyethylene glycol or trimethylolpropane-propylene oxide
One kind of polyethers, its molecular weight is 1000~3000；
The polyisocyanates be IPDI, hexamethylene diisocyanate, toluene di-isocyanate(TDI),
One or more in methyl diphenylene diisocyanate；
The catalyst is dibutyltindilaurylmercaptide cinnamic acid；The carboxylic monomer is dihydromethyl propionic acid, dimethylolpropionic acid；
The nertralizer is triethylamine or N, N- dimethylethanolamine；Its degree of neutralization is 95~105%.
The PPG, polyisocyanates, carboxylic monomer, double hydroxyl fluorescence chain extenders based on carbazole derivates
Mol ratio is (15~20)：(15~25)：(3~6)：(1~3)；The mol ratio of the catalyst and carboxylic monomer for (0.02~
0.04)：(3~6)；The water is (40~50) with the mol ratio of carboxylic monomer：(3~6).
Organic solvent described in step (3) is METHYLPYRROLIDONE, dimethylformamide DMF or dimethyl sulfoxide (DMSO)
DMSO；The time of the dropwise addition is 20~25min；The cooling refers to be cooled to 35~45 DEG C, the time of the neutralization reaction
It is 30~35min；
The rotating speed of high speed shear described in step (4) is 4000~5000rpm, 15~20min of high speed shearing emulsification.
WPU emulsion solid contents prepared by the present invention are 50~58%, and storage stability was up to more than 6 months；Particle diameter 180~
210nm；Water absorption rate 4.3~5.7% after film forming, fluorescence intensity declines 4.1~6.8% after ethanol immersion 8h.
Compared with prior art, the invention has the advantages that and beneficial effect：
(1) the double hydroxyl fluorescence chain extenders of the present invention, structure is novel, and preparation process is simple, yield is high, and production cost is relatively low.
(2) chain extender prepared by the present invention has fluorescence intensity higher, and resistance to ultraviolet stability is good, and anti-fatigue performance is excellent
It is different, have wide practical use.
(3), admittedly containing height, viscosity is low, and storage stability is good for the WPU emulsions prepared by the present invention；It is latex film water resistance, resistance to molten
Agent excellent performance, and with lasting fluorescence property is stablized, it is applied to fluorescence falsification preventing coating.
Brief description of the drawings
Fig. 1 be carbazole (a) in embodiment 1,9- propinyls carbazole (b) and embodiment 2 prepare based on carbazole derivates
The infrared spectrum of double hydroxyls fluorescence chain extender (c)；
Fig. 2 is the double hydroxyls based on carbazole derivates of carbazole, 9- propinyls carbazole and embodiment 2 preparation in embodiment 1
The fluorescence spectrum comparison diagram of fluorescence chain extender；
Fig. 3 (a) is the grain size distribution of aqueous fluorescent polyaminoester emulsion prepared by embodiment 6；
Fig. 3 (b) is the grain size distribution of aqueous fluorescent polyaminoester emulsion prepared by embodiment 7；
Fig. 3 (c) is the grain size distribution of aqueous fluorescent polyaminoester emulsion prepared by embodiment 8.
Specific embodiment
Make further specific detailed description to the present invention with reference to specific embodiment, but embodiments of the present invention are not
It is limited to this, for especially not dated technological parameter, can refer to routine techniques is carried out.
Embodiment 1
(1) DMF solvent of 5g carbazoles, the 3- propargyl bromides, 1.8g NaOH and 100ml of 5.36g is mixed, stirring and dissolving
To the transparent solution of system, oil bath stops after being warming up to 50 DEG C of isothermal reaction 24h；
(2) add water to staticly settle, after distilling water washing, filtering three times, be filtrated to get after adding hexamethylene recrystallization
Yellow solid, in 75 DEG C of dryings of convection oven, obtains intermediate 9- propinyl carbazole 6.36g, yield 74.2%.Click in the present embodiment
Infrared figure such as Fig. 1 institutes of the double hydroxyl fluorescence chain extenders based on carbazole derivates prepared by azoles, 9- propinyls carbazole and embodiment 2
Show；The double hydroxyl fluorescence chain extenders based on carbazole derivates that in the present embodiment prepared by carbazole, 9- propinyls carbazole and embodiment 2
Fluorescence spectrum comparison diagram it is as shown in Figure 2.
Intermediate 9- propinyls carbazole prepared by embodiment 1 is used for the double hydroxyls based on carbazole derivates in embodiment 2~5
The preparation of fluorescence chain extender.
Embodiment 2
(1) by intermediate 9- propinyl carbazoles 5g, double hydroxy azides (double hydroxyl azido compounds of formula I) 1.81g
(9- propinyls carbazole is 2.5 with double hydroxy azide mol ratios:1), stannous chloride solid 0.610g and sodium ascorbate
(volume ratio of DMF and distilled water is 9 during 0.725g is dissolved in the mixed solvent of 100ml:1), vacuumize, lead to nitrogen displacement air number
It is secondary, and flow rate of nitrogen is kept, under nitrogen atmosphere, magnetic agitation passes through click-reaction 1h at room temperature；
(2) distillation water sedimentation is added after reaction terminates, there is faint yellow solid to separate out, after distilling water washing, filtering three times,
Faint yellow solid is filtrated to get after adding hexamethylene recrystallization, in 75 DEG C of dryings (18h) of convection oven, is obtained based on carbazole derivates
Double hydroxyl fluorescence chain extender 4.89g, theoretical yield 5.80g, yield 84.3%.
Carbazole, 9- propinyls carbazole and the double hydroxyl fluorescence based on carbazole derivates manufactured in the present embodiment in embodiment 1
The infrared figure of chain extender is as shown in Figure 1；Carbazole, 9- propinyls carbazole are spread out with manufactured in the present embodiment based on carbazole in embodiment 1
The fluorescence spectrum comparison diagram of biological double hydroxyl fluorescence chain extenders is as shown in Figure 2.
Embodiment 3
(1) by intermediate 9- propinyl carbazoles 5g, double hydroxy azides (double hydroxyl azido compounds of formula I) 2.27g
(9- propinyls carbazole is 2 with double hydroxy azide mol ratios:1), stannous chloride solid 0.610g and sodium ascorbate
(volume ratio of DMF and distilled water is 9 during 0.725g is dissolved in the mixed solvent of 100ml:1), vacuumize, lead to nitrogen displacement air number
It is secondary, and flow rate of nitrogen is kept, under nitrogen atmosphere, magnetic agitation passes through click-reaction 1h at room temperature；
(2) add distilled water after reaction terminates, there is faint yellow solid to separate out, after distilling water washing, filtering three times, add ring
Faint yellow solid is filtrated to get after hexane recrystallization, in 75 DEG C of dryings (18h) of convection oven, the double hydroxyls based on carbazole derivates is obtained
Base fluorescence chain extender 6.13g, theoretical yield 7.27g, yield 84.3%.
Embodiment 4
(1) by intermediate 9- propinyl carbazoles 3g, double hydroxy azides (double hydroxyl azido compounds of formula II) 2.32g
(9- propinyls carbazole is 1 with double hydroxy azide mol ratios:1), stannous chloride solid 0.366g and sodium ascorbate
(volume ratio of DMF and distilled water is 9 during 0.435g is dissolved in the mixed solvent of 100ml:1), vacuumize, lead to nitrogen displacement air number
It is secondary, and flow rate of nitrogen is kept, under nitrogen atmosphere, magnetic agitation passes through click-reaction 1h at room temperature；
(2) add distilled water after reaction terminates, there is faint yellow solid to separate out, after distilling water washing, filtering three times, add ring
Faint yellow solid is filtrated to get after hexane recrystallization, in 75 DEG C of dryings (18h) of convection oven, the double hydroxyls based on carbazole derivates is obtained
Base fluorescence chain extender 4.29g, theoretical yield 5.32g, yield 80.6%.
Embodiment 5
(1) by intermediate 9- propinyl carbazoles 3g, double hydroxy azides (double hydroxyl azido compounds of formula III) 2.12g
(9- propinyls carbazole is 1 with double hydroxy azide mol ratios:1), stannous chloride solid 0.366g and sodium ascorbate
(volume ratio of DMF and distilled water is 9 during 0.435g is dissolved in the mixed solvent of 100ml:1), vacuumize, lead to nitrogen displacement air number
It is secondary, and flow rate of nitrogen is kept, under nitrogen atmosphere, magnetic agitation is in room temperature reaction 1h；
(2) add distilled water after reaction terminates, there is faint yellow solid to separate out, after distilling water washing, filtering three times, add ring
Faint yellow solid is filtrated to get after hexane recrystallization, in 75 DEG C of dryings (18h) of convection oven, the double hydroxyls based on carbazole derivates is obtained
Base fluorescence chain extender 4.04g, theoretical yield 5.12g yield 78.9%.
Double hydroxyl fluorescence chain extenders based on carbazole derivates prepared by embodiment 2 are used to prepare the poly- ammonia of aqueous fluorescent
Ester, is shown in embodiment 6~7；Embodiment 8 is comparative example.
Embodiment 6
(1) 15 molar part PPG (1000) are heated to 120 DEG C, insulation water removal 2h obtains the PPG (1000) of water；
(2) under conditions of stirring (mixing speed 200rmp) and 65 DEG C, 0.03 molar part two is added dropwise in the PPG to water removal
Butyl tin tin dilaurate, it is disposable afterwards to add 20 molar part IPDIs, adjustment temperature to 70 DEG C, insulation reaction
85 DEG C of reaction 2h are warming up to after 1h, pre-product is obtained；
(3) fluorescence chain extender prepared by 4 molar part dihydromethyl propionic acids and 1 molar part embodiment 2 is dissolved in 10ml's
METHYLPYRROLIDONE, is added drop-wise in pre-product (pre-product system temperature is 80 DEG C), controls time for adding for 20min, drop
Add after finishing, insulation continues to react 2h, and period system viscosity changes, it is 300mPa.s that acetone regulation system viscosity is added in good time；
Under the rotating speed of 400rmp, 45 DEG C are cooled to, add triethylamine (degree of neutralization is 100%) to neutralize 30min, obtain neutralized reaction product；
(4) to being slowly added to 45 molar part distilled water, 4000rpm high speed shearing emulsifications 15min in neutralized reaction product；
(5) solvent in emulsion is removed with revolving instrument, aqueous fluorescent polyaminoester emulsion product is obtained, solid content is
56.37%, and the film forming in polyfluortetraethylene plate.The grain size distribution of aqueous fluorescent polyaminoester emulsion such as Fig. 3 in the present embodiment
Shown in (a).
Embodiment 7
(1) 15 molar part PPG (1000) are heated to 120 DEG C, insulation water removal 2h obtains the PPG (1000) of water；
(2) under conditions of stirring (mixing speed 200rmp) and 65 DEG C, 0.03 molar part two is added dropwise in the PPG to water removal
Butyl tin tin dilaurate, it is disposable afterwards to add 20 molar part IPDIs, adjustment temperature to 70 DEG C, insulation reaction
85 DEG C of reaction 2h are warming up to after 1h, pre-product is obtained；
(3) fluorescence chain extender prepared by 3 molar part dihydromethyl propionic acids and 2 molar part embodiments 2 is dissolved in 10ml's
METHYLPYRROLIDONE, is added drop-wise in pre-product (pre-product system temperature is 80 DEG C), controls time for adding for 20min, drop
Add after finishing, insulation continues to react 2h, and period notes system viscosity change in flask, adds proper amount of acetone regulation system to stick in good time
It is 300mPa.s to spend；Under the rotating speed of 400rmp, 45 DEG C are cooled to, add triethylamine (degree of neutralization is 100%) to neutralize 30min,
Obtain neutralized reaction product；
(4) to being slowly added to 45 molar part distilled water, 4000rpm high speed shearing emulsifications 15min in neutralized reaction product；
(5) solvent in emulsion is removed with revolving instrument, aqueous fluorescent polyaminoester emulsion product is obtained, solid content is
55.68%, and the film forming in polyfluortetraethylene plate.The grain size distribution of aqueous fluorescent polyaminoester emulsion prepared by embodiment 7 is such as
Shown in Fig. 3 (b).
Embodiment 8
(1) 15 molar part PPG (1000) are heated to 120 DEG C, insulation water removal 2h obtains the PPG (1000) of water；
(2) under conditions of stirring (mixing speed 200rmp) and 65 DEG C, 0.03 molar part two is added dropwise in the PPG to water removal
Butyl tin tin dilaurate, it is disposable afterwards to add 20 molar part IPDIs, adjustment temperature to 70 DEG C, insulation reaction
85 DEG C of reaction 2h are warming up to after 1h, pre-product is obtained；
(3) 4 molar part dihydromethyl propionic acids and 2 molar part reaction intermediate 9- propinyl carbazoles are weighed, is completely dissolved in
The METHYLPYRROLIDONE of 10ml, drops in pre-product (adjustment pre-product system temperature is to 80 DEG C), controls time for adding
It is 20min, after completion of dropping, insulation continues to react 2h, and period notes system viscosity change in flask, proper amount of acetone is added in good time
Regulation system viscosity is 300mPa.s；Under the rotating speed of 400rmp, be cooled to 45 DEG C, add triethylamine (degree of neutralization is 100%)
30min is neutralized, neutralized reaction product is obtained；
(4) to being slowly added to 45 molar part distilled water, 4000rpm high speed shearing emulsifications 15min in neutralized reaction product；
(5) solvent in emulsion is removed with revolving instrument, aqueous fluorescent polyaminoester emulsion product is obtained, solid content is
57.35%, and the film forming in polyfluortetraethylene plate.The grain size distribution of aqueous fluorescent polyaminoester emulsion prepared by embodiment 8 is such as
Shown in Fig. 3 (c).
Example 7 and the gained polyurethane film sample 1g of embodiment 8, are placed in 30mL ethanol respectively, and immersion takes after 8 hours
Go out drying, and be configured to the DMF solution of same concentrations and survey its fluorescence intensity respectively, test result is as shown in table 1.
The solvent resistance contrast of the fluorescence polyurethane material of table 1
* note：The excitation wavelength of fluorescence spectrometry is 343nm.
Data can be seen that the double hydroxyl fluorescence based on carbazole derivates using method of the present invention synthesis from table 1
The aqueous fluorescent polyurethane of chain extender copolymerization, than the aqueous fluorescent that synthesis is directly blended using intermediate 9- propinyls carbazole
Polyurethane has more preferable solvent resistant extraction ability, and with preferable storage stability, emulsion preserves be uniformly dispersed for a long time,
Without sedimentation.
Difference Example 6, embodiment 7 and the gained polyurethane film sample 1g of embodiment 8, are placed in 50mL water, immersion 24
Taken out after hour, dry the water on surface, and weigh quality, calculate water absorption rate, test result is as shown in table 2.
The fluorescence polyurethane material water resistance of table 2 is contrasted
| Sample | Soaked preceding quality (g) | Soaked rear quality (g) | Water absorption rate % |
| Embodiment 6 | 1 | 1.057 | 5.7 |
| Embodiment 7 | 1 | 1.043 | 4.3 |
| Embodiment 8 | 1 | 1.116 | 11.6 |
As can be seen from the above table, the water absorption rate of the polyurethane of copoly type with fluorescence chain extender monomer ratio in reactant increasing
Greatly and slightly reduce, possible cause is that hydrophobic monomer consumption is increased slightly；The polyurethane water absorption rate of embodiment 8 is substantially than implementing
Example 6 and 7 is high, illustrates that the water resistance of copoly type fluorescence polyurethane is more good with respect to the water resistance of blending type fluorescence polyurethane,
Illustrate that the stability of copoly type fluorescence polyurethane is higher.
Fig. 1 be carbazole (a) in embodiment 1,9- propinyls carbazole (b) and embodiment 2 prepare based on carbazole derivates
The infrared spectrum of double hydroxyls fluorescence chain extender (c).The present invention is surveyed using Germany's BRUKER companies VECTER33 types infrared spectrometer
Test agent.Known by a, in 3417cm-1Place occurs in that the stretching vibration absworption peak of N-H, and the absworption peak after reaction in b, c disappears
, illustrate successfully to there occurs substitution reaction；In 2101cm in figure b-1Place is the stretching vibration absworption peak of C ≡ C, illustrates what is obtained
Contain alkynyl in product；2101cm in figure c-1The absworption peak at place substantially weakens, and almost disappears, and illustrates the alkynyl nitrine under copper catalysis
There occurs click-reaction, 3690cm-1Locate to be the stretching vibration peak of 0-H in monomer, 1326cm-1It is the characteristic absorption peak of C-N；It is
The C-H out-of-plane bending vibration absworption peaks of benzene, due to being unimodal and in the range of 770~735cm-1, can determine whether that phenyl ring is present adjacent
Position is disubstituted；3302.82-3052.56cm-1Locate the C-H stretching vibration absworption peaks for phenyl ring；1596cm-1、1486cm-1And
1457cm-1Three peaks at place are the skeletal vibrations of phenyl ring；2933cm-1And 2882cm-1For-CH2Stretching vibration；
Fig. 2 is the double hydroxyls based on carbazole derivates of carbazole, 9- propinyls carbazole and embodiment 2 preparation in embodiment 1
The fluorescence spectrum comparison diagram of fluorescence chain extender.The present invention is tested using Hitachi F-4500 type sepectrophotofluorometers, solution
Concentration is 1mg/L. as we can see from the figure in maximum excitation wavelength XexUnder the ultraviolet excitation of 343nm, three kinds of maximums of material
Emission wavelength lambdaemAll near 377nm, closely, without the obvious red shift of generation or blue shift.But it is dense at identical mole
Spending the corresponding fluorescence intensity under maximum excitation wavelength of lower three kinds of materials has obvious difference.From carbazole, 9- propinyl clicks
The fluorescence intensity that azoles arrives the double hydroxyl fluorescence chain extenders based on carbazole derivates again is remarkably reinforced.In phase co-wavelength (λex) excite
Under light irradiation, the fluorescence intensity of fluorescence emission spectrum is relevant with the structure of molecule, such as conjugation, rigid planar structure, substitution
Base effect etc..Increasing conjugation degree can strengthen fluorescence intensity and produce red shift；Formation rigid planar structure can reduce molecule and shake
It is dynamic, strengthen fluorescence intensity, meanwhile, planar structure is conducive to the flowing of whole intramolecular pi-electron, further enhances fluorescence efficiency；
Electron donating group is connected on aromatic ring can make Fluorescence Increasing, on the contrary, connection electron withdraw group can then weaken fluorescence.
Fig. 3 (a) is the grain size distribution of aqueous fluorescent polyaminoester emulsion prepared by embodiment 6；Fig. 3 (b) makes for embodiment 7
The grain size distribution of standby aqueous fluorescent polyaminoester emulsion；Fig. 3 (c) is aqueous fluorescent polyaminoester emulsion prepared by embodiment 8
Grain size distribution.The present invention uses Malvern companies ZS Nano S type nano-particle size analysis instrument test samples.Known by figure, this hair
The aqueous fluorescent polyaminoester emulsion particle diameter of bright synthesis is basic at 200nm or so (180~210nm), independent uniform each other,
Without adhesion, emulsion particle diameter narrow distribution, peak shape is sharp.
WPU emulsion solid contents prepared by the present invention are 50~58%, and storage stability was up to more than 6 months；Particle diameter 180~
210nm；Water absorption rate 4.3~5.7% after film forming, fluorescence intensity declines 4.1~6.8% after ethanol immersion 8h.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of double hydroxyl fluorescence chain extenders based on carbazole derivates, it is characterised in that：Its chemical structural formula is in formula I~III
It is a kind of：
2. the preparation method of double hydroxyl fluorescence chain extenders of carbazole derivates is based on according to claim 1, it is characterised in that：
Comprise the following steps：
(1) in the basic conditions, with organic solvent as reaction medium, carbazole is reacted with 3- propargyl bromides, subsequent treatment is obtained
To intermediate 9- propinyl carbazoles；The carbazole is 1 with 3- propargyl bromides mol ratio:1.1~2；
(2) in the atmosphere of inert gas and under conditions of catalyst and reducing agent, by intermediate 9- propinyls carbazole with it is double
Hydroxy azide is reacted in solvent, subsequent treatment, obtains the double hydroxyl fluorescence chain extenders based on carbazole derivates；
Double hydroxy azides described in step (2) are one kind in formula I~III：
3. the preparation method of double hydroxyl fluorescence chain extenders of carbazole derivates is based on according to claim 2, it is characterised in that：
Solvent described in step (2) be dimethylformamide, dimethyl sulfoxide (DMSO), tetrahydrofuran or water in more than one；Institute in step (2)
Catalyst is stated for stannous chloride, cuprous bromide or cuprous iodide, the reducing agent is sodium ascorbate or sodium citrate；
Organic solvent described in step (1) is dimethylformamide, dimethyl sulfoxide (DMSO) or tetrahydrofuran；
The condition reacted described in step (1) is to be reacted 12~24 hours in 30~60 DEG C；
The condition reacted described in step (2) is to be reacted 1~2 hour in 25~50 DEG C.
4. the preparation method of double hydroxyl fluorescence chain extenders of carbazole derivates is based on according to claim 2, it is characterised in that：
Alkalescence condition described in step (1) refers to add highly basic in system；Subsequent treatment described in step (1) refer to reaction after the completion of,
Water is added, is stood, precipitation is recrystallized, filtering is dried；
Intermediate 9- propinyls carbazole described in step (2) is (1~2.5) with the mol ratio of double hydroxy azides:1；
Catalyst described in step (2) is (1~3) with the mol ratio of intermediate 9- propinyl carbazoles:10, reducing agent and intermediate
The mol ratio of 9- propinyl carbazoles is (1~3):15；
Subsequent treatment described in step (2) refers to after the completion of reacting, to add water, is stood, and precipitation is recrystallized, and is filtered, and is dried.
5. the preparation method of double hydroxyl fluorescence chain extenders of carbazole derivates is based on according to claim 4, it is characterised in that：
The highly basic of step (1) is the one kind in NaOH, potassium hydroxide；The addition of the highly basic is 3- propargyl bromide moles
1~3 times；
The recrystallization of step (1) refers to be recrystallized using hexamethylene or cyclohexanone, the dry condition be 50~
80 DEG C of 12~24h of drying.
The recrystallization of step (2) refers to be recrystallized using hexamethylene or cyclohexanone, the dry condition be 50~
80 DEG C of 12~24h of drying.
6. the application of the double hydroxyl fluorescence chain extenders based on carbazole derivates according to claim 1, it is characterised in that：It is described
Fluorescence chain extender based on carbazole derivates is used to prepare aqueous fluorescent polyaminoester emulsion.
7. application according to claim 6, it is characterised in that：Comprise the following steps：
(1) PPG is removed water, the PPG after being removed water；The water removal refers to be heated to 120
~130 DEG C, 2~3h of insulation water removal；
(2) under agitation, in 60~75 DEG C, to catalyst is added dropwise in the PPG after water removal, it is subsequently added polyisocyanate
Cyanate, at 60~80 DEG C, 1~1.5h of insulation reaction is warming up to 80~85 DEG C to control temperature, and 1.5~2.5h of insulation reaction is obtained
To pre-product；
(3) carboxylic monomer and double hydroxyl fluorescence chain extenders based on carbazole derivates are dissolved in organic solvent, are then added dropwise
Enter in step (2) pre-product, 2~3h is reacted in 80~85 DEG C；Acetone control system viscosity is added in 200~300mPa.s, drop
Temperature, adds nertralizer to carry out neutralization reaction, obtains neutralized reaction product；
(4) to adding water, high speed shearing emulsification, desolvation to obtain aqueous fluorescent polyaminoester emulsion in neutralized reaction product.
8. application according to claim 7, it is characterised in that：The PPG is polyoxypropyleneglycol, polyoxy
Change one kind of ethylene glycol or trimethylolpropane-propylene oxide polyethers, its molecular weight is 1000~3000；
The polyisocyanates is IPDI, hexamethylene diisocyanate, toluene di-isocyanate(TDI), hexichol
One or more in dicyclohexylmethane diisocyanate；
The catalyst is dibutyltindilaurylmercaptide cinnamic acid；The carboxylic monomer is dihydromethyl propionic acid, dimethylolpropionic acid；
The nertralizer is triethylamine or N, N- dimethylethanolamine, and its degree of neutralization is 95~105%；
The PPG, polyisocyanates, carboxylic monomer, the double hydroxyl fluorescence chain extenders based on carbazole derivates mole
Than being (15~20)：(15~25)：(3~6)：(1~3)；The mol ratio of the catalyst and carboxylic monomer for (0.02~
0.04)：(3~6)；The water is (40~50) with the mol ratio of carboxylic monomer：(3~6).
9. application according to claim 7, it is characterised in that：Organic solvent described in step (3) is N- methyl -2- pyrroles
Alkanone, dimethylformamide or dimethyl sulfoxide (DMSO)；The time of the dropwise addition is 20~25min；The cooling refers to be cooled to 35
~45 DEG C, the time of the neutralization reaction is 30~35min；
The rotating speed of high speed shear described in step (4) is 4000~5000rpm, 15~20min of high speed shearing emulsification.
10. application according to claim 7, it is characterised in that：The aqueous fluorescent polyaminoester emulsion solid content be 50~
58%, storage stability was up to more than 6 months；180~210nm of particle diameter；Water absorption rate 4.3~5.7% after film forming, after ethanol immersion 8h
Fluorescence intensity declines 5.6~6.8%.
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