CN106883168A - The method for manufacturing thin film and application of a kind of triphenylamine derivative and its doping - Google Patents
The method for manufacturing thin film and application of a kind of triphenylamine derivative and its doping Download PDFInfo
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Abstract
The invention discloses a kind of triphenylamine derivatives and its doping SEBS films with the double changes of sour stimuli responsive color and fluorescence, the reversible soda acid stimuli responsive color and fluorescence property of the triphenylamine derivative doping SEBS films have that aberration is big, fluorescent quenching rate feature high respectively；The mechanical property of the film has stretchable, bending, compression, recoverable feature；And the Film synthesis method is simple, greatly widening reversible acid stimulates reality of the change in fluorescence material in senser element.
Description
Technical field
The present invention relates to technical field of environmental detection, more particularly to a kind of triphenylamine derivative and its doping film preparation
Methods and applications.
Background technology
Hydrogen chloride, sulfur dioxide, sulfur trioxide etc. are a kind of industrial common accessory substances, and directly discharge is to environment and people
Body health causes serious harm.In addition, this kind of gas can cause acid rain, acid rain to be referred to as " aerial Death " abroad, its
It is potentially hazardous mainly to show following：(1) generation to aquatic system, terrestrial ecosystems endangers.(2) to building, machine
The corrosion of tool and urban operating mechanism.(3) to the influence of human body.One is the heavy metals such as mercury, lead is entered human body by food chain, is induced
Cancer and senile dementia；Two is that acid mist invades lung, induces pulmonary edema or causes death；Three is to live in containing Acid Preciptation for a long time
Environment in, lure into and produced polyoxygenated fat, cause the disease such as artery sclerosis, heart infarction probability increase.Therefore, to sour gas and
Quick, the low cost of water body, high-sensitivity detection has important science and practical value.
When nitrogen-atoms is with electronegativity nonmetallic formation compound higher, sp can be taken with nitrogen-atoms3Hybrid state, forms three
Individual covalent bond, retains a pair of lone electron pairs, and in addition, nitrogen-atoms takes sp2Hybrid state, forms 1 double covalent bonds and 1 list
Key, and remain with a pair of lone electron pairs.Obviously because the presence to lone electron shows electron, so as to have receive proton (H+) ability, finally, it can have good recognition capability to acid.At present, can detect the nitrogenous organic fluorescence molecule of acid mainly has
Pyridine, schiff bases, fatty amine, porphyrin etc..Above-mentioned organic fluorescence molecule to-draw electronic capability can be divided into two major classes：(1) local
State is conjugated organic fluorescence molecule, and such material has fluorescence quantum efficiency (brightness) higher, but it is used as changing color resulting from acid material
Have that contrast is low, the small problem of aberration (Analyst, 2016,141,4108-4120；Chem.Commun.,2013,49,
3878-3880；J.Mater.Chem.C,2014,2,1539–1544；Chem.Commun.,2015,51,13830-13833).
(2) Intramolecular electron transfer class fluorescence molecule, such substance sensitive degree is high, but due to strong charge transport capability fluorescent quantum
Efficiency is very low, so as to cause its optical contrast it is low (J.Am.Chem.Soc.2009,131,3158-3159,
Chem.Commun.,2014,50,1608--1610).Therefore, design a kind of based on luminous Intramolecular electron transfer behavior high
Sensor molecules have great importance.In addition, the changing color resulting from acid material of report at present, mainly organic molecule, but it does not have
Mechanical property also needs to coordinate other carriers to use, such as be deposited with, and is spun on glass, and with high cost, invertibity
Difference and in-convenience in use shortcoming.Therefore, its in field of fast detection using there is significant limitation.That reports at present can examine
The proton acid gas polymer or small molecule doped polymer of survey mainly include NIPA, poly- (silica
Alkane), poly- (aniline), (Sensors and Actuators B, 2010,150,764-769Adv.Funct.Mater.2016,
26,5987-5996, Chem.Commun., 2014,50,4251-4254, Sensors and Actuators B, 2008,130,
842-847) there is a problem of, but all that aberration is small, fluorescent quenching rate is low or mechanical property is poor.Another question be it is current
The material of synthesis detects proton hydrogen only by colour difference or fluorescent quenching rate, and has colour difference and fluorescent quenching rate double
The molecule report of display function is also fewer.
The content of the invention
Based on the technical problem that background technology is present, it is glimmering that first purpose of the invention is to provide a kind of triphenylamine derivative
Optical molecule and it has fluorescence quantum efficiency characteristic high；The triphenylamine derivative can be in solution, powder or film simultaneously
Proton hydrogen (H in water is detected under form+) or air acid and with aberration is big and the characteristics of fluorescent quenching rate high.
Second object of the present invention is that the triphenylamine derivative is doped to polymer hydrogenation Styrene-Butadiene block
Copolymer (SEBS), then by simple spin-coating film.Triphenylamine derivative doping SEBS film tools with above-mentioned performance
There are the comprehensive mechanical properties such as the stretchable, bending of SEBS materials, and the changing color resulting from acid property of triphenylamine derivative can be retained, can conduct
The simple device of acid vapor in a kind of quick detection air.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of triphenylamine derivative shown in formula (I)：
Described triphenylamine derivative in the case of stress, due to molecule conformation transition causes fluorescence intensity change and presents can
Inverse power stimuli responsive fluorescence changes phenomenon, i.e.,：Various fluorescent emission states are converted to from a kind of fluorescent emission under external force stimulation,
The fluorescent state before non-stress can be returned to through the post-stimulatory material of external force.
Specifically, described triphenylamine derivative is after the grinding pressure effect by mortar, by not pressing under uviol lamp
Preceding bright green fluorescence become be pressurized after glassy yellow fluorescence, it is high with contrast, fluorescence color transformation it is many characteristics of.
The change in fluorescence performance of described triphenylamine derivative (I) can be recovered by the stifling mode of solvent, such as in grinding
After pressure effect, described triphenylamine derivative (I) under the uviol lamp by not pressing before green fluorescence become to be pressurized after it is bright orange
Color fluorescence, then described triphenylamine derivative is carried out into alcohol solvent fumigation action, it can voluntarily return to original under uviol lamp
Come the green fluorescence before not exerting pressure.
In addition, the characteristics of change in fluorescence performance of described triphenylamine derivative (I) also has changing color resulting from acid：Due to fluorescence
Protonation and the deprotonation transformation of molecule cause fluorescence color to change and reversible sour stimuli responsive fluorescence are presented and change phenomenon,
I.e.：Various fluorescent emission states are converted to from a kind of fluorescent emission in the case where acid stimulates, can be returned to through the post-stimulatory material of outer alkali
Original fluorescent state.
Present invention also offers the preparation method of the triphenylamine derivative shown in a kind of formula (I), described preparation method is：
Shown in formula (II) the 4- boric acid triphenylamine shown in bromobenzylcyanide and formula (III) is generated through suzuki reactions shown in (IV) three
Aniline intermediate；Triphen amine intermediate shown in formula (IV) is passed through with the pyridine-2-formaldehyde shown in formula (V) again
Triphenylamine derivative shown in Knoevenagel condensation reactions generation formula (I)；
Specifically, a kind of preparation method of the triphenylamine derivative shown in formula (I), the preparation method is entered as follows
OK：
(1) under nitrogen protection, to bromobenzylcyanide and 4- boric acid triphenylamines shown in formula (III) shown in formula (II), in catalyst Pd [P
(C6H5)3]4In the presence of alkaline matter, back flow reaction 16-48h, reaction solution is post-treated afterwards, obtains mesh shown in formula (IV)
Mark product triphenylamine derivative；The organic solvent is toluene/tetrahydrofuran volume 1：The mixed liquor of (0.5-1)；The alkalescence
Material is sodium carbonate or potassium carbonate；To bromobenzylcyanide and 4- boric acid triphenylamine, catalyst shown in formula (III) shown in the formula (II)
Pd[P(C6H5)3]4, alkaline matter the ratio between the amount of the material that feeds intake be 1：(0.8-1.2)：(0.01-0.03)：(1.2-2)；
(2) in solvent chromatographic ethanol, triphen amine intermediate and pyridine -2- shown in formula (V) shown in the formula (IV) that step (1) is obtained
Under the catalytic action of sodium methoxide, in room temperature reaction 3-5h, solid is separated out formaldehyde in reaction system, filtering, Washing of Filter Cake, drying
Afterwards, triphenylamine derivative shown in formula (I) is obtained；
Formula (IV) the triphen amine intermediate and the ratio between amount for the material that feeds intake of pyridine-2-formaldehyde shown in formula (V) are (0.6-
1.5)：1；The sodium methoxide is 1 with the amount ratio of the material that feeds intake of triphen amine intermediate shown in formula (IV)：(5-15)；
In step (1), the volumetric usage of the toluene in the organic solvent is in terms of the quality of 4- boric acid triphenylamines shown in formula (III)
It is 20-40mL/g；
In step (2), the volumetric usage of the solvent chromatographic ethanol is calculated as 25-45mL/g with the quality of triphen amine intermediate；
In step (1), the method for the reaction solution post processing is：After reaction terminates, reaction solution is cooled to room temperature, after being concentrated under reduced pressure
Extracted with dichloromethane, extraction gained organic phase is respectively through saturated aqueous sodium carbonate washing, saturated common salt water washing, anhydrous sulphur
Sour magnesium is dried, filtering, is taken filtrate and is concentrated under reduced pressure, and gained concentrate carries out silica gel column chromatography separation, with petroleum ether/chloroform body
Product compares 45：1 mixed liquor is eluant, eluent, collects the eluent containing target compound, is dried after solvent is evaporated off, and obtains formula (IV) institute
Show triphen amine intermediate.
The characteristics of described triphenylamine derivative (I) has changing color resulting from acid：The protonation and deprotonation of fluorescence molecule turn
Change causes Intramolecular electron transfer ability to change, its fluorescence and color change, therefore reversible sour stimuli responsive fluorescence is presented and changes
Become phenomenon, i.e.,：In the case where acid (solution or steam of acid) stimulates, fluorescence and color change, can be extensive through the post-stimulatory material of amine
Original fluorescent state is arrived again.
There is triphenylamine derivative (I) of the present invention reversible acid stimulation to swash fluorescent switch performance, therefore can be used as one
The fluorescent optical sensor of acid in quick detection air is planted, for example, the crystalline solid or powder solid of the triphenylamine derivative (I),
The film that can be mixed to prepare triphenylamine derivative and SEBS particles by existing film technique has many stimulation response performances
The simple device of change in fluorescence, method is：Triphenylamine derivative is dissolved in tetrahydrofuran (THF) solvent, SEBS is added
Grain, is prepared into the sticky liquor of 0.1%-5% triphenylamine derivative contents, is then spin coated onto film forming, obtains triphenylamine derivative
SEBS films.
Compared with prior art, the beneficial effects of the present invention are：There is sour stimuli responsive face the invention provides one kind
The triphenylamine derivatives and its doping SEBS films of the double changes of color and fluorescence, the triphenylamine derivative doping SEBS films can
Inverse Acid-Base stimuli responsive color and fluorescence property have that aberration is big, fluorescent quenching rate feature high respectively；The triphenylamine derivative
The mechanical property of SEBS films has stretchable, bending, compression, recoverable feature；And triphenylamine derivative doping SEBS is thin
Film synthetic method is simple, and greatly widening reversible acid stimulates reality of the change in fluorescence material in senser element.
Brief description of the drawings
Fig. 1 is the aqueous solution (THF/water=of the solid powder of triphenylamine derivative (I) in embodiment of the present invention 1-2
1/99) in pH value be 0.98 and 3.34 when, its fluorescence spectra is changed over time；
Fig. 2 is that the solid powder of triphenylamine derivative (I) in the embodiment of the present invention 3 is placed on 10ppm hydrogen chloride 15s, and it is certainly
Photo under right light and uviol lamp；
Fig. 3 is that the solid powder of triphenylamine derivative (I) in the embodiment of the present invention 3 is placed on 20ppm hydrogen chloride 15s, and it is certainly
Photo under right light and uviol lamp；
Fig. 4 be triphenylamine derivative (I) doping in the embodiment of the present invention 6 the spin coating of SEBS solid powders into after film in natural light
And the photo under uviol lamp；
Fig. 5 is photo of the SEBS films of doping in the embodiment of the present invention 9 after hydroperoxide stimulation under natural light；
Fig. 6 is photo of the SEBS films of doping in the embodiment of the present invention 14 after hydroperoxide stimulation under natural light.
Specific embodiment
Technical scheme is described further with specific embodiment below, but protection scope of the present invention is not limited
In this.
Embodiment 1
Triphenylamine derivative (I) solid powder is dissolved in tetrahydrofuran solvent, concentration is configured to for 1x10-4mol/L.So
After take 0.01mL add 10mL volumetric flasks, be subsequently adding HCl/water solution (9.99m) L that pH value is 0.98, after 3 minutes test, its
Solution fluorescence is quenched (quenching rate is more than 97%) completely.(details please see Figure 1a)
Embodiment 2
Triphenylamine derivative (I) solid powder 0.1g is dissolved in 3mL tetrahydrofuran solvents, concentration is configured to for 1x10- 5mol/L.Then take 0.01mL and add 10mL volumetric flasks, be subsequently adding HCl/water solution (9.99m) L that pH value is 3.34,3 minutes
After test, its solution fluorescence intensity significantly reduces (be quenched rate more than 50%).(details please see Figure 1b)
Embodiment 3
Triphenylamine derivative solid powder (I) 0.05g of the invention is spread on quartz plate, is light yellow under natural light,
Bright green fluorescence is shown under uviol lamp.15s is put in the decentralization of 10ppm chlorinations hydrogen atmosphere, its fluorescence is changed into kermesinus, and the rate of being quenched is
83.4%.Its powder is also changed into peony under natural light, and Δ E reaches 18.7.(referring to accompanying drawing 2)
Embodiment 4
Triphenylamine derivative solid powder (I) 0.05g of the invention is spread on quartz plate, is light yellow under natural light,
Bright green fluorescence is shown under uviol lamp.15s is put in the decentralization of 20ppm chlorinations hydrogen atmosphere, its fluorescence is changed into kermesinus, and the rate of being quenched is
88.4%.Its powder is also changed into peony under natural light, and Δ E reaches 21.2.(referring to accompanying drawing 3)
Embodiment 5
Triphenylamine derivative solid powder (I) 0.009g is dissolved in the THF solvents of 10mL, SEBS particle 1g are added, carried out
Ultrasound, while being continuously added THF solution until dissolving, final to obtain the triphenylamine derivative SEBS mixing that doping is 0.9%
Solution, by its spin coating, drying and forming-film obtains the SEBS films that doping is 0.9% triphenylamine derivative, in natural light and ultraviolet
Under lamp, the film can be stretched, and be bent and with stronger fluorescence.
Embodiment 6
Triphenylamine derivative solid powder (I) 0.02g is dissolved in the THF solvents of 10mL, SEBS particle 1g are added, is surpassed
Sound, while THF solution is continuously added until dissolving, it is final to obtain the triphenylamine derivative SEBS mixed solutions that doping is 2%,
By its spin coating, drying and forming-film obtains the SEBS films that doping is 2% triphenylamine derivative, under natural light and uviol lamp, should
Film can be stretched, and be bent and with stronger fluorescence.(see accompanying drawing 4).
Embodiment 7
Film in embodiment 6 is placed in 2s in 20ppm hydrogen-chloride ambients, its fluorescence is slightly dimmed from initially very strong green, glimmering
Optical quenching rate reaches 46.3%, and high-visible red lines occurs in green film under natural light, and aberration Δ E reaches 12.5.
Embodiment 8
Film in embodiment 6 is placed in 10s in 20ppm hydrogen-chloride ambients, its fluorescence is from initially very strong green dimmed, fluorescence
The rate of being quenched reaches color under 80.3%, natural light also from green to kermesinus, and aberration Δ E reaches 18.6.
Embodiment 9
Film in embodiment 6 is placed in 48s in 20ppm hydrogen-chloride ambients, its fluorescence disappears substantially from initially very strong green
Completely dimmed, the color that fluorescent quenching rate is reached under 97.7%, natural light is also changed into kermesinus, aberration Δ E completely from green
Reach 21.9.The stifling 10s of excessive ammonia is placed on, its fluorescence returns to original state.(details is shown in Fig. 5)
Embodiment 10
Film in embodiment 6 is placed in 48s in 20ppm hydrogen-chloride ambients, its fluorescence disappears substantially from initially very strong green
Completely dimmed, the color that fluorescent quenching rate is reached under 97.7%, natural light is also changed into kermesinus, aberration Δ E completely from green
Reach 21.9.
Embodiment 11
Film in embodiment 6 is placed in 20s in 1ppm hydrogen-chloride ambients, its fluorescence is from initially very strong green macroscopic
Blackening, fluorescent quenching rate reaches 12.4%, and naked eyes red color visible lines occurs in green film under natural light, and aberration Δ E reaches
2.9.(generally naked eyes can subregion aberration Δ E be 2)
Embodiment 12
Film in embodiment 6 is placed in 20s in 20ppm fluoroform acid environments, its fluorescence disappears substantially from initially very strong green
Mistake is completely dimmed, and the color that fluorescent quenching rate is reached under 96.8%, natural light is also changed into kermesinus, aberration Δ completely from green
E reaches 22.1.
Embodiment 13
Film in embodiment 6 is placed in 20s in 20ppm fluoroform acid environments, its fluorescence disappears substantially from initially very strong green
Mistake is completely dimmed, and the color that fluorescent quenching rate is reached under 91.8%, natural light is also changed into kermesinus, aberration Δ completely from green
E reaches 20.3.
Embodiment 14
Film in embodiment 5 is placed in 10s in 20ppm hydrogen-chloride ambients, its fluorescence is from initially very strong green dimmed, fluorescence
The rate of being quenched reaches color under 78.2%, natural light also from green to kermesinus, and aberration Δ E reaches 16.8.(details
See Fig. 6)
Embodiment 15
Film in embodiment 5 is placed in 40s in 20ppm hydrogen-chloride ambients, its fluorescence is completely dimmed from initially very strong green,
The color that fluorescent quenching rate is reached under 92.7%, natural light is also changed into kermesinus completely from green, and aberration Δ E reaches 19.7.
Embodiment 17
Film in embodiment 5 is placed in 40s in 10ppm hydrogen-chloride ambients, its fluorescence is very weak from initially very strong green change,
The color that fluorescent quenching rate is reached under 81.5%, natural light is also changed into kermesinus completely from green, and aberration Δ E reaches 16.9.
It is below the specific embodiment of the preparation method of triphenylamine derivative (I).
Embodiment 18
Will be to bromobenzylcyanide (I) 0.97g (5mmol), 4- boric acid triphenylamines 1.73g (6mmol), tetrakis triphenylphosphine palladium 0.11g
(0.1mmol) is dissolved in toluene 45mL/ tetrahydrofuran 35mL mixed solutions, adds aqueous sodium carbonate (2.0M, 5mL).In nitrogen
Under atmosphere is enclosed, 90 DEG C of reaction 36h are warming up to.Reaction solution is cooled down, and after removing solvent under reduced pressure, (60mL × 3) is extracted with dichloromethane
It is secondary, merge organic phase, respectively through saturated aqueous sodium carbonate and saturated common salt water washing, finally dried with anhydrous magnesium sulfate.Cross
Filter, through concentrated under reduced pressure, residue silica gel column chromatography separation, eluant, eluent is 45/ for the volume ratio of petrol ether/ethyl acetate to filtrate
1 mixed solvent, collects the eluent containing target compound, removes under reduced pressure and dry after solvent, in obtaining yellow powder triphenylamine
Between product (IV) 1.62g, yield is 90%.
The structural confirmation of material is characterized as below：1H NMR (500MHz, CDCl3) δ 7.60 (d, J=8.0Hz, 2H), 7.47
(d, J=8.5Hz, 2H), 7.39 (d, J=8.0Hz, 2H), 7.30 (d, J=8.5Hz, 4H), 7.16 (d, J=8.5Hz, 6H),
7.06 (t, J=7.5Hz, 2H), 3.80 (s, 2H)；MS(EI):m/z 360.0.
Embodiment 19
Will be to bromobenzylcyanide (I) 0.97g (5mmol), 4- boric acid triphenylamines 1.56g (4mmol), tetrakis triphenylphosphine palladium 0.16g
(0.15mmol) is dissolved in toluene 45mL/ tetrahydrofuran 25mL mixed solutions, adds aqueous sodium carbonate (2.0M, 5mL).In nitrogen
Under atmosphere is enclosed, 90 DEG C of reaction 24h are warming up to.Reaction solution is cooled down, and after removing solvent under reduced pressure, (60mL × 3) is extracted with chloroformic solution
It is secondary, merge organic phase, respectively through saturated aqueous sodium carbonate and saturated common salt water washing, finally dried with anhydrous magnesium sulfate.Cross
Filter, through concentrated under reduced pressure, residue silica gel column chromatography separation, eluant, eluent is 45/ for the volume ratio of petrol ether/ethyl acetate to filtrate
1 mixed solvent, collects the eluent containing target compound, is dried after removing solvent under reduced pressure, obtains yellow powder product triphen
Amine intermediate (IV) 1.35g, yield is 70%.
Embodiment 20
Weigh formula (IV) triphen amine intermediate 4.32g (12mmol), pyridine-2-formaldehyde 1.07g (10mmol) and sodium methoxide
0.06g (1mmol) is dissolved in 30ml chromatographic ethanols.Reaction 4h is stirred at room temperature, terminates when there are a large amount of solid particles to separate out
Reaction.Then reaction system is put into -20 DEG C of refrigerator overnights, is filtered afterwards, filter cake is secondary with ethanol rinse (50mL × 3), it is natural
Light yellow powder, i.e. target product triphenylamine derivative (I) 4.26g are obtained after drying, yield is 95%.
The structural confirmation of material is characterized as below：1H NMR (500MHz, DMSO) δ 8.76 (d, J=4.1Hz, 1H), 8.10
(s, 1H), 7.97 (td, J=7.7,1.8Hz, 1H), 7.90 (d, J=8.5Hz, 2H), 7.82 (d, J=8.6Hz, 2H), 7.78
(d, J=7.8Hz, 1H), 7.70 (d, J=8.7Hz, 2H), 7.51-7.45 (m, 1H), 7.38-7.32 (m, 4H), 7.11 (d, J
=7.4Hz, 2H), 7.10 (d, J=0.9Hz, 2H), 7.07 (dd, J=8.8,5.3Hz, 4H) .MS m/z:449.2
Embodiment 20
Weigh formula (IV) triphen amine intermediate 2.89 (8mmol), pyridine-2-formaldehyde 1.07g (10mmol) and sodium methoxide 0.03g
(0.5mmol) is dissolved in 30ml chromatogram straight alcohols.Reaction 3h is stirred at room temperature, terminates anti-when there are a large amount of solid particles to separate out
Should.Then reaction system is put into -20 DEG C of refrigerator overnights, is filtered afterwards, filter cake is secondary with ethanol rinse (50mL × 3), done naturally
Light yellow powder, i.e. target product triphenylamine derivative (I) 2.89g are obtained after dry, yield is 80%.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept is subject to equivalent or change, should all be included within the scope of the present invention.
Claims (9)
1. a kind of triphenylamine derivative, it is characterised in that its structural formula such as formula（I）It is shown：
（I）.
2. triphenylamine derivative as claimed in claim 1, it is characterised in that it causes off-color material as reversible stimuli responsive
Using.
3. application as claimed in claim 2, it is characterised in that described application is that triphenylamine derivative is applied into sour stimulation
In response change in fluorescence detection.
4. application as claimed in claim 3, it is characterised in that affiliated triphenylamine derivative can in nano particle, powder,
Under crystal grain or filminess, to proton hydrogen in the environment detect that its fluorescence is from bright dimmed.
5. a kind of preparation method of triphenylamine derivative, it is characterised in that comprise the following steps：Formula（II）It is shown to bromobenzene second
Nitrile and formula（III）Shown 4- boric acid triphenylamine reacts through suzuki and generates（IV）Shown triphen amine intermediate；Formula（IV）
Shown triphen amine intermediate again with formula（V）Shown pyridine-2-formaldehyde is through Knoevenagel condensation reaction productions（I）
Shown triphenylamine derivative；
（I）
（II）（III）（IV）（V）.
6. the preparation method of triphenylamine derivative as claimed in claim 5, it is characterised in that comprise the following steps：
（1）Under nitrogen protection, formula（II）It is shown to bromobenzylcyanide and formula（III）Shown 4- boric acid triphenylamine, in catalyst Pd [P
(C6H5)3]4In the presence of alkaline matter, back flow reaction 16-48h, reaction solution is post-treated afterwards, obtains formula（IV）Shown mesh
Mark product triphenylamine derivative；The organic solvent is toluene/tetrahydrofuran volume 1：（0.5-1）Mixed liquor；The alkalescence
Material is sodium carbonate or potassium carbonate；The formula（II）It is shown to bromobenzylcyanide and formula（III）Shown 4- boric acid triphenylamine, catalyst
Pd[P(C6H5)3]4, alkaline matter the ratio between the amount of the material that feeds intake be 1：（0.8-1.2）：（0.01-0.03）：（1.2-2）；
(2) in solvent chromatographic ethanol, step（1）The formula for obtaining（IV）Shown triphen amine intermediate and formula（V）Shown pyridine-
Under the catalytic action of sodium methoxide, in room temperature reaction 3-5h, solid is separated out 2- formaldehyde in reaction system, filtering, Washing of Filter Cake, dry
After dry, formula is obtained（I）Shown triphenylamine derivative；
The formula（IV）Triphen amine intermediate and formula（V）The ratio between amount for the material that feeds intake of shown pyridine-2-formaldehyde is（0.6-
1.5）：1；The sodium methoxide and formula（IV）The amount ratio of the material that feeds intake of shown triphen amine intermediate is 1：（5-15）；
Step（1）In, the volumetric usage of the toluene in the organic solvent is with formula（III）The quality meter of shown 4- boric acid triphenylamine
It is 20-40mL/g；
Step（2）In, the volumetric usage of the solvent chromatographic ethanol is calculated as 25-45mL/g with the quality of triphen amine intermediate；
Step（1）In, the method for the reaction solution post processing is：After reaction terminates, reaction solution is cooled to room temperature, after being concentrated under reduced pressure
Extracted with dichloromethane, extraction gained organic phase is respectively through saturated aqueous sodium carbonate washing, saturated common salt water washing, anhydrous sulphur
Sour magnesium is dried, filtering, is taken filtrate and is concentrated under reduced pressure, and gained concentrate carries out silica gel column chromatography separation, with petroleum ether/chloroform body
Product compares 45：1 mixed liquor is eluant, eluent, collects the eluent containing target compound, is dried after solvent is evaporated off, and obtains formula（IV）Institute
Show triphen amine intermediate.
7. the preparation method of the film of a kind of triphenylamine derivative doping SEBS, it is characterised in that comprise the following steps：By triphen
Amine derivative is dissolved in tetrahydrofuran solvent, adds SEBS particles, is prepared into the sticky of 0.1-5% triphenylamine derivative contents
Liquor, is then spin coated onto film forming, obtains the SEBS films of triphenylamine derivative；
The structural formula of described triphenylamine derivative such as formula（I）It is shown：
（I）.
8. as claim 7 triphenylamine derivative doping SEBS film preparation method, it is characterised in that preparation film tool
There are the comprehensive mechanical properties such as stretchable, bending, and the changing color resulting from acid property of triphenylamine derivative can be retained.
9. as claim 7 triphenylamine derivative doping SEBS film preparation method, it is characterised in that the SEBS of preparation is thin
Film can be used as a kind of simple device of acid vapor in quick detection air.
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| CN110117253A (en) * | 2018-02-05 | 2019-08-13 | 三峡大学 | A kind of organic fluorescent dye with piezallochromy characteristic, preparation method and applications |
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| CN102911082B (en) * | 2012-06-08 | 2014-09-03 | 浙江工业大学 | Triphenylamine derivatives, and preparation method and application thereof |
| CN103102286B (en) * | 2012-12-08 | 2014-12-03 | 浙江工业大学 | Triphenylamine derivatives as well as preparation method and application thereof |
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| CN110117253A (en) * | 2018-02-05 | 2019-08-13 | 三峡大学 | A kind of organic fluorescent dye with piezallochromy characteristic, preparation method and applications |
| CN114085195A (en) * | 2021-11-30 | 2022-02-25 | 浙江播下环保科技有限公司 | Biodegradable film material with light conversion function, preparation method thereof and film doping material thereof |
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| CN117682979A (en) * | 2024-02-04 | 2024-03-12 | 有研工程技术研究院有限公司 | Acid-induced color compound, and preparation method and application thereof |
| CN117682979B (en) * | 2024-02-04 | 2024-05-31 | 有研工程技术研究院有限公司 | Acid-induced color compound, and preparation method and application thereof |
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